U.S. patent number 3,664,961 [Application Number 05/024,395] was granted by the patent office on 1972-05-23 for enzyme detergent composition containing coagglomerated perborate bleaching agent.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Russell Norris.
United States Patent |
3,664,961 |
Norris |
May 23, 1972 |
ENZYME DETERGENT COMPOSITION CONTAINING COAGGLOMERATED PERBORATE
BLEACHING AGENT
Abstract
An enzyme granular detergent composition having improved enzyme
stability which comprises at least one water soluble organic
synthetic detergent, at least one water soluble detergency builder,
an enzyme, and from about 0.005 to 50 percent by weight of a
coagglomerated sodium perborate bleaching agent consisting
essentially of sodium perborate, a water-soluble polymeric organic
agglomerating agent which forms a tacky solution with water at 72
.degree. F., and a water-soluble granular coagglomerant.
Inventors: |
Norris; Russell (Sycamore
Township, Hamilton County, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
21820368 |
Appl.
No.: |
05/024,395 |
Filed: |
March 31, 1970 |
Current U.S.
Class: |
510/305; 264/117;
23/313R; 510/306; 510/309; 510/318; 510/444; 510/530; 510/476;
510/374; 510/307 |
Current CPC
Class: |
C11D
3/38609 (20130101); C11D 3/394 (20130101) |
Current International
Class: |
C11D
3/39 (20060101); C11D 3/386 (20060101); C11D
3/38 (20060101); C11d 007/56 () |
Field of
Search: |
;252/95,99 ;23/313
;264/117 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3558498 |
January 1971 |
Pierre et al. |
3227790 |
January 1966 |
Bretschneider et al. |
|
Primary Examiner: Weinblatt; Mayer
Claims
Having described and illustrated the present invention by test and
examples, I claim:
1. An enzyme granular detergent composition having improved enzyme
stability which consists essentially of at least one water-soluble
organic synthetic detergent, at least one water-soluble detergency
builder salt, the proportion by weight of said detergent to said
builder being from 10:1 to 1:20; an effective amount of enzyme, and
from 0.005 percent to 50 percent by weight of a coagglomerated
dust-free concentrated sodium perborate bleaching agent said
coagglomerated sodium perborate consisting essentially (1) sodium
perborate, (2) a water-soluble polymeric organic agglomerating
agent which forms a tacky solution with water at 72.degree. F. and
is selected from the group consisting of a linear interpolymer of
methyl vinyl ether and maleic anhydride having a specific viscosity
of 0.1 - 0.5 as measured on a solution of 1 g. of the copolymer in
100 ml. of MEK at 25.degree. C.; polyacrylic acid; cross-linked,
pregelatinized amylopectin; amylopectin; poly(ethylene oxide)
homopolymer; linear copolymer of ethylene and maleic anhydride;
methyl cellulose; starch; gelatin; and polysaccharide gum, and (3)
as a water-soluble coagglomerant a spray-dried granular detergent
composition consisting essentially of at least one water-soluble
organic synthetic detergent and at least one water-soluble builder
salt selected from organic or inorganic sequestering builder salts,
the proportion of said detergent to said builder in said perborate
coagglomerant being in the range of 5:1 to 1:20.
2. A composition of claim 1 in which the amount coagglomerated
perborate is 1 percent to 40 percent.
3. A composition of claim 2 in which the ratio of detergent to
builder is 5:1 to 1:10.
4. A coagglomerated sodium perborate composition consisting
essentially of (1) sodium perborate, (2) a water-soluble polymeric
organic agglomerating agent which forms a tacky solution with water
at 72.degree. F. and which is selected from the group consisting of
a linear interpolymer of methyl vinyl ether and maleic anhydride
having a specific viscosity of 0.1 - 0.5 as measured on a solution
of 1 g. of the copolymer in 100 ml. of MEK at 25.degree. C;
polyacrylic acid; cross-linked, pre-gelatinized amylopectin;
amylopectin; poly(ethylene oxide) homopolymer; linear copolymer of
ethylene and maleic anhydride; methyl cellulose; starch; gelatin;
and polysaccharide gum, and (3) as a water-soluble coagglomerant a
spray-dried granular detergent composition consisting essentially
of at least one water-soluble organic synthetic detergent and at
least one water-soluble builder salt selected from organic or
inorganic sequestering builder salts, the proportion of said
detergent to said builder being in the range of 5:1 to 1:20.
5. A nonsegregating granular laundry detergent composition
consisting essentially of a water-soluble organic synthetic
detergent and a water-soluble detergency builder selected from
organic or inorganic sequestering builder salts, the proportion by
weight of said detergent to said builder being in the range of 5:1
to 1:20, and from 1 percent to about 60 percent by weight of the
composition of a coagglomerated perborate product of claim 4.
6. A process for preparing a coagglomerated sodium perborate
composition which comprises the steps of agitating a dry mixture of
1 to 99 percent by weight sodium perborate granules and 1 - 99
percent by weight water-soluble granular coagglomerant selected
from the group consisting of sodium sulfates, sodium thiosulfates,
carboxymethyl cellulose, starch, an organic synthetic detergent
selected from anionic, nonionic, ampholytic, or zwitterionic
detergents, a builder salt selected from organic or inorganic
sequestering builder salts, or a spray-dried granular detergent
composition consisting essentially of at least one water-soluble
organic synthetic detergent and at least one water-soluble builder
salt selected from organic or inorganic sequestering builder salts,
the proportion of said detergent to said builder being in the range
of 5:1 to 1:20, and spraying said dry mixture with an aqueous
slurry of water-soluble polymeric agglomerating agent which forms a
tacky aqueous solution at about 72.degree. F. and which is selected
from the group consisting of a linear interpolymer of methyl vinyl
ether and maleic anhydride having a specific viscosity of 0.1 - 0.5
as measured on a solution of 1.g of the copolymer in 100 ml. of MEK
at 25.degree. C.; polyacrylic acid; cross-linked, pre-gelatinized
amylopectin; amylopectin; poly(ethylene oxide) homopolymer; linear
copolymer of ethylene and maleic anhydride, methyl cellulose;
starch; gelatin; and polysaccharide gum, the concentration of said
polymeric agglomerating agent in said aqueous slurry being from 1
to 40 percent by weight, and said slurry having a temperature in
the range of 50.degree. F. to 180.degree. F.
