U.S. patent number 3,609,075 [Application Number 04/739,631] was granted by the patent office on 1971-09-28 for cleaning and softening detergent compositions.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Melvin A. Barbera.
United States Patent |
3,609,075 |
Barbera |
September 28, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
CLEANING AND SOFTENING DETERGENT COMPOSITIONS
Abstract
Detergent compositions containing a synthetic organic nonsoap
detergent and an organo-phosphorus softener compound which provide
conjoint cleaning and softening properties are described. The
organo-phosphorus compounds employed in an amount of about 1 to 15
percent of the composition include alkylphosphinic compounds having
the formula wherein R is alkyl of about 12 to 30 carbon atoms,
R.sup.1 is hydrogen or alkyl of one to about 30 carbon atoms, and M
is a water-solubilizing cation, e.g., hydrogen, alkali metal,
ammonium or substituted-ammonium or alkyl of about one to about
eight carbon atoms; and alkyldiphosphonic compounds having the
formula ##SPC1## wherein R is alkyl of about 12 to about 30 carbon
atoms and each M is a water-solubilizing cation, e.g., hydrogen,
alkali metal, ammonium, substituted ammonium or alkyl of one to
about eight carbon atoms. Also disclosed is a process of conjointly
washing and softening textile materials which comprises washing
textiles at a temperature of about 40.degree. to about 180.degree.
F. with an aqueous solution of a detergent composition of the
present invention, said solution having at least about 16 p.p.m. of
the organo-phosphorus softener compound.
Inventors: |
Barbera; Melvin A. (Mt.
Healthy, OH) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
24973160 |
Appl.
No.: |
04/739,631 |
Filed: |
June 25, 1968 |
Current U.S.
Class: |
510/327; 8/137;
562/8; 562/21; 510/325; 510/494; 510/328; 510/469 |
Current CPC
Class: |
D06M
13/285 (20130101); C11D 1/342 (20130101); C11D
3/001 (20130101) |
Current International
Class: |
C11D
1/02 (20060101); D06M 13/00 (20060101); C11D
1/34 (20060101); D06M 13/285 (20060101); C11D
3/00 (20060101); D06m 013/28 (); C11d
003/065 () |
Field of
Search: |
;252/8.8,8.6,135,8.75,137,138,161 ;117/139.5O |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Guynn; Herbert B.
Claims
What is claimed is:
1. A softening and cleaning detergent composition consisting
essentially of a synthetic organic nonsoap detergent selected from
the group consisting of anionic detergents, nonionic detergents,
ampholytic detergents and zwitterionic detergent and about 1 to
about 15 percent of a detergent-compatible organic
phosphorus-containing softener compound having the formula
wherein R and R' are each alkyl of about 16 to about 24 carbon
atoms and M is a water-solubilizing cation selected from the group
consisting of hydrogen, alkali metal cations, ammonium,
methylammonium, dimethylammonium, trimethylammonium,
tetramethylammonium, dimethylpiperdinium and alkyl of 1 to about 8
carbon atoms.
2. The detergent composition of claim 1 wherein there is present a
water-soluble builder salt in a ratio of water-soluble builder salt
to synthetic organic nonsoap detergent of about 30:1 to about
0.25:1.
3. The detergent composition of claim 2 wherein M is hydrogen.
4. The detergent composition of claim 3 wherein the
dialkylphosphinic compound is present in an amount of about 2 to
about 7 percent and the synthetic organic nonsoap detergent is an
anionic detergent.
5. The detergent composition of claim 4 wherein the synthetic
organic nonsoap detergent is an alkali metal alkylbenzene sulfonate
having an alkyl group of about nine to about 18 carbon atoms.
6. The detergent composition of claim 5 wherein the water-soluble
builder is sodium tripolyphosphate and is present in a ratio of
sodium tripolyphosphate to alkali metal alkylbenzene sulfonate of
about 9:1 to about 0.5:1.
7. The detergent composition of claim 2 wherein M is alkali
metal.
8. The composition of claim 7 wherein the dialkylphosphinic
compound is present in an amount of about 2 to about 7 percent and
the synthetic nonsoap detergent is an anionic detergent.
9. The detergent composition of claim 8 wherein the synthetic
organic nonsoap detergent is an alkali metal alkylbenzene sulfonate
having an alkyl group of about nine to about 18 carbon atoms.
10. The detergent composition of claim 9 wherein the water-soluble
builder is sodium tripolyphosphate and is present in a ratio of
sodium tripolyphosphate to alkali metal alkylbenzene sulfonate of
about 9:1 to about 0.5:1.
11. The process of conjointly washing and softening textile
materials which comprises washing said textile materials at a
temperature of about 40.degree. to about 180.degree. F. with an
aqueous solution of a detergent composition of claim 1, said
aqueous solution having at least about 16 p.p.m. of the organic
phosphorous-containing softener compound.
Description
BACKGROUND OF THE INVENTION
This invention relates to detergent compositions. More
particularly, it relates to detergent compositions exhibiting
superior softening as well as cleaning properties.
The use of synthetic detergent compositions in heavy-duty
laundering is a widespread practice. The compositions
conventionally employed generally comprise a synthetic detergent
and an alkaline builder material which functions to enhance the
cleaning level of the detergent compound. Such detergent
formulations have been known to have a tendency to react with the
metal ions present in the washing solution precipitating out
insoluble salts which deposit on the textile material being
laundered. These deposited mineral salts weaken the laundered
fabric, particularly at those areas of the fabric which are exposed
to frictional and creasing effects such as collars and cuffs. This
weakening of laundered fabrics and resulting loss of useful life
which is encountered in the course of frequent laundering have in
part resulted in the need for softener formulations capable of
improving the softness or "hand" of laundered textiles. It has been
found that the treatment of such textiles with softening agents
improves their softness or feel and prolongs their useful life. In
addition, it has been found that such a treatment generally results
in a reduced tendency of the treated fabric to accumulate
electrical charges which facilitates the ironing of such
fabric.
The compositions most commonly employed in home laundering
processes for the treatment of fabrics to improve softness or
"hand" normally are liquid fabric softener compositions which
contain a quaternary ammonium active component in a water vehicle.
These quaternary compounds have an affinity for negatively charged
fibers and normally have at least one long-chain alkyl group of
from 16 to about 20 carbon atoms.
Inasmuch as quaternary ammonium compounds are often incompatible
with certain detergent compounds, particularly anionic detergent
compounds, and interact to form complexes which exhibit neither the
desired washing nor softening properties, the use of such materials
together in the same formulation has been largely avoided. This
incompatibility problem has been obviated in part by employing
quaternary ammonium-containing softener formulations in the final
rinse of the laundering process, i.e., at a time subsequent to the
washing step.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide compositions
useful for laundering textile materials to provide conjointly
superior levels of cleaning and softening.
It is a further object of the present invention to provide
laundering compositions containing an organic detergent and a
softener component compatible therewith.
It is another object of the present invention to provide a process
of laundering textile materials whereby the laundered materials are
subjected to the conjoint action of cleaning and softening.
Other objects of the present invention will become apparent from
the description of the invention which hereinafter follows.