7. A process of claim 6 in which said dry mixture consists
essentially of 50 - 95 percent sodium perborate granules and 5 - 50
percent of said granular coagglomerant, the concentration of
polymeric agglomerating agent in the slurry is 5 - 25 percent and
the temperature of the slurry is 70.degree.-160.degree. F.
Description
FIELD OF THE INVENTION
This invention relates to a process of incorporating a sodium
perborate granular bleaching agent into an enzyme containing
granular laundry detergent composition in a manner which
effectively overcomes the problem of product segregation while
maintaining the perborate in a stable form and simultaneously
provides a more improved stable enzyme product. The invention also
relates to the improved products formed by this process.
BACKGROUND OF THE INVENTION
Sodium perborate is a well-known granular oxidizing bleaching
agent. It is widely used in combination with granular detergents
and builders to aid in a laundry cleaning process, e.g., an
ordinary home laundry situation. It is possible to prepare granular
mechanical mixtures of these ingredients in preparing such
products. However, a major problem in such granular mixtures is
that the commercially available, sodium perborate granules are much
smaller than ordinary spray-dried detergent granules, and as a
result, they tend to segregate to the bottom of a carton or
package. This results in uneven dispensing and usage of the sodium
perborate bleaching agent when a granular detergent product is
poured from a container.
Sodium perborate in its ordinary commercially available form is a
fine granular or powder material. Particle size analysis indicates
that typically about 99 percent of the sodium perborate granules
pass through a 28 Tyler mesh, and about 75 percent pass through a
35 Tyler mesh. Particle sizes ordinarily range from about 0.0234
inch to smaller than 0.003 inch.
By comparison, ordinary spray-dried detergent composition granules
are considerably larger. A major portion, e.g., more than about 75
percent is retained on a 35 Tyler mesh. Less than about 25 percent
of the granules are in the smaller ordinary sodium perborate
particle size range.
Because of these significant particle size differences, the smaller
sodium perborate granules tend to separate towards the bottom of a
granular mechanical mixture of spray-dried detergent granules and
fine sodium perborate powdery granules. This as been a problem in
the detergent manufacturing industry for a long time.
One method of incorporating the fine sodium perborate granules
described above into a granular spray-dried detergent composition
includes a step of fusing the fine sodium perborate granules onto
larger spray-dried granules at the base of a spray tower while the
granules are still hot from spray-drying, e.g., ranging from about
160.degree.-220.degree. F. This is accomplished by mixing perborate
granules with hot spray-dried granules and agitating the mixture.
The heat causes the perborate granules to melt on the surface of
the larger spray-dried granules and become fused to them upon
cooling. While this process is effective in securing attachment to
the larger detergent granules and thus achieving fairly uniform
distribution of a sodium perborate bleaching agent in a detergent
composition, this embodiment has certain considerable
disadvantages. For instance, the fusion temperature can result in
the partial degradation of the sodium perborate and the premature
release and partial loss of available oxygen. In addition, the
fused form of the sodium perborate granules can result in decreased
stability of the fused sodium perborate bleaching agent due to the
continuing release of oxygen. Moreover, since the fused sodium
perborate is primarily present on the surface of the larger
spray-dried detergent granules it is thereby exposed and can
undesirably come into contact with and react with other ingredients
in the composition.
It is an object of this invention to provide a process which not
only provides a non-segregating coagglomerated perborate-containing
granular composition, but also a coagglomerated sodium perborate
composition which retains the maximum amount of available oxygen
content and which is protected from the other possibly degrading
ingredients which comprise an ordinary granular built detergent
composition.
One of the unexpected discoveries of the present invention is that
the coagglomerated sodium perborate product prepared in the manner
described herein is less harmful in its attack on enzymes when both
are present in a granular detergent composition. This is all the
more surprising because the perborate is in a highly concentrated
form in the agglomerated physical form and it might be expected
that this would increase the danger to the enzyme component.
SUMMARY OF THE INVENTION
This invention provides a coagglomerated sodium perborate
composition composed of sodium perborate, a water-soluble polymeric
agglomerating agent, and a granular coagglomerant which can be any
water-soluble granular composition which is compatible with the
sodium perborate and ordinary ingredients of a granular detergent
composition and which does not interfere with the primary objective
of formulating an effective laundry detergent composition.
The process for producing the coagglomerated sodium perborate
composition of this invention comprises the steps of agitating a
dry mixture of sodium perborate granules and coagglomerant
granules, and spraying said dry granular mixture with a slurry of
water and a water-soluble polymeric agglomerating agent which forms
a tacky solution with water at about 72.degree. F., the temperature
of said slurry ranging from 50.degree. F. to 180.degree. F.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, a process is provided for
preparing a coagglomerated sodium perborate composition which
comprises the steps of (1) blending a dry mixture of 1 to 99
percent by weight sodium perborate granules and 1 - 99 percent by
weight of a water-soluble granular coagglomerant selected from the
group consisting of sulfates, thiosulfates, carboxymethyl
cellulose, starch, an organic synthetic detergent selected from
anionic, nonionic, ampholytic, or zwitterionic detergents, a
builder salt selected from organic or inorganic sequestering
builder salts, or a spray-dried granular detergent composition
consisting essentially of at least one water-soluble organic
synthetic detergent and at least one water-soluble builder salt
selected from organic or inorganic sequestering builder salts, the
proportion of said detergent to said builder being in the range of
5:1 to 1:20, and (2) spraying said dry mixture with an aqueous
slurry of a water-soluble polymeric agglomerating agent which forms
a tacky aqueous solution at about 72.degree. F., the concentration
of said polymeric agglomerating agent in said aqueous slurry being
from 1 to 40 percent by weight, said slurry having a temperature in
the range of 50.degree. F. to 180.degree. F. While the preceding
ranges for conditions are permissible for practicing this
invention, best results are achieved when the dry mixture is
comprised of 50 to 95 percent sodium perborate granules and 5 to 50
percent of coagglomerant granules, the concentration of the
polymeric agglomerating agent in the slurry is 5 to 25 percent and
the temperature of the slurry is 70.degree. to 160.degree. F.
There are no known limitations on the sodium perborate granular
bleaching agent which can be used in practicing this invention.
Examples of permissible water-soluble coagglomerants are sodium
sulfate, sodium thiosulfate, sodium carboxymethyl cellulose, and
starch. The following synthetic detergents also are useful.
A. ANIONIC SOAP AND NON-SOAP SYNTHETIC DETERGENTS
This class of detergents includes ordinary alkali metal soaps such
as the sodium, potassium, ammonium and alkylolammonium salts of
higher fatty acids containing from about eight to about 24 carbon
atoms and preferably from about 10 to about 20 carbon atoms.
Suitable fatty acids can be obtained from natural sources such as,
for instance, from plant or animal esters (e.g., palm oil, coconut
oil, babassu oil, soybean oil, caster oil, tallow, whale and fish
oils, grease, lard, and mixtures thereof). The fatty acids also can
be synthetically prepared (e.g., by the oxidation of petroleum, or
by hydrogenation of carbon monoxide by the Fischer-Tropsch
process). Resin acids are suitable such as rosin and those resin
acids in tall oil. Napthenic acids are also suitable. Sodium and
potassium soaps can be made by direct saponification of the fats
and oils or by the neutralization of the free fatty acids which are
prepared in a separate manufacturing process. Particularly useful
are the sodium and potassium salts of the mixtures of fatty acids
derived from coconut oil and tallow, i.e., sodium or potassium
tallow and coconut soap.
This class of detergents also includes 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 sulfonic
acid or sulfuric acid ester radical. (Included in the term alkyl is
the alkyl portion of higher acyl radicals.) Examples of this group
of synthetic detergents which form a part of the preferred built
detergent 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, in straight
chain or branched chain configuration, e.g., those of the type
described in U.S. Pats. Nos. 2,220,099 and 2,477,383 (especially
valuable are linear straight chain alkyl benzene sulfonates in
which the average of the alkyl groups is about 13 carbon atoms
abbreviated hereinafter as C.sub.13 LAS); sodium alkyl glyceryl
ether sulfonates, especially those ethers of higher alcohols
derived from tallow and coconut oil; sodium coconut oil fatty acid
monoglyceride sulfonates and sulfates; sodium or potassium salts of
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 about eight to about 12 carbon atoms.
Additional examples of anionic non-soap synthetic detergents which
come within the terms of the present invention are 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 methyl tauride in which the fatty acids, for
example, are derived from coconut oil. Other anionic synthetic
detergents of this variety are set forth in U.S. Pat. Nos.
2,486,921; 2,486,922; and 2,396,278.
Still other anionic synthetic detergents include the class
designated as succinamates. This class includes such surface active
agents as disodium N-octadecylsulfo succinamate; tetrasodium
N-(1,2-dicarboxyethyl)-N-octadecyl-sulfo-succinamate; diamyl ester
of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic
acid; dioctyl ester of sodium sulfosuccinic acid.
Anionic phosphate surfactants are also useful in the present
invention. These are surface active materials having substantial
detergent capability in which the anionic solubilizing group
connecting hydrophobic moieties is an oxy acid of phosphorus. The
more common solubilizing groups, of course, are --SO.sub.4 H,
--SO.sub.3 H, and --CO.sub.2 H. Alkyl phosphate esters such as
(R--O).sub.2 PO.sub.2 H and ROPO.sub.3 H.sub.2 in which R
represents an alkyl chain containing from about eight to about 20
carbon atoms are useful.
These esters can be modified by including in the molecule from one
to about 40 alkylene oxide units, e.g., ethylene oxide units.
Formulae for these modified phosphate anionic detergents are
##SPC1##
in which R represents an alkyl group containing from about eight to
20 carbon atoms, or an alkylphenyl group in which the alkyl group
contains from about eight to 20 carbon atoms, and M represents a
soluble cation such as hydrogen, sodium, potassium, ammonium or
substituted ammonium; and in which n is an integer from 1 to about
40.
A specific anionic detergent which has also been found excellent
for use in the present invention is described more fully in the
U.S. Pat. No. 3,332,880 of Phillip F. Pflaumer and Adriaan Kessler,
issued July 25, 1967, titled Detergent Composition. This detergent
comprises by weight 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:
a. 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;
b. 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 3, 4, and
5 positions; and
c. said Component C is a mixture comprising from about 30 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.
B. NONIONIC SYNTHETIC DETERGENTS
Nonionic synthetic detergents may 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.
For example, a well known class of nonionic synthetic detergents is
made available on the market 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 polyoxyethylene content is about 50
percent of the total weight of the condensation product.
Other suitable nonionic synthetic detergents include:
1. 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.
2. Those 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 an excess
propylene oxide, said base having a molecular weight of the order
of 2,500 to 3,000, are satisfactory.
3. 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 30 moles of
ethylene oxide per mole of coconut alcohol, the coconut alcohol
fraction having from 10 to 14 carbon atoms.
4. Nonionic detergents include nonyl phenol condensed with either
about 10 or about 30 moles of ethylene oxide per mole of phenol and
the condensation products of coconut alcohol with an average of
either about 5.5 or about 15 moles of ethylene oxide per mole of
alcohol and the condensation product of about 15 moles of ethylene
oxide with one mole of tridecanol.
Other examples include dodecylphenol condensed with 12 moles of
ethylene oxide per mole of phenol; dinonylphenol condensed with 15
moles of ethylene oxide per mole of phenol; dodecyl mercaptan
condensed with 10 moles of ethylene oxide per mole of mercaptan;
bis-(N-2-hydroxyethyl) lauramide; nonyl phenol condensed with 20
moles of ethylene oxide per mole of nonyl phenol; myristyl alcohol
condensed with 10 moles of ethylene oxide per mole of myristyl
alcohol; lauramide condensed with 15 moles of ethylene oxide per
mole of lauramide; and di-iso-octylphenol condensed with 15 moles
of ethylene oxide.