SUMMARY OF THE INVENTION
These and other objects were achieved in accordance with the
present invention which comprises detergent compositions consisting
essentially of 1 a synthetic organic nonsoap detergent; and (2 )
about 1 percent to about 15 percent of a compatible organic
phosphorus-containing softener compound selected from the group
consisting of
a. alkylphosphinic compounds having the formula
wherein R is alkyl of about 12 to 30 carbon atoms, R.sup.1 is
hydrogen or alkyl of one to about 30 carbon atoms, and M is a
water-solubilizing cation, e.g., hydrogen, alkali metal, ammonium
or substituted-ammonium or alkyl of about one to about eight carbon
atoms; and
b. alkyldiphosphonic compounds having the formula ##SPC2## 2
wherein R is alkyl of about 12 to about 30 carbon atoms and each M
is a water-solubilizing cation, e.g., hydrogen, alkali metal,
ammonium, substituted ammonium or alkyl of one to about eight
carbon atoms.
Also provided by the present invention is a process of conjointly
washing and softening textile materials which comprises washing
textile materials at a temperature of about 40.degree. to about
180.degree. F. with an aqueous solution of a detergent composition
hereinbefore described, the solution containing at least about 16
p.p.m. of organic phosphorus-containing softener compound.
DETAILED DESCRIPTION OF THE INVENTION
The organo-phosphorus softening agents of the present invention are
effective in the presence of a wide variety of synthetic organic
detergents. These detergents are synthetic anionic, nonionic,
ampholytic and zwitterionic nonsoap detergents characterized by
their high solubility in water, their resistance to precipitation
by the constituents of hard water and their surface active and
effective detergent properties.
Synthetic nonsoap detergents utilizable herein include:
1. Anionic synthetic detergents: This class of synthetic detergents
can be broadly described as the water-soluble salts, particularly
the alkali metal (sodium, potassium, etc.) salts, or organic
sulfuric reaction products having in the 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. 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 produced by reducing the glycerides of tallow or coconut
oil; sodium or potassium alkyl benzene sulfonates, in which the
alkyl group in a straight or branched chain contains from about
nine to about 18 carbon atoms, especially those of the types
described in U.S. Pat. Nos. 2,220,099 and 2,477,383; sodium alkyl
glyceryl ether sulfonates, especially those ethers of the higher
alcohols derived from tallow and coconut oil; sodium salts of
sulfonated .alpha. -olefins containing eight to 22 carbon atoms,
e.g., those described in U.S. Pat. No. 3,332,880, issued July 25,
1967 to Kessler et al., sodium coconut oil fatty acid monoglyceride
sulfates and sulfonates; 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 three
moles of ethylene oxide; sodium or potassium salts of alkyl phenol
ethylene oxide ether sulfate with about four units of ethylene
oxide per molecule and in which the alkyl radicals contain about
nine 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 taurine in which
the fatty acids, for example, are derived from coconut oil; and
others known in the art, a number being specifically set forth in
U.S. Pat. Nos. 2,486,921, 2,486,922 and 2,396,278 .
2. Nonionic synthetic detergents: This class of 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 products is
retained up to the point where the polyoxyethylene content is about
50 percent of the total weight of the condensation product.
Other suitable nonionic synthetic detergents include:
i. 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 10 to 25
moles of ethylene oxide per mole of alkyl phenol. The alkyl
substituent in such compounds may be derived from polymerized
propylene, diisobutylene, octane, or nonane, for example.
ii. Those derived from the condensation of ethylene oxide with the
product resulting from the reaction of propylene oxide and ethylene
diamine-- products which may be varied in composition depending
upon the balance between the hydrophobic and hydrophilic elements
which is desired. For example, compounds containing from about 20
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 on the order
of 2,500 to 3,000 , are satisfactory.
iii. The condensation product of aliphatic alcohols having from
eight to 18 carbon atoms, in either straight chain or branched
chain configuration, with ethylene oxide, e.g., a coconut alcohol
ethylene oxide condensate having from 10 to 30 moles of ethylene
oxide per mole of coconut alcohol, the coconut alcohol fraction
having from 10 to 14 carbon atoms.
3. Long chain tertiary amines oxides (nonionic detergents)
corresponding to the following general formula, R.sub.1 R.sub.2
R.sub.3 N 0, wherein R.sub.1 contains an alkyl alkenyl or
monohydroxy alkyl radical of from about eight to about 18 carbon
atoms from zero to about 10 ethylene oxide moieties, and from zero
to one glyceryl moiety, and R.sub.2 and R.sub.3 contain from one to
about three carbon atoms and from zero to about one hydroxy group,
e.g., methyl, ethyl, propyl, hydroxy ethyl, or hydroxy propyl
radicals. The arrow in the formula is a conventional representation
of a semipolar bond. Examples of amine oxides suitable for use in
this invention include dimethyldodecyl amine oxide, oleyldi(2
-hydroxyethyl) amine oxide, dimethyloctylamine oxide,
dimethyldecylamine oxide, dimethyltetradecylamine oxide, 3, 6, 9
trioxaheptadecyldiethylamine oxide, di(2 -hydroxyethyl)
tetradecylamine oxide, 2 -dodecoxy ethyl dimethylamine oxide, 3
-dodecoxy-2 -hydroxy propyl di(3 -hydroxypropyl) -amine oxide,
dimethylhexadecylamine oxide.
4. Long chain tertiary phosphine oxides (nonionic detergents)
corresponding to the following general formula RR' R" P 0 wherein R
contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from
eight to 18 carbon atoms in chain length from zero to about 10
ethylene oxide moieties and from zero to one glyceryl moiety 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:
dodecyldimethylphosphine oxide,
tetradecyldimethylphosphine oxide,
tetradecylmethylethylphosphine oxide,
3, 6, 9 -trioxaoctadecyldimethylphosphine oxide,
cetyldimethylphosphine oxide,
3 -dodecoxy-2 -hydroxypropyldi (2 -hydroxyethyl) phosphine
oxide,
stearyldimethylphosphine oxide,
cetylethylpropylphosphine oxide,
oleyl diethylphosphine oxide,
dodecyldiethylphosphine oxide,
tetradecyldiethylphosphine oxide,
dodecyldipropylphosphine oxide,
dodecyldi(hydroxymethyl) phosphine oxide,
dodecyldi(2 -hydroxyethyl) phosphine oxide,
tetradecylmethyl-2 -hydroxypropyl phosphine oxide,
oleydimethylphosphine oxide, and
2 -hydroxydodecyldimethylphosphine oxide. 5 Long chain dialkyl
sulfoxides containing one short chain alkyl or hydroxy alkyl
radical of one to about three carbon atoms (usually methyl) and one
long hydrophobic chain which contains alkyl, alkenyl, hydroxy
alkyl, or keto alkyl radicals containing from about eight to about
20 carbon atoms, from zero to about 10 ethylene oxide moieties and
from zero to one glyceryl moiety. Examples include:
octadecyl methyl sulfoxide, 2-ketotridecyl methyl sulfoxide
3, 6, 9-trioxaoctadecyl 2 -hydroxyethyl sulfoxide dodecyl methyl
sulfoxide
oleyl 3 -hydroxy propyl sulfoxide
tetradecyl methyl sulfoxide
3 -methoxytridecyl methyl sulfoxide
3-hydroxytridecyl methyl sulfoxide
3 -hydroxy-4 -dodecoxybutyl methyl sulfoxide
6. Ampholytic synthetic detergents can be broadly described as
derivatives of aliphatic secondary and tertiary amines in which the
aliphatic radical can be straight chain or branched and wherein one
of the aliphatic substituents contains from about eight to about 18
carbon atoms and one contains an anionic water solubilizing group,
e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
Examples of compounds falling within this definition are sodium 3
-dodecylaminopropionate, sodium 3 -dodecylaminopropane sulfonate,
dodecyl-beta-alanine, N-alkyl-taurines such as the one prepared by
reacting dodecylamine with sodium isethionate according to the
teaching of U.S. Pat. No. 2,658,072, N-higher alkyl aspartic acids
such as those produced according to the teaching of U.S. Pat. No.
2,438,091, and the products sold under the trade name "Miranol" and
described in U.S. Pat. No. 3,528,378.
7. Zwitterionic synthetic detergents can be broadly described as
derivatives of aliphatic quaternary ammonium, phosphonium, and
sulfonium compounds, in which the aliphatic radicals can 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,
sulfonate, sulfate, phosphate, or phosphonate. A general formula
for these compounds is:
wherein R.sup.2 contains an alkyl, alkenyl, or hydroxy alkyl
radical of from about eight to about 18 carbon atoms, from zero to
10 ethylene oxide moieties and from zero to one glyceryl moiety; Y
is selected from the group consisting of nitrogen, phosphorous, and
sulfur atoms; R.sup.3 is an alkyl or monohydroxy alkyl group
containing one to about three carbon atoms x is 1 when Y is a
sulfur atom and 2 when Y is a nitrogen or phosphorous atom, R.sup.4
is an alkylene or hydroxy alkylene of from one to about four carbon
atoms and Z is a radical selected from the group consisting of
carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
Other examples include:
4 -[ N,N-di(2 -hydroxyethyl)-N-octadecylammonio] -butane-1
carboxylate;
5 -[ S-3 hydroxypropyl-S-hexadecylsulfonio]-3 -hydroxypentane-1
-sulfate;
3 [ P,P-diethyl-P-3, 6, 9 -trioxatetracosanephosphonio] -2
-hydroxypropane-1 phosphate;
3 -[ N,N-dipropyl-N-3 -dodecoxy-2 -hydroxypropylammonio] propane-1
-phosphonate;
3 -(N,N-dimethyl-N-hexadecylammonio)propane-1 -sulfonate, 3
(N,N-dimethyl-N-hexadecylammonio)-2 -hydroxypropane-1 sulfonate, 4
[ N-N-di(2-hydroxyethyl)- N-(2 -hydroxydodecyl)ammonio] -butane-1
-carboxylate, 3 -[ S-ethyl-S-(3 -dodecoxy-2 hydroxypropyl)sulfonio]
-propane-1 -phosphate, 3 [ P,P-dimethyl-P-dodecylphosphonio]
-propane-1 -phosphonate, and S-[ N,N-di(3
-hydroxypropyl)-N-hexadecylammonio] 2 -hydroxypentane-1
-sulfate.
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.
The alkyl groups contained in said detergents can be straight or
branched, preferably straight, and saturated or unsaturated as
desired. The above list of detergents is exemplary and not
limiting. Mixtures of the above detergents can be used.
Particularly preferred organic detergents include alkali metal
(sodium, potassium, lithium) alkyl benzene sulfonates, alkali metal
alkyl sulfates, and mixtures thereof wherein the alkyl group is of
straight or branched chain configuration and contains about nine to
about 18 carbon atoms. Specific compounds preferred from the
standpoints of superior performance characteristics and ready
availability include the following:
sodium decyl benzene sulfonate, sodium dodecyl benzene sulfonate,
sodium tridecyl benzene sulfonate, sodium tetradecyl benzene
sulfonate, sodium hexadecyl benzene sulfonate, sodium octadecyl
sulfate, sodium hexadecyl sulfate and sodium tetradecyl
sulfate.
The detergent compositions of the present invention can contain
water-soluble, builder salts either of the organic or inorganic
type. Thus, the softening effects of the organic
phosphorus-containing softener compounds of the present invention
can be embodied in both built and unbuilt detergent compositions.
Since built detergent formulations are preferred from the
standpoint of enhanced cleaning, preferred compositions herein are
those containing builders of the hereinbefore-described type. These
builder materials are employed in the compositions of the present
invention in ratio by weight of builder to organic detergent of
about 30:1 to 0.25:1. Preferably, a ratio of builder to detergent
of about 9:1 to about 0.5:1 is employed.
Examples of suitable water-soluble, inorganic alkaline detergency
builder salts are alkali metal carbonates, borates, phosphates,
polyphosphates, bicarbonates, silicates and sulfates. 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, nitrilotriacetates and N-(2
-hydroxyethyl)-nitrile 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, polyphosphonates, including
specifically, sodium, potassium and lithium salts of
ethane-1-hydroxy- 1,1-diphosphonic acid, sodium potassium and
lithium salts of methylene diphosphonic acid, sodium, potassium and
lithium salts of ethylene diphosphonic acid, and sodium, potassium
and lithium salts of ethane-1,1,2 -triphosphonic acid. Other
examples include the alkali metal salts of ethane-2 -carboxy- 1,1
-diphosphonic acid, hydroxymethanediphosphonic acid,
carbonyldiphosphonic acid, ethane-1 -hydroxy- 1,1,2 -triphosphonic
acid, ethane-2-hydroxy-1,1,2 -triphosphonic acid, propane- 1,1,3,3
-tetraphosphonic acid, propane- 1,1,2,3 -tetraphosphonic acid, and
propane- 1,2,2,3-tetraphosphonic acid; (3) Water-soluble salts of
polycarboxylate polymers and copolymers as described in the patent
of Francis L. Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967.
Specifically, a detergent 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 (5) mixtures thereof.
Mixtures of organic and/or inorganic builders can be used and are
generally desirable. One such mixture of builders is disclosed in
Canadian Pat. No. 755,038 of Burton H. Gedge, e.g., ternary
mixtures of sodium tripolyphosphate, sodium nitrilotriacetate and
trisodium ethane-1 -hydroxy-1, 1 -diphosphonate. The
above-described builders can also be utilized singly in this
invention. Especially preferred builders that can be used singly or
in combination in this invention include tetra sodium pyrophosphate
and sodium tripolyphosphate.
The fabric-substantive organic phosphorus-containing softener
compounds employed in detergent compositions according to the
present invention impart improved hand or feel to the laundered
fabrics. As there will be considerable variation in the strengths
of washing solutions employed by different users, i.e., some users
may tend to use more or less than others, the requisite amount of
softener compound employed in the detergent compositions of the
present invention is an amount sufficient to impart improved hand
or feel to the laundered fabric. Normally, the fabric-substantive
softener compounds of the present invention are employed in a range
of about 1 percent to about 15 percent by weight of the detergent
composition to provide about 16 to about 240 p.p.m. of softener
compound in washing solution. A preferred range of softener
compound is about 2 percent to about 7 percent and is preferred
from the standpoints of superior softening effects and economy; it
provides about 32 to about 112 p.p.m. in washing solution.