5. A detergent having a formula R.sup.1 R.sup.2 R.sup.3 N.fwdarw.O
(amine oxide detergent) wherein R.sup.1 is an alkyl group
containing from about 10 to about 28 carbon atoms, from zero to
about two hydroxy groups and from zero to about five ether
linkages, there being at least one moiety of R.sup.1 which is an
alkyl group containing from about 10 to about 18 carbon atoms and
zero ether linkages, and each R.sup.2 and R.sup.3 are selected from
the group consisting of alkyl radicals and hydroxyalkyl radicals
containing from one to about three carbon atoms;
Specific examples of amine oxide detergents include:
dimethyldodecylamine oxide
dimethyltetradecylamine oxide
ethylmethyltetradecylamiine oxide
cetyldimethylamine oxide
dimethylstearylamine oxide
cetylethylpropylamine oxide
diethyldodecylamine oxide
diethyltetradecylamine oxide
dipropyldodecylamine oxide
bis-(2-hydroxyethyl)dodecylamine oxide
bis-(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropyl amine oxide
(2-hydroxypropyl)methyltetradecylamine oxide
dimethyloleyamine oxide
dimethyl-(2-hydroxydodecyl)amine oxide
and the corresponding decyl, hexadecyl and octadecyl homologs of
the above compounds.
6. A detergent having the formula R.sup.1 R.sup.2 R.sup.3
P.fwdarw.O (phosphine oxide detergent) wherein R.sup.1 is an alkyl
group containing from about 10 to about 28 carbon atoms, from zero
to about two hydroxy groups and from zero to about five ether
linkages, there being at least one moiety of R.sup.1 which is an
alkyl group containing from about 10 to about 18 carbon atoms and
zero ether linkages, and each of R.sup.2 and R.sup.3 are selected
from the group consisting of alkyl radicals and hydroxyalkyl
radicals containing from one to about three carbon atoms.
Specific examples of the phosphine oxide detergents include:
dimethyldodecylphosphine oxide
dimethyltetradecylphosphine oxide
ethylmethyltetradecylphosphine oxide
cetyldimethylphosphine oxide
dimethylstearylphosphine oxide
cetylethylpropylphosphine oxide
diethyldodecylphosphine oxide
diethyltetradecylphosphine oxide
dipropyldodecylphosphine oxide
bis-(hydroxymethyl)dodecylphosphine oxide
bis-(2-hydroxyethyl)dodecylphosphine oxide
(2-hydroxypropyl)methyltetradecylphosphine oxide
dimethyloleylphosphine oxide, and
dimethyl-(2-hydroxydodecyl)phosphine oxide
and the corresponding decyl, hexadecyl, and octadecyl homologs of
the above compounds.
7. A detergent having the formula
(sulfoxide detergent) where R.sup.1 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.1 being an alkyl radical containing zero
ether linkages and containing from about 10 to about 18 carbon
atoms, and wherein R.sup.2 is an alkyl radical containing from one
to three carbon atoms and from one to two hydroxyl groups.
octadecyl methyl sulfoxide
dodecyl methyl sulfoxide
tetradecyl methyl sulfoxide
3-hydroxytridecyl methyl sulfoxide
3-methoxytridecyl methyl sulfoxide
3-hydroxy-4-dodecoxybutyl methyl sulfoxide
octadecyl 2-hydroxyethyl sulfoxide
dodecylethyl sulfoxide
C. AMPHOLYTIC SYNTHETIC DETERGENTS
Ampholytic synthetic detergents can be broadly described as
derivatives of aliphatic or aliphatic derivatives of heterocyclic
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 at
least one contains an anionic water-solubilizing group, e.g.,
carboxy, sulfo, sulfato, phosphato, or phosphono. Examples of
compounds falling within this definition are ##SPC2## ##SPC3##
##SPC4##
D. ZWITTERIONIC SYNTHETIC DETERGENTS
Zwitterionic synthetic detergents can be broadly described as
derivatives of aliphatic quaternary ammonium and phosphonium or
tertiary sulfonium compounds, in which the cationic atom may be
part of a heterocyclic ring, and in which the aliphatic radical may
be straight chain or branched, and wherein one of the aliphatic
substituents contains from about three to 18 carbon atoms, and at
least one aliphatic substituent contains an anionic
water-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato,
or phosphono. Examples of compounds falling within this definition
are ##SPC5## ##SPC6## ##SPC7##
Some of these detergents are described in the following U.S. Pat.
Nos. 2,129,264; 2,178,353; 2,774,786; 2,813,898; and 2,828,332.
Water-soluble inorganic in builder salts which can be used i this
invention alone or in admixture are alkali metal carbonates,
borates, phosphates, polyphosphates, bicarbonates and silicates.
Ammonium or substituted ammonium, e.g., triethanol ammonium, salts
of these materials can also be used. Specific examples of suitable
salts are sodium tripolyphosphate, sodium carbonate, sodium
tetraborate, sodium and potassium pyrophosphate, sodium and
ammonium bicarbonate, potassium tripolyphosphate, sodium
hexametaphosphate, sodium sesquicarbonate, sodium orthophosphate
and potassium bicarbonate. The preferred inorganic alkaline
builders according to this invention are alkali metal
tripolyphosphates for built granular compositions.
Examples of suitable organic alkaline sequestrant builder salts
used in this invention alone or in admixture are alkali metal,
ammonium or substituted ammonium, aminocarboxylates, e.g., sodium
and potassium ethylenediaminetetraacetate, sodium and potassium
N-(2-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassium
nitrilotriacetates and sodium, potassium and triethanolammonium
N-(2-hydroxyethyl)-nitrilodiacetates. Mixed salts of these
polycarboxylates are also suitable. The alkali metal salts of
phytic acid, e.g., sodium phytate are also suitable as organic
alkaline sequestrant builder salts (see U.S. Pat. No. 2,739,942).