The phosphinate softener compounds utilizable herein to impart
lubricity and improved feel or hand to laundered textiles have the
formula
wherein R is alkyl of about 12 to about 30 carbon atoms, R.sup.1 is
hydrogen or alkyl of one to about 30 carbon atoms, and M is a
water-solubilizing cation or alkyl as defined hereinbefore.
These compounds can be characterized generally as having one or two
P-C linkages in their molecules and are described herein by the
general terms phosphinic acids, salts of phosphinic acids and
esters of phosphinic acids. As employed herein, the general term
phosphinate compound is intended as embracing the acid, salt and
ester forms described herein.
The phosphinate compounds of the present invention are
characterized by the presence of at least one long chain alkyl
group of at least 12 carbon atoms which serves to provide improved
softness or hand to treated textile materials. This alkyl, which
corresponds to R in the hereinbefore described formula, can be
either branched or unbranched and can be primary, secondary or
tertiary. The phosphinate compounds of the present invention can
also contain an additional P-C linkage in the form of an alkyl of
up to about 30 carbon atoms which can also be branched, unbranched,
primary, secondary or tertiary.
Preferred phosphinate compounds are dialkylphosphinates
characterized by the presence of two identical alkyl groups of
about 16 to 24 carbon atoms. They are preferred inasmuch as they
impart excellent softening properties to laundered textiles, are
remarkably compatible with anionic surfactants and are readily
prepared by conventional means. These dialkylphosphinate compounds
are preferably employed in their acid and alkali metal forms.
The phosphinate compounds utilized herein in their salt or ester
forms are those corresponding to the hereinbefore described formula
wherein M is a water-solubilizing cation or alkyl of one to about
eight carbon atoms. Water-solubilizing cations include alkali metal
cations (e.g., sodium, potassium, lithium), ammonium ions and
substituted ammonium cations (e.g., methyl- dimethyl-, trimethyl-
and tetramethylammonium, dimethyl piperdinium). Suitable alkyl M
groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl,
n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, and the like, alkyl
groups of one to four carbon atoms being preferred. Alkali metal
cations are preferred from the standpoints of excellent results and
ready availability.
The following compounds are illustrative of the phosphinate
compounds of the present invention. It will be appreciated that
these are merely illustrative and not be regarded as limitative:
n-dodecylphosphinic acid; n-tridecylphosphinic acid;
n-tetradecylphosphinic acid; n-pentadecylphosphinic acid;
n-hexadecylphosphinic acid; n-heptadecylphosphinic acid;
n-octadecylphosphinic acid; n-nonadecylphosphinic acid;
n-eicosylphosphinic acid; n-heneicosylphosphinic acid;
n-docosylphosphinic acid; n-tricosylphosphinic acid;
n-tetracosylphosphinic acid; n-pentacosylphosphinic acid;
n-hexacosylphosphinic acid; n-heptacosylphosphinic acid;
n-octacosylphosphinic acid; n-nonascosylphosphinic acid;
n-triacontylphosphinic acid; sodium dodecylphosphinate; potassium
n-tetradecylphosphinate; lithium n-hexadecylphosphinate; sodium
octadecylphosphinate; potassium n-eicosylphosphinate; sodium
n-docosylphosphinate; potassium n-tetracosylphosphinate; sodium
n-hexacosylphosphinate; lithium n-octacosylphosphinate; lithium
n-triacontylphosphinate; methyl n-dodecylphosphinate; ethyl
n-tetradecylphosphinate; isopropyl n-tetradecylphosphinate;
2-ethylhexyl n-hexadecylphosphinate; methyl n-eicosylphosphinate;
ethyl n-tetracosylphosphinate; butyl n-octacosylphosphinate; butyl
n-triacontylphosphinate; ammonium n-hexadecylphosphinate; ammonium
n-octadecylphosphinate; dimethylammonium n-eicosylphosphinate;
trimethylammonium n-eicosylphosphinate; ammonium
n-tetracosylphosphinate; n-dodecylmethylphosphinic acid;
n-tridecylmethylphosphinic acid; ethyl-n-tetradecylphosphosphinic
acid; ethyl-n-hexadecylphosphinic acid;
methyl-n-octadecylphosphinic acid; n-eicosylmethylphosphinic acid;
n-docosylhexylphosphinic acid; di-n-dodecylphosphinic acid;
di-n-hexadecylphosphinic acid; di-n-octadecylphosphinic acid;
sodium methyl-n-octacosylphosphinate; potassium
di-n-dodecylphosphinate; sodium di-n-tetradecylphosphinate;
potassium di-n-hexadecylphosphinate; lithium
di-n-octadecylphosphinate; ammonium di-n-eicosylphosphinate; sodium
di-n-eicosylphosphinate; trimethylammonium di-n-docosylphosphinate;
sodium di-n-hexacosylphosphinate, sodium di-n-octacosylphosphinate;
sodium di-n-triacontylphosphinate; methyl di-n-eicosylphosphinate;
2-ethylhexyl di-n-eicosylphosphinate; and the isomers thereof.
The class of phosphinate compounds of the present invention are
known compounds and can be prepared by methods known to those
skilled in the art. Generally, the phosphinate compounds of the
present invention can be prepared by reacting an .alpha. -olefin or
mixture of .alpha. olefins with hypophosphorous acid or a salt
thereof in the presence of a free-radical catalyst, e.g., t-butyl
peroxide at a temperature of about 0 to 100.degree. C. to provide a
phosphinic acid or salt thereof. When hypophosphorous acid is
employed, a phosphinic acid product is obtained. Similarly, when a
salt of hypophosphorous acid is employed, the phosphinate compound
is obtained in the form of the salt. Depending upon molar
proportions, phosphinate compounds having one or two P-C bonds are
obtained, the former resulting when an excess of the hypophosphorus
acid or salt is employed, the latter when about 2 moles of .alpha.
-olefin are employed per mole of hypophosphorous acid or salt.
Esters of phosphinate compounds are conveniently obtained by
conventional esterification methods employing the phosphinic acid
form and an alkanol or by reacting an .alpha. -olefin with an ester
of hypophosphorous acid. Suitable methods of preparing phosphinate
compounds of the present invention are found in U.S. Pat. No.
2,957,931 issued Oct. 25, 1960 to Hamilton et al., and in U.S. Pat.
No. 3,092,650 issued June 4, 1963, to McBride, Jr. et al. These
patents are incorporated herein by reference.
While applicant does not wish to be bound by any particular theory
or mechanism as to the precise manner in which the softeners
function to improve the feel or hand of laundered textiles, it is
believed that the phosphinate compound attaches to the laundered
textile material at the acid, salt or ester portion of the
molecule. The one or two pendant long chain alkyl groups are
believed to exert a lubricity effect on the fibers of the laundered
textile thereby improving the feel or hand. This belief is
substantiated at least in part by the observation that
alkylphosphonate compounds belonging to the class of compounds
having the formula
wherein R is a long chain alkyl and the M' s are hydrogen also
exhibit some fabric-softening properties.
Another class of phosphorus-containing fabric substantive softener
compounds of the present invention corresponds to the formula
##SPC3##
hereinbefore described.
These compounds are characterized by the presence of a P-C-P
linkage in their molecules and are generically termed methylene
diphosphonic acids, salts of methylene diphosphonic acids and alkyl
esters of methylene diphosphonic acids. As employed hereinafter the
general term methylene diphosphonate is intended as embracing the
acid, salt and ester forms.
The methylene diphosphonates of the present invention are
characterized by the presence of a long-chain alkyl group of about
12 to about 30 carbon atoms. These compounds, like the phosphinate
compounds described hereinbefore, are believed to function
according to the mechanism whereby the methylene diphosphonate
compound attaches to laundered textile material, the pendant alkyl
group serving to provide lubricity to the textile fibers thereby
imparting improved feel or hand to the laundered fabric.
The methylene diphosphonate compounds of the present invention can
be employed to advantage as fabric softeners in either their acid,
salt or ester forms as hereinbefore stated. Thus, each M is
selected from hydrogen, alkali metal (e.g., sodium, potassium,
lithium), ammonium, substituted ammonium, or alkyl of about one to
about eight carbon atoms.
Preferred methylene diphosphonate compounds of the present
invention are the acid and alkali metal salt forms of methylene
diphosphonic acids having a pendant alkyl of about 16 to about 24
carbon atoms, these being preferred from the standpoints of
excellent softening properties, remarkable compatibility with
anionic surfactants and ease of preparation. Examples of methylene
diphosphonate compounds include the following which are intended as
being illustrative rather than limitative: tridecylidene
diphosphonic acid; tetradecylidene diphosphonic acid;
pentadecylidene diphosphonic acid; hexadecylidene diphosphonic
acid; heptadecylidene diphosphonic acid; octadecylidene
diphosphonic acid; nonadecylidene diphosphonic acid; eicosylidene
diphosphonic acid; heneicosylidene diphosphonic acid; docosylidene
diphosphonic acid; tricosylidene diphosphonic acid; tetracosylidene
diphosphonic acid; pentacosylidene diphosphonic acid;
hexacosylidene diphosphonic acid; heptacosylidene diphosphonic
acid; octacosylidene diphosphonic acid; nonacosylidene diphosphonic
acid; triacontylidene diphosphonic acid; hentriacontylidene
diphosphonic acid; trisodium tridecylidene diphosphonate;
tetrasodium pentadecylidene diphosphonate; tetrapotassium
heptadecylidene diphosphonate; tetraammonium nonadecylidene
diphosphonate; tripotassium heneicosylidene diphosphonate; disodium
dicosylidene diphosphonate; dipotassium pentacosylidene
diphosphonate; diammonium hentriacontylidene diphosphonate;
tetramethyl heptadecylidene diphosphonate; tetrabutyl
nonadecylidene diphosphonate; tetrahexylhencosylidene
diphosphonate; tetraoctyl tricosylidne diphosphonate.
The class of methylene disphosphonate compounds of the present
invention are known compounds and can be prepared by methods known
to those skilled in the art. The methylene diphosphonate esters
hereinbefore described can be conveniently prepared by preparing a
metallo-derivative of a methylene diphosphonate ester and reacting
this metallo-derivative with an organo-halide to produce the
desired methylene diphosphonate ester. Methylene disphosphonic acid
compounds can be conveniently prepared by hydrolysis of the
corresponding ester compounds with a concentrated mineral acid
(e.g. NaOH) while the salts of methylene diphosphonic acid can be
readily prepared by neutralizing the acid compound with an
appropriate basic compound (e.g. NaOH). Methods of preparing
methylene diphosphonate compounds are described in U.S. Pat. No.
3,299,123 issued Jan. 17, 1967 to Fitch et al. This reference is
hereby incorporated by reference.
The detergent softener compositions of the present invention can be
formulated into any of the several commercially desirable
composition forms, for example, granular, flake, liquid and tablet
forms. In a finished formulation of this invention there will often
be added in minor amounts materials which make the product more
effective or more attractive. The following are mentioned by way of
example. A soluble sodium carboxymethylcellulose can be added in
minor amounts to inhibit soil redeposition. A tarnish inhibitor
such as benzotriazole or ethylenethiourea may also be added in
amounts up to about 2 percent. Fluorescers, perfume and color while
not essential in the compositions of the invention, can be added in
amounts up to about 1 percent. An alkaline material or alkali such
as sodium hydroxide or potassium hydroxide can be added in minor
amounts as supplementary pH adjusters. There might also be
mentioned as suitable additives moisture, brightening agents,
sodium sulfate, fatty acid soaps, enzymes and sodium carbonate.
Corrosion inhibitors generally are also added. Soluble silicates
are highly effective inhibitors and can be added to certain
formulas of this invention at levels of from about 3 percent to
about 8 percent. Alkali metal, preferably potassium or sodium,
silicates having a weight ratio of SiO.sub.2 M.sub.2 O of from
1.0:1 to 2.8:1 will be used. M in this ratio refers to sodium and
potassium. A sodium silicate having a ratio of SiO.sub.2 :Na.sub.2
O of about 1.6:1 to 2.45:1 is especially preferred for economy and
effectiveness.
In the embodiment of this invention which provides for a built
liquid detergent, a hydrotropic agent may at times be found
desirable. Suitable hydrotropes are water-soluble alkali metal
salts of toluenesulfonate, benzenesulfonate, and xylenesulfonate.
The preferred hydrotropes are the potassium or sodium
toluenesulfonates. The hydrotrope salt may be added, if desired, at
levels of 0 percent to about 12 percent. While a hydrotrope will
not ordinarily be found necessary, it can be added if so desired
for any reason such as to produce a product which retains its
homogeneity at a low temperature.
The detergent softener compositions of the present invention can be
employed to advantage in home and commercial laundry situations to
provide conjoint washing and softening effects. These compositions
impart excellent softening effects to all types of textile
materials including cottons, woolens, silks and synthetics such as
nylon, dacron, creslan or the like. The advantageous conjoint
washing and softening effects described herein are not limited to
any essential temperature conditions; they can be achieved, for
instance, by conducting the washing process at temperatures of
about 40.degree. F. to about 180.degree. F. Cool water washing as
used herein contemplates washing at temperatures below the very hot
water washing commonly encountered in general household laundering
situations and contemplates washing at about 40.degree. F. to about
100.degree. F. Normally, the conjoint washing and softening effects
can be obtained by conducting the laundering process in an aqueous
solution of a detergent softener composition described hereinbefore
and is conducted in the presence of at least about 16 p.p.m. of the
organic phosphorus-containing softener compound of the present
invention. When so treated, most textile materials are
characterized by excellent hand or feel. Preferably, a washing
solution having about 32 to about 112 p.p.m. of the organic
phosphorus-containing softener compound is employed for superior
softening effects and economy.
The following examples are presented to illustrate the invention,
with parts by weight being used in the examples unless otherwise
indicated.
EXAMPLE I
A granular detergent composition was prepared by mixing the
individual ingredients in a crutcher in a conventional manner with
sufficient water to form a detergent slurry. The slurry was oven
dried to remove excess moisture and to form detergent granules.