Sodium ethane-1-hydroxy-1-diphosphonate, and sodium citrate can
also be used as builders either alone or in mixtures with other
builder compounds. Other suitable builders include methylene and
ethylene diphosphonates and their derivatives,
ethene-1-hydroxy-1,1,2-triphosphonate, sodium itaconate, and sodium
polymaleate.
An especially preferred coagglomerant is a spray-dried granular
built detergent consisting essentially of a water-soluble synthetic
detergent and a builder salt, the proportion by weight of said
detergent to said builder being from 5:1 to 1:20. The detergent
ingredient and the builder salt can be selected from those
mentioned above. The preferred class of detergents is the anionic
class and specifically sodium linear alkyl benzene sulfonate, the
alkyl having eight to 20 carbon atoms, sodium fatty alcohol
sulfates (tallow and coconut), and sodium olefin sulfonates. The
preferred builders are sodium tripolyphosphate, sodium
nitrilotriacetate, or a mixture of these two builders in a ratio by
weight of 4:1 to 1:4.
The polymeric agglomerating agent used in practicing this invention
can be selected from a large number of materials. It is
contemplated that any polymeric agglomerating agent can be used
which when mixed with water at about 72.degree. F. forms a tacky
solution. No material has been found unsatisfactory for practicing
this invention which satisfies this one criteria. The following
materials are examples of useful polymeric agglomerating agents: a
linear interpolymer of methyl vinyl ether and maleic anhydride
having a specific viscosity of 0.1 - 0.5 as measured on a solution
of 1 g. of the copolymer in 100 ml. of MEK at 25.degree. C.;
polyacrylic acid; cross-linked, pre-gelatinized amylopectin;
amylopectin; poly(ethylene oxide) homopolymer; linear copolymer of
ethylene and maleic anhydride; methyl cellulose; starch; gelatin;
and polysaccharide gum. The preferred agglomerating agents are the
linear interpolymer of methyl vinyl ether and maleic anhydride and
the cross-linked pre-gelatinized amylopectin.
Practicing the process for preparing the coagglomerated perborate
product is relatively simple. The previously mentioned granular dry
mixture is prepared in any convenient manner. An aqueous slurry of
the agglomerating agent is prepared and sprayed into the agitated
dry mixture. Any suitable spraying device can be used to spray the
mixture of water and the agglomerating agent onto the dry mixture
of the perborate and coagglomerant. Coagglomeration occurs in an
even and uniform manner. Virtually no additional processing step is
required. The coagglomerated product dries readily and is available
for use almost immediately.
The amount of agglomerating agent applied to the dry granular
mixture need only be sufficient to effect the desired degree of
agglomeration. This can readily be determined by taking into
consideration the ultimate use of the coagglomerated perborate
product. On a weight basis the amount of agglomerating agent can
range from 0.05 percent to about 4 percent of the combined weight
of the perborate, coagglomerant and agglomerating agent; preferably
from 0.1 to about 3 percent.
The coagglomerated product provides alternative uses. For instance,
if the coagglomerant used is a detergent composition, the
coagglomerated product can be used directly as a useful laundering
composition. Alternatively the coagglomerated product can be used
as an additive to a complete detergent or laundering composition in
an amount sufficient to provide the desired level of sodium
perborate bleaching agent. A preferred embodiment of this invention
is a laundry detergent composition consisting essentially of a
spray-dried mixture comprising a water-soluble synthetic detergent
and a water-soluble builder salt in a proportion by weight of 5:1
to 1:20, and a coagglomerated sodium perborate granular product
consisting essentially of sodium perborate; a water-soluble
polymeric agglomerating agent which forms a tacky slurry with water
at about 72.degree. F.; and a water-soluble granular coagglomerant
which is selected from sodium sulfate, sodium thiosulfate, sodium
carboxymethyl cellulose, natural unmodified starch, an organic
synthetic detergent, an organic or inorganic sequestering builder
salt, and a spray-dried granular composition consisting essentially
of an organic synthetic detergent and an organic or inorganic
sequestering builder salt, the proportion by weight of said
detergent to said builder being from 5:1 to 1:20, the amount of
said coagglomerated perborate product being sufficient o provide
from 1 percent to 60 percent by weight of the composition,
preferably from 5 percent to 50 percent, sodium perborate bleaching
agent.
The spray-dried granular detergent composition mentioned the in the
examples below has the following composition:
16.8% A 55%-45% mixture by weight of sodium linear tridecyl benzene
sulfonate and sodium tallow alkyl sulfate
49.5% Sodium tripolyphosphate
6.0% Sodium silicate
14.0% Sodium sulfate
10.0% Water
3.7% Optical brighteners, benzotriazole, carboxymethyl cellulose
and minors
Having described the invention in detail above, the invention is
now illustrated by the following examples.
EXAMPLE I
Three hundred pounds of sodium perborate powder, having a particle
size distribution ranging from Tyler 35 mesh to smaller than Tyler
100 mesh (0.0165 inches to smaller than 0.0016 inches) with about
75 percent of the total sodium perborate particles smaller than
Tyler 35 mesh (0.00165 inch), were added to a baffled drum mixer.
To this mixer were added 300 pounds of a spray dried granular
detergent composition described above having a particle size
distribution ranging from Tyler 10 mesh (0.0661 inches) to smaller
than Tyler 100 mesh with about 75 percent of the total granular
detergent particles larger than Tyler 35 mesh.
The granular mixture of these two materials was dry mixed by
rotating the baffled drum mixer.
As the drum was rotating, a slurry of 75 percent water and 25
percent of an agglomerating agent which was a linear interpolymer
of methyl vinyl ether and maleic anhydride having a specific
viscosity (nsp) of 0.1 - 0.5 as measured on a solution of 1 gm. of
the copolymer in 100 ml. of MEK at 25.degree. C., and comprised of
the following repeating unit:
was uniformly sprayed onto the agitating dry mixture. The
agglomerating agent was obtained from The General Aniline and Film
Corporation and is identified as Gantrez AN-119. (Technical
Bulletin 7543-017). The slurry was prepared by mixing 17 pounds of
the agglomerating agent with 51 pounds of water at a temperature of
150.degree. F. There is a substantial temperature loss in the
slurry between the spray nozzles and the dry granular particles.