---------------------------------------------------------------------------
Ingredients Parts by Weight
__________________________________________________________________________
Sodium straight chain alkyl benzene sulfonate having an average
chain length of about 5 11.8 carbon atoms 15.0 Sodium
tripolyphosphate 50.0 Sodium silicate having an SiO.sub.2 Na.sub.2
O ratio of 1.6 : 1 6.0
__________________________________________________________________________
Sodium carboxymethylcellulose 0.3 Sodium sulfate 15.7
__________________________________________________________________________
Di-n-eicosylphosphinic acid 3.0
__________________________________________________________________________
Water 10.0
__________________________________________________________________________
This composition employed in an aqueous washing solution in an
amount sufficient to provide at least about 16 p.p.m. of the
dieicosylphosphinic acid results in superior levels of cleaning and
softening to textile materials.
Substantially similar results are obtained when the following
phosphinate compounds are employed in lieu of
di-n-eicosylphosphinic acid in that products combining cleaning and
softening properties in the same formulation are obtained:
n-dodecylphosphinic acid; n-tridecylphosphinic acid;
n-tetradecylphosphinic acid; n-pentadecylphosphinic acid;
n-hexadecylphosphinic acid; n-heptadecylphosphinic acid;
n-octadecylphosphinic acid; n-nonadecylphosphinic acid;
n-eicosylphosphinic acid; n-heneicosylphosphinic acid;
n-docosylphosphinic acid; n-tricosylphosphinic acid;
n-tetracosylphosphinic acid; n-pentacosylphosphinic acid;
n-hexacosylphosphinic acid; n-heptacosylphosphinic acid;
n-octacosylphosphinic acid; n-nonacosylphosphinic acid;
n-triacontylphosphinic acid; sodium n-dodecylphosphinate; potassium
n-tetradecylphosphinate; lithium n-hexadecylphosphinate; sodium
octadecylphosphinate; potassium n-eicosylphosphinate; sodium
n-docosylphosphinate; potassium n-tetracosylphosphinate; sodium
n-hexacosylphosphinate; lithium n-octacosylphosphinate; lithium
n-triacontylphosphinate; methyl n-dodecylphosphinate; ethyl
n-tetradecylphosphinate; isopropyl n-tetradecylphosphinate;
2-ethylhexyl n-hexadecylphosphinate; methyl n-eicosylphosphinate;
ethyl n-tetracosylphosphinate; butyl n-octacosylphosphinate; butyl
n-triacontylphosphinate; ammonium n-hexadecylphosphinate; ammonium
n-octadecylphosphinate; dimethylammonium n-eicosylphosphinate,
trimethylammonium n-eicosylphosphinate; ammonium
n-tetracosylphosphinate; n-dodecylmethylphosphinic acid;
n-tridecylmethylphosphinic acid; ethyl-n-tetradecylphosphinic acid;
ethyl-n-hexadecylphosphinic acid; methyl-n-octadecylphosphinic
acid; n-eicosylmethylphosphinic acid; n-do-cosylhexylphosphinic
acid; di-n-dodecylphosphinic acid; di-n-hexadecylphosphinic acid;
di-n-octadecylphosphinic acid; sodium
methyl-n-octacosylphosphinate; potassium di-n-dodecylphosphinate;
sodium di-n-tetradecylphosphinate; potassium
di-n-hexadecylphosphinate; lithium di-n-octadecylphosphinate;
ammonium di-n-eicosylphosphinate; sodium di-n-eicosylphosphinate;
trimethylammonium di-n-docosylphosphinate; sodium
di-n-hexacosylphosphinate, sodium di-n-octacosylphosphinate; and
sodium di-n-triacontylphosphinate; methyl di-n-eicosylphosphinate;
2-ethylhexyl di-n-eicosylphosphinate; and the isomers thereof.
EXAMPLE II
A granular detergent composition was prepared according to the
procedure of example I except that five parts of the
di-n-eicosylphosphinic acid were employed. The two additional parts
of softener compound replaced two parts of the sodium sulfate.
This composition imparts excellent softness to laundered textiles
when employed in a laundering solution containing about 240 p.p.m.
It is an effective cleaning composition.
EXAMPLES III AND IV
Granular detergent compositions were prepared according to the
procedures of examples I and II, respectively, except that in each
instance the phosphinate employed was a mixture of
dialkylphosphinic acid compounds having a random distribution of
alkyl groups ranging from 14 to 22 carbon atoms, prepared by
reaction at 85.degree. C. of 2 moles of a mixture of .alpha.
-olefins with one mole of hypophosphorous acid. The distribution of
.alpha. -olefins employed in the reaction with hypophosphorous acid
was as follows:
C.sub.14 3.8 percent (by weight) C.sub.16 12.9 percent C.sub.18
33.9 percent C.sub.20 37.6 percent C.sub.22 11.8 percent
These compositions combine advantageous softening and cleaning
effects in the laundering of most textile materials.
When the following builder salts are employed in place of sodium
tripolyphosphate, substantially similar results are obtained in
that effective cleaning and softening formulations are employed:
sodium tetraborate; potassium bicarbonate; sodium carbonate; sodium
pyrophosphate; sodium orthophosphate, potassium hexametaphosphate;
sodium ethylenediaminetetraacetate, potassium nitrilotriacetate;
sodium N-(2-hydroxyethyl)nitrilo diacetate; sodium phytate; sodium,
potassium and lithium salts of ethane-1 -hydroxy-1,1 -diphosphonic
acid; sodium, potassium and lithium salts of ethylene diphosphonic
acid; sodium, potassium and lithium salts of 1,1,2 -triphosphonic
acid; sodium, potassium and lithium salts of ethane-2-carboxy-1,1
-disphosphonic acid, hydroxymethanediphosphonic acid,
carbonyldiphosphonic acid, ethane-1-hydroxy-1 ,1,2-triphosphonic
acid, ethane-2-hydroxy-1,1,2,-triphosphonic acid, 3,
propane-1,1,3,3-tetraphosphonic acid,
propane-1,1,2,3-tetraphosphonic acid, and salts of polymers of
itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric
acid, methylene malonic acid and citraconic acid and copolymers
with themselves and/or ethylene and/or acrylic acid in, e.g.,1:1
molar ratios and having molecular weights of 75,000; 100,000; and
125,000 (the copolymers with ethylene and/or acrylic acid having
equivalent weights, based on the acid form of 65, 70 and 75); in
the form of their sodium, potassium, triethanolammonium,
diethanolammonium and monoethanolammonium salts.
EXAMPLE V
A granular detergent composition having the following composition
was prepared according to the procedure of example I:
---------------------------------------------------------------------------
parts by Weight
__________________________________________________________________________
Sodium straight chain alkyl benzene sulfonate having an average
chain length of about 11.8 carbon atoms 20 Sodium tripolyphosphate
50 Sodium silicate having a SiO.sub.2 :Na.sub.2 O ratio of 1.6 : 1
6 Sodium carboxymethylcellulose 0.3 Sodium sulfate 10.7
Heptadecylidene diphosphonic acid C.sub.16 H .sub.33 CH [ PO
(OH).sub.2 ] .sub.2 3.0 Water 10.0
__________________________________________________________________________
This composition combines cleaning and softening properties in the
same formulation.