Upon contact with the particles, the slurry spray has a temperature
of about 100.degree. F. The 68 pounds of slurry was uniformly
sprayed at a pressure of about 160 pounds per square inch over a
time period of about 6 minutes onto the 600 pounds of dry granular
mix in the drum mixer.
The resultant agglomerated mixture contained 44.9 percent sodium
perborate, 44.9 percent spray-dried granular detergent, 2.5 percent
polymeric methyl vinyl ether/maleic anhydride agglomerating agent
and 7.7 percent water.
As the slurry of the agglomerating agent was sprayed onto the dry
powder mixture coagglomeration began immediately. To determine how
fast and how efficient coagglomeration was taking place, uniform
samples were removed from the drum during the mixing and spraying
operation at specific time intervals (15 seconds, 30 seconds, 1
minute, 2 minutes, etc.). the granular samples were examined for
changes in particle size distribution. By observing the rate at
which the small particles were disappearing (i.e., how quickly and
uniformly large particles were forming from the smaller particles),
it was determined that the desired coagglomeration had taken
place.
The following data shows the agglomerating effect upon the small
particles with short time increments. ##SPC8##
It can be seen from the data in the table that the coagglomeration
proceeded smoothly and rapidly. The resulting coagglomerated
perborate particles were spherical, substantially dust-free, freely
flowing particles requiring no further processing such as cooling
and drying. A very significant aspect of this process is that
analytical measurements showed no measurable loss in available
oxygen content of the perborate agglomerates thereby indicating the
processing steps had not degraded the sodium perborate.
This example demonstrates preparing a coagglomerated perborate
bleaching granular product having a particle size distribution
approximating the particle size distribution of ordinary
spray-dried detergent granules with which the perborate bleaching
granule can be mixed without concern for substantial segregation of
the particles. This advantage provides a detergent composition
offering a housewife uniform cleaning and bleaching
characteristics.
The following table compares the particle sizes of typical
perborate particles, typical spray-dried granular detergent
particles, and coagglomerated perborate particles prepared by the
present invention to illustrate the value of this invention.
##SPC9##
The virtual elimination of particles smaller than 35 mesh
remarkably reduces the segregation tendencies of the sodium
perborate.
EXAMPLE II
Three hundred pounds of sodium perborate powder having a particle
size distribution (as in Example I) were added to a baffled mixer.
To this mixture was added 300 pounds of a spray-dried granular
detergent with a particle size distribution (as in Example I).
The granular mixture was dry mixed in a rotating baffled drum. As
the drum was rotating, 68 pounds of a slurry composed of 97.75
percent water and 2.25 percent of a polymerized acrylic acid
agglomerating agent having as a fundamental repeating unit,
was uniformly sprayed into the agitating dry mixture.
This specific material was obtained from B. F. Goodrich Chemical
Company as Carbopol. Properties of this material are described in
B. F. Goodrich Service Bulletin GC-36 entitled "Carbopol
Water-Soluble Resins." The slurry was prepared by mixing 1.53
pounds of Carbopol with 66.47 pounds of water. The 68 pounds of
slurry were sprayed on in the manner described in Example I. The
resultant agglomerated mixture contained 0.23 percent agglomerating
agent, 9.97 percent water, 44.9 percent sodium perborate, and 44.9
percent granular detergent.
During the spraying operation, samples were taken as in Example I
and analyzed for particle size distribution in the prescribed way.
Similar observations were observed as in Example I. The small
perborate particles were coagglomerated with the spray-dried
detergent granules to very substantially reduce the level of small
particles.
EXAMPLE III
Three hundred pounds of a sodium perborate powder having a particle
size distribution, as described in Example I, were added to a
baffled mixer. To this mixer were added 300 pounds of a spray-dried
granulated detergent composition having a particle size
distribution as described in Example I. The granular mixture of
these two materials was dry-mixed by rotating the baffled drum
mixer.
As the drum was rotating, a slurry of 93 percent water and 7
percent of Instant Clearjel, a cross-linked pre-gelatinized
amylopectin was uniformly sprayed into the agitating dry mixture.
This material, Instant Clearjel, was obtained from National Starch
and Chemical Corporation, and is described in the Company's No. 241
Technical Bulletin. The slurry was prepared by mixing 4.8 pounds of
the Instant Clearjel powdered material with 63.2 pounds of water.
General physical property descriptions of the slurry are similar to
those in Example I. Sixty-eight pounds of slurry was uniformly
sprayed into the drum mixture in a procedure as described in
Example I. The resultant mixture contained 0.72 percent Instant
Clearjel, 9.48 percent water, 44.9 percent sodium perborate, and
44.9 percent spray-dried granule detergent. During the spraying
operation, samples were taken and removed from the mixer as
described in Example I. The samples were analyzed and the particle
size distributions were determined. It was observed that the small
perborate particles were coagglomerated with the spray-dried
detergent granules to significantly reduce the level of small
particles as had been previously observed.
EXAMPLE IV
The procedure is similar to the procedure in Example I. As the drum
was rotating, 68 pounds of a slurry composed of 94.6 percent water
and 5.4 percent Purity HPC agglomerating agent was uniformly
sprayed into the agitating dry mixture. Purity HPC was obtained
from the National Starch and Chemical Corporation. It is an
amylopectin food starch derived from waxy maize. The slurry was
prepared by mixing together 3.7 pounds of Purity HPC and 64.3
pounds of water. The slurry was sprayed on in the manner as
described in Example I. During the spraying operation, samples were
taken as in Example I, and analyzed for particle size distribution.
Similar observations were made as in Example I, and it was
concluded that the small perborate particles were coagglomerated to
the spray-dried detergent granules. The resultant coagglomerated
perborate particles contained 0.55 percent Purity HPC, 9.65 percent
water, 44.9 percent granular detergent material, and 44.9 percent
sodium perborate.
EXAMPLE V
The following laundry composition is an example of a preferred
embodiment of this invention. It is a nonsegregating laundry
product combining excellent bleaching and cleaning properties.
20% Sodium linear tridecylbenzene
40% Sodium tripolyphosphate
14% Sodium sulfate
6% Sodium silicate
10% Water
10% Coagglomerated sodium perborate product of Example I
The sodium tripolyphosphate can be replaced with an equal weight
percent of sodium nitrilotriacetate and an excellent composition is
obtained.
EXAMPLE VI
A dry mixture of sodium perborate granules and spray-dried granular
detergent were mixed together as described in Example I. Five
hundred grams of the granular detergent material were mixed woth
500 grams of sodium perborate following the general procedure
described in Example I. As the drum was rotating, 100 grams of a
slurry composed of 5 grams of a polymerized ethylene oxide polymer
agglomerating agent and 95 grams were sprayed onto the mixture. The
polymerized ethylene oxide polymer was obtained from Union Carbide
Company under the trade name "Polyox" and is a nonionic
poly(ethylene oxide) homopolymer ranging in molecular weight from
several hundred thousand to over five million. The material is
described in a company bulletin Poly-Ox Water Soluble Resins. The
same coagglomerated products were formed as in Example I, composed
of 0.45 percent agglomerating agent, 8.55 percent water, 45.5
percent sodium perborate and 45.5 percent spray-dried detergent
composition.
EXAMPLE VII
Five hundred grams of a granular detergent material were mixed with
500 grams of sodium perborate particles in a baffled mix drum, as
described in Example I. One hundred grams of a slurry composed of
15 grams of an agglomerating agent which is a linear copolymer
prepared by reacting ethylene with maleic anhydride and 85 grams of
water were sprayed into the drum as the drum was rotating. The
copolymer is an anhydride having a viscosity of 5.0 cps (2 percent
solution at normal product pH). The specific material used is
EMA-21 obtained from Monsanto Company and is described in Technical
Bulletin 1-261 "EMA* (*EMA is a trademark of Monsanto Company.)
Ethylene Maleic Anhydride Resins."
Analysis of coagglomerated perborate product showed general
particle size distribution as described in Example I. The
coagglomerated perborate product was composed of 1.36 percent
agglomerating agent, 7.64 percent water, 45.5 percent sodium
perborate and 45.5 percent spray-dried detergent composition.
EXAMPLE VIII
Following the general procedure of Example I, 500 grams of a
granular detergent material and 500 grams of sodium perborate were
mechanically mixed in a baffled mix drum. One hundred grams of
slurry composed of 7 grams of carboxy methyl cellulose
agglomerating agent and 93 grams of water were sprayed into the
mixture as the drum rotated. The carboxy methyl cellulose was
obtained from the Dow Cehmical Company as Methocel. The final
coagglomerated perborate composition was composed of 0.63 percent
methyl cellulose, 8.37 percent water, 45.5 percent sodium perborate
and 45.5 percent spray-dried detergent composition.
EXAMPLE IX
Following the general procedure of Example I, 500 grams of a
spray-dried granular detergent were mixed with 500 grams of sodium
perborate particles, in a baffled mixer. One hundred grams of a
slurry composed of 10 grams of starch agglomerating agent and 90
grams of water were sprayed into the drum as the drum rotated. The
final coagglomerated perborate composition was composed of 0.91
percent coagglomerating agent, 8.09 percent water, 45.5 percent
sodium perborate, and 45.5 percent spray-dried detergent
composition. Particle size distribution was generally the same as
Example I.
EXAMPLE X
Following the general procedure of Example I, 500 grams of a
spray-dried granular detergent material and 500 grams of sodium
perborate were charged to a baffled mix drum. One hundred grams of
a slurry composed of 5 grams of cross-linked pregelatinized
amylopectin agglomerating agent (Amaizo 727-A) and 95 grams of
water were sprayed into the tumbling mixture. The agglomerating
agent was obtained from American Maize Products Company.
Coagglomeration occurred uniformly and the general particle size
distribution of Example I was achieved. The coagglomerated
perborate composition was composed of 0.45 percent amylopectin
agglomerating agent, 8.55 percent water, 45.5 percent sodium
perborate and 45.5 percent spray-dried detergent composition.
EXAMPLE XI
Following the general procedure of Example I, 500 grams of a
spray-dried granular detergent material and 500 grams of sodium
perborate were added to a baffled mixer. Into the mixer was sprayed
100 grams of a slurry composed of 25 grams of corn starch (57
percent amylose, 43 percent amylopectin) and 75 grams of water. The
corn starch was obtained as Amylon from National Starch and
Chemical Corporation. Uniform coagglomeration resulted in particle
size distribution similar to Example I and the product was composed
of 2.3 percent agglomerating agent, 6.7 percent water, 45.5 percent
spray-dried detergent composition, and 45.5 percent sodium
perborate.
EXAMPLE XII
Following the general procedure of Example I, 500 grams of a
granular detergent material were mixed with 500 grams of sodium
perborate in a baffled mixer. As the mixer was rotating, 100 grams
of a slurry consisting of 1.1 gram of polysaccharide gum
agglomerating agent and 98.9 grams of water was sprayed into the
mixer. The polysaccharide gum material was obtained from the Kelco
Company and is identified in Bulletin DB-14 as Kelgum. Uniform
coagglomeration resulted in particle size distribution similar to
Example I; the product was composed of 0.1 percent agglomerating
agent, 8.9 percent water, 45.5 percent sodium perborate, 45.5
percent spray-dried detergent composition.
EXAMPLE XIII
In the procedure of Example VI, similar results are obtained when
500 grams of sodium citrate granules are used in place of the
spray-dried detergent composition.
EXAMPLE XIV
In the procedure of Example VI, similar results are obtained when
sodium nitrilotriacetate granules are used in place of the
spray-dried detergent composition.