Substantially similar results are obtained when the following
softener compounds are employed in lieu of heptadecylidene
diphosphonic acid: tridecylidene diphosphonic acid; tetradecylidene
diphosphonic acid; pentadecylidene diphosphonic acid;
hexadecylidene diphosphonic acid; octadecylidene diphosphonic acid;
nonadecylidene diphosphonic acid; eicosylidene diphosphonic acid;
heneicosylidene diphosphonic acid; docosylidene diphosphonic acid;
tricosylidene diphosphonic acid; tetracosylidene diphosphonic acid;
pentacosylidene diphosphonic acid; hexacosylidene diphosphonic
acid; heptacosylidene diphosphonic acid; octacosylidene
diphosphonic acid; nonacosylidene diphosphonic acid;
triacontylidene diphosphonic acid; hentriacontylidene diphosphonic
acid; trisodium tridecylidene diphosphonate; tetrasodium
pentadecylidene diphosphonate; tetrapotassium heptadecylidene
diphosphonate; tetraammonium nonadecylidene diphosphonate;
tripotassium heneicosylidene diphosphonate; disodium discosylidene
diphosphonate; dipotassium diphosphonate; diammonium
hentriacontylidene diphosphonate; tetramethyl heptadecylidene
diphosphonate; tetrabutyl nonadecylidene diphosphonate; tetrahexyl
hencosylidene diphosphonate; tetraoctyl tricosylidene
diphosphonate.
EXAMPLE VI
An excellent built liquid detergent formation according to this
invention which combines superior cleaning and softening properties
has the following composition, in which amounts are expressed in
percentage by weight.
Sodium dodecylbenzenesulfonate (the dodecyl radical being a
polypropylene, predominantly tetrapropylene averaging 12 carbon
atoms) 6.0 Dimethyldodecylamine oxide 6.0% Trisodium
ethane-1-hydroxy- 1.1-diphosphonate 20.0% Potassium
toluenesulfonate 8.0% Sodium silicate (ratio SiO.sub.2 :Na.sub.2 O
of 2.45:1) 3.8% Carboxymethyl hydroxyethyl cellulose 0.3%
Sodium-n-eicosylmethylphosphinate 5.0% Water Balance
Substantially similar results are obtained when the following
softener compounds are employed in lieu of sodium
eicosylmethylphosphinate in that a product exhibiting both cleaning
and softening properties is obtained: sodium
dodecylmethylphosphinate; sodium-n-tetradecylmethylphosphinate;
potassium n-hexadecylmethylphosphinate;
potassium-n-octadecyl-n-propylphosphinate;
lithium-n-eicosylmethylphosphinate;
lithium-n-docosylmethylphosphinate; ammonium
methyl-n-tetracosylphosphinate; trimethylammonium
methyl-n-triacontylphosphinate.
When in the the above example the following organic detergents are
substituted, either wholly or in part (e.g., a 1:1 ratio) for the
said sodium alkyl benzene sulfonate having an average chain length
of about 12 carbon atoms, substantially equivalent results are
obtained in that the detergent composition is an effective cleaning
and softening formulation:
1. The following anionic synthetic detergents wherein the cations
are sodium, potassium, ammonium, monoethanolammonium,
diethanolammonium, triethanolammonium cations. Alkyl sulfates
wherein the alkyl group is derived from tallow or coconut oil;
alkyl benzene sulfonates in which the alkyl groups contain nine,
11, 12, 13 or 15 carbon atoms; alkyl glycidyl ether sulfonates
derived from tallow or coconut oils; coconut fatty acid
monoglyceride sulfates and sulfonates; salts of sulfuric esters of
the reaction product of 1 mole of tallow or coconut oil fatty
alcohols and 3 or 4 moles of ethylene oxide; alkyl phenol ethylene
oxide ether sulfates containing four or nine ethylene oxide
moieties per molecule and in which the alkyl radical contains nine,
12, 13 or 15 carbon atoms; the neutralized reaction product of
coconut fatty acids with isethionic acid; coconut fatty acid amide
of methyl taurine salts;
2. The following nonionic detergents: the condensation product of
propylene oxide with propylene glycol, the ethylene oxide portion
of the compound being 50 percent of the total weight of the
compound and the total molecular weight of the compound being about
1,700; the condensation product of alkyl phenols containing nine or
12 carbon atoms in the alkyl group with 10, 15 or 20 moles of
ethylene oxide per mole of alkyl phenol; the condensation product
of ethylene oxide with the condensation product of propylene oxide
and ethylene diamine wherein the product contains about 65 percent
polyethylene oxide by weight and the total molecular weight of the
compound is about 6,000; the condensation product of coconut oil
fatty alcohol and about 15 moles of ethylene oxide per mole of
coconut alcohol;
3. The following semipolar detergents:
dimethyldodecyl amine oxide,
oleyldi (2-hydroxyethyl) amine oxide,
dimethyloctylamine oxide,
dimethyldecylamine oxide,
dimethyltetradecylamine oxide,
3,6,9 trioxaheptadecyldiethylamine oxide,
di(2-hydroxyethyl) tetradecylamine oxide,
2-dodecoxyethyl dimethylamine oxide,
3-dodecoxy-2-hydroxy propyl di(3-hydroxypropyl)-amine oxide,
dimethylhexadecylamine oxide,
dodecyldimethylphosphine oxide,
tetradecyldimethylphosphine oxide,
tetradecylmethylethylphosphine oxide,
3,6,9-trioxaoctadecyldimethylphosphine oxide,
cetyldimethylphosphine oxide,
3-dodecoxy-2-hydroxypropyldi(2-hydroxyethyl)phosphine oxide,
stearyldimethylphosphine oxide,
cetylethylpropylphosphine oxide,
oleyl diethylphosphine oxide,
dodecyldiethylphosphine oxide,
tetradecyldiethylphosphine oxide,
dodecyldipropylphosphine oxide,
dodecyldi (hydroxymethyl) phosphine oxide,
dodecyldi (2-hydroxyethyl) phosphine oxide,
tetradecylmethyl-2-hydroxypropyl phosphine oxide,
oleyldimethylphosphine oxide,
2-hydroxydodecyldimethylphosphine oxide,
octadecyl methyl sulfoxide,
3,6,9-trioxaoctadecyl 2-hydroxyethyl sulfoxide,
dodecyl methyl sulfoxide,
oleyl 3-hydroxy propyl sulfoxide,
tetradecyl methyl sulfoxide,
3-methoxytridecyl methyl sulfoxide,
3-hydroxytridecyl methyl sulfoxide,
3-hydroxy-4-dodecoxybutyl methyl sulfoxide,
4. The following ampholytic detergents: sodium
3-dodecylaminopropionate, sodium 3-dodecylaminopropane-1-sulfonate,
dodecyl-beta-alanine, N-alkyltaurines; N-higher alkyl aspartic
acids, wherein the alkyl group contains about 12 carbon atoms;
5. The following zwitterionic detergents:
4-[N,N-di(2-hydroxyethyl-N -octadecylammonio]-butane-1-carboxylate;
5-[S-(3-hydroxypropyl)-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate;
3-[P,P-diethyl-P-(3,6,9-trioxatetracosanephosphonio)]-2-hydroxypropane-1-p
hosphate; 3-[N,N,-dipropyl-N-(3-dodecoxy-2-hydroxypropylamminio)]
-propane-1-phosphonate; 3-N,N-dimethyl-N-hexadecylammonio)
propane-1-sulfonate,
3-(N,N,-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate,
4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl
ammonio]-butane-1-carboxylate, 3-[S-ethyl-S-(3-do-decoxy-2-hydroxy
propylsulfonio)]-propane-1-phosphate,
3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate, and
5-[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxypentane-1-sulfate;
and
6. mixtures thereof in, e.g., 1:1 ratios.
EXAMPLE VII
An excellent granular detergent composition providing outstanding
cleaning and softening in washing situations has the following
ingredients in the percentages indicated:
Sodium dodecylbenzenesulfonate (dodecylgroup derived from
tetrapropylene 17.5% Potassium toluenesulfonate 2.0% Sodium
tripolyphosphate 45.0% Sodium silicate (ratio SiO.sub.2 :Na.sub.2 0
of 2:1) 6.0% Sodium sulfate 11.8% Coconut fatty acid ethanolamide
2.7% Ammonium ethyl-n-tetracosylphosphinate 4.0% Moisture
Balance
Substantially similar results are obtained when the following
organic detergents are employed in place of sodium
dodecylbenzenesulfonate in that effective cleaning and softening
formulations are obtained: sodium decylbenzene sulfonate; sodium
tridecylbenzene sulfonate, sodium hexadecylbenzene sulfonate,
sodium octadecylbenzene sulfonate, sodium octadecyl sulfate sodium
hexadecyl sulfate, sodium tetradecyl sulfate, and sodium dodecyl
sulfate, sodium tetradecene sulfonate, sodium dodecyl glyceryl
ether sulfonate, sodium salts of the sulfated reaction product of 1
mole of coconut fatty alcohol and 3 moles of ethylene oxide.
EXAMPLE VIII
A granular detergent composition providing excellent cleaning and
softening properties has the following formulation:
Sodium alkylbenzenesulfonate (the alkyl group being a mixture of
C.sub.12' C.sub.13' and C.sub.14 carbon atoms, averaging C.sub.13)
7.5% Nonionic active (a mixture of 1.5% Ucon and 0.5% Pluronic
L-64).sup.1 2.0% Hydrogenated marine oil fatty acid 2.2% Sodium
tripolyphosphate 47.6% Sodium nitrilotriacetate 10.0% Sodiium
silicate (ratio Si0.sub.2 :Na.sub.2 0 of 2:1) 9.7% Sodium sulfate
11.5% 2-ethylhexyl ester of n-tetracosylphosphinic acid 4.0% Water
Balance .sup.1 Condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide with
propylene glycol and having molecular weights of approximately
characteristi s of this composition are exceptionally good from the
point of view of general cleaning and whiteness maintenance
performance.
EXAMPLE IX
An effective cool water built liquid detergent which performs
exceptionally well as a heavy-duty detergent composition,
especially in the areas of cleaning and softening, has the
following composition:
3(N,N-dimethyl-N-hexadecylammonio)- 2-hydroxypropane-1-sulfonate
11.0% Sodium pyrophosphate 18.0% Sodium silicate (Si0.sub.2
:Na.sub.2 0 = 1.6:1) 3.8% Potassium toluenesulfonate 8.5% Sodium
carboxymethyl hydroxyethyl cellulose 0.3% Fluorescent 0.12% Perfume
0.15% Benzotriazole 0.02% Tetraethyl tridecylidene diphosphonate
(C.sub.12 H.sub.25 CH[P(0)(C.sub.2 H.sub.5).sub.2].sub.2 4.0% Water
54.11%
Substantially similar results are obtained when the following
softener compounds are employed in place of tetraethyl
tridecylidene diphosphonate in that formulations combining
effective cleaning and softening properties are obtained:
tetramethyl heptadecylidene diphosphonate; tetrabutyl
octadecylidene diphosphonate; tetrapropyl nondecylidene,
diphosphonate; tetrabutyl eicosylidene diphosphonate; tetramethyl
hencosylidene diphosphonate; tetraoctyl triacosylidene
diphosphonate; tetramethyl pentacosylidene diphosphonate.
EXAMPLE X
An effective built granular composition providing superior cleaning
and softening has the following compositions:
Sodium hexadecyl sulfate 17.0% Sodium tripolyphosphate 43.0% Sodium
silicate (Na.sub.2 0:Si0.sub.2 = 1:2.5) 6.0% Sodium carboxymethyl
cellulose 0.3% Sodium sulfate 26. % Sodium
di-n-octadecylphosphinate 4.0% Water 3.5% Miscellaneous Balance
Substantially similar results are obtained when the following
softener compounds are employed in place of sodium
dioctadecylphosphinate in that a superior cleaning and softening
formulation is obtained: sodium di-n-dodecylphosphinate; sodium
di-n-tridecylphosphinate; sodium di-n-tetradecylphosphinate; sodium
di-n-pentadecylphosphinate; potassium di-n-hexadecylphosphinate;
potassium di-n-heptadecylphosphinate; potassium
di-n-octadecylphosphinate; lithium di-n-nonadecylphosphinate;
lithium di-n-eicosylphosphinate; sodium di-n-docosylphosphinate;
sodium di-n-tricosylphosphinate; potassium
di-n-tetracosylphosphinate; lithium di-n-pentacosylphosphinate;
lithium di-n-hexacosylphosphinate; lithium
di-n-heptacosylphosphinate; lithium di-n-octacosylphosphinate;
sodium di-n-triacontylphosphinate.
EXAMPLE XI
An unbuilt granular composition which provides superior cleaning
and softening effects to laundered fabrics has the following
composition:
Sodium hexadecyl sulfate 93.5 Di-n-eicosylphosphinic acid 6.5
All or a portion of the di-n-eicosylphosphinic acid can be replaced
with eicosylidene diphosphonic acid with substantially similar
results.
The excellent softening properties of detergent compositions of the
present invention were evaluated according to the following
procedure. Three 15 inches .times. 15 inches cotton terrycloth
swatches were laundered with a washing solution of the test
composition in water of 7-grain hardness and 120.degree. F.
temperature using a miniature 1-gallon washing machine equipped
with a mechanical agitator. The detergent softener composition
identified below in table I as examples I-V were those specifically
described and listed above under the corresponding example numbers.
The test products were employed in amounts sufficient to provide
the concentration of softener compound in washing solution shown in
table I. Following a 10-minute washing cycle and two rinse cycles,
the fabrics were dried. This procedure, representing one cycle, was
repeated for a total of six cycles for each test composition. A
panel of five experts evaluated the dried swatches for softness
after the second, fourth and sixth cycles, comparing the softness
of the treated swatches with the feel of swatches treated with a
washing solution containing 6 gms. of a control composition
corresponding to that of example I but having no phosphinic acid
softener compound present. The results tabulated below in table I
indicate the percentage of expert graders preferring the softness
and feel of terrycloths treated with compositions of the present
invention as compared to those treated in the same manner with the
control composition.
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TABLE I
Cycle Concentration of Softener Compound Formulation p.p.m. 2 4 6
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Example I 48 40% 80% 80% Example II 80 100% 100% 80% Example III 48
100% 100% 100% Example IV 80 100% 100% 100% Example V 48 80% 100%
80%
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by this procedure, the softening effects of each of the specific
organic phosphorus compounds used was demonstrated. This embodiment
illustrates the compatibility of the synthetic detergents with the
phosphorus containing softener compounds. Likewise, the
compositions provide excellent cleaning properties.
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