EXAMPLE XV
In the procedure of Example VI, similar results are obtained when
sodium pyrophosphate granules are used in place of the spray-dried
detergent granules.
EXAMPLES XVI
In the procedure of Example VI, similar results are obtained when
sodium bicarbonate granules are used in place of the spray-dried
detergent granules.
EXAMPLES XVII
In the procedure of Example VI, similar results are obtained when
sodium phosphate granules are used in place of the spray-dried
detergent granules.
EXAMPLE XVIII
In the procedure of Example VI, similar results are obtained when
sodium thiosulfate granules are used in place of the spray-dried
detergent granules.
EXAMPLE XIX
In the procedure of Example VI, similar results are obtained when
sodium borate granules are used in place of the spray-dried
detergent granules
EXAMPLE XX
In the procedure of Example VI similar results are obtained when
sodium sulfate granules are used in place of the spray-dried
detergent granules.
The coagglomerated perborate composition described herein can be
readily dyed to form aesthetically attractive speckles for
incorporation into ordinary spray-dried granular detergent
compositions.
All proportions and ratios given herein are on a weight basis
unless otherwise specified.
In preparing spray-dried granular detergent compositions as
described herein, the preferred proportion of organic synthetic
detergent to the detergency builder is in the range of 2:1 to
1:10.
The term "coagglomerant " is used in the description of this
invention to mean any solid granular product or composition with
which the sodium perborate bleaching agent is to be
coagglomerated.
The improved enzyme effectiveness and stability results enjoyed
with the coagglomerated concentrated sodium perborate composition
of this invention are demonstrated and described below.
The following spray dried laundry detergent composition was
prepared:
12.9% Sodium tridecyl benzene sulfonate
45.5% Sodium tripolyphosphate
15.6% Sodium sulfate
5.4% Sodium silicate
4.0% Sodium perborate NaBO.sub.3 .sup.. 4H.sub.2 O (added as
described below)
8.7% Water
3.43% Miscellaneous
4.3% Sodium fatty acid soap consisting of 3 parts sodium tallow
soap and 1 part marine fatty acid soap
0.17% Enzyme composition described below
The enzyme composition was prepared by blending the following
materials. The enzyme powder mixture so prepared had a particle
size distribution ranging from Tyler 80 mesh to smaller than Tyler
100 mesh (0.007 inch to smaller than 0.0016 inch) with almost 95
percent smaller than Tyler 80 mesh (0.007 inch):
(1) 14.78 parts of an enzyme preparation comprising 6.86 percent of
a .alpha.-amylase having 755,000 amylase activity units per gram,
6.33 percent alkaline protease having about 465,000 protease
activity units per gram and the balance inert materials such as
calcium sulfate and sodium sulfate; (2) 5.58 parts of an enzyme
preparation comprising 5.68 percent of .alpha.-amylase having about
635,000 amylase activity units per gram, 5.10 percent alkaline
protease having about 375,000 protease activity units per gram and
the balance inert materials such as calcium sulfate and sodium
sulfate; (3) 4.78 parts of an enzyme preparation comprising 1.82
percent of .alpha.-amylase having about 200,000 amylase activity
units per gram, 5.44 percent of an alkaline protease having about
400,000 protease activity units per gram and the balance inert
materials such as calcium sulfate and sodium sulfate; (4) 23.72
parts of an enzyme preparation comprising 16.33 percent alkaline
protease having about 1,200,000 protease activity units per gram
and the balance inert materials such as sodium and calcium sulfate;
(5) 11.14 parts of an enzyme preparation comprising 6.25 percent of
an alkaline protease having about 458,000 protease activity units
per gram and the balance inert materials such as sodium and calcium
sulfate.
In order to provide products for comparison, sodium perborate was
added to one composition, Composition A, by fusing 4 percent by
weight of the perborate particles to the hot spray-dried granules
at the base of the spray tower. This is a conventional way of
incorporating fine perborate powders into a spray-dried composition
to prevent segregation in a carton.
This invention was practiced to prepare a comparison product,
Composition B. In this product, 4 percent by weight of an
coagglomerated, concentrated, dust-free sodium perborate
composition was prepared by following the precedure of Example I
above. The resulting product was dust-free, non-segregating and an
excellent laundry product combining both oxidizing bleaching and
enzyme activity.
The improved enzyme stability of Composition B containing a
preferred embodiment of this invention was shown by an amylase test
and an Azocoll test.
The two detergent compositions were separately packaged in
cardboard containers and stored at 90.degree. F. and 80 percent
relative humidity for 12 days. This represents a severe laboratory
evaluation of enzyme-containing detergent products. Enzyme
stability was periodically tested as illustrated by the data in the
table below.
Amylase enzyme activity was measured of these two compositions, A
and B, and the results in Table II indicate clearly the improved
stability results of Composition B in comparison to Composition
A.
TABLE II
Percent Remaining Activity .sup.1
0 3 6 9 12 days days days days days Composition A 5% 0% 0% 0% 0%
Composition B 100% 85% 60% 40% 25%
__________________________________________________________________________
An Azocoll test.sup.1 proteolytic activity was also performed and
this also revealed a significant directional enzyme stability
improvement although not as significant as with amylase
activity.
TABLE I
---------------------------------------------------------------------------
Percent Remaining Enzyme Activity.sup.1
0 days 3 days 6 days 12 days Composition A 100% 95% 66% 50%
Composition B 100% 95% 90% 75%
__________________________________________________________________________
as can be readily seen from the data in the table, proteolytic
enzyme activity of Composition B was very substantially more
evident than Composition A.
The enzymes which can be usefully employed in conjunction with the
dust-free concentrated coagglomerated sodium perborate composition
of this invention are those mentioned and described in U.S. Pat.
No. 3,451,935 and they include proteases, amylases, lipases and the
like.
The coagglomerated concentrated dust-free sodium perborate
composition employed herein is described in a co-pending
application, Ser. No. 889,325 filed Dec. 30, 1969, now abandoned in
favor of a Continuation-In-Part Application, Ser. No. 24,329, filed
Mar. 31, 1970, now abandoned.
* * * * *