DETERGENT COMPOSITIONS

DETERGENTS

English Abstract

DETERGENT COMPOSITIONS
Abstract
Described are detergent compositions, which contain
little or no phosphate materials, containing, as an im-
proved builder system, a mixture of aluminosilicate
materials and polyacetal carboxylate builders. These
compositions deliver improved cleaning performance at
reduced phosphate levels.

Claims

- 23 -
Claims:
1. A detergent composition, which contains from 0 to about
25% phosphate materials, comprising:
(a) from about 13 to about 95% by weight of surfactant;
(b) from about 5% to about 99% of a detergency builder
mixture consisting essentially of:
(i) a water-insoluble sodium aluminosilicate
material, having the formula
Naz(AlO2)z(SiO2)y.xH2O,
wherein z and y are integers equal to at least
6, the molar ratio of z to y is from about
1.0:1 to about 0.5:1, and x is an integer from
about 15 to about 264, said material having a
calcium ion exchange capacity of at least 200
milligrams equivalent/gram, a calcium ion
exchange rate of at least about 2 grains/
gallon/ minute/gram, and a particle size
diameter of from about 0.1 microns to about
100 microns; and
(ii) a stabilized water-soluble polymer comprising
polyacetal carboxylate segments having the
structure
<IMG> ,
wherein M is selected from the group consisting
of alkali metal, ammonium, tetralkyl ammonium
and alkanol amine groups having from 1 to
about 4 carbon atoms in the alkyl and alkanol
chains; n averages at least 4; and the total
number of polyacetal carboxylate segments
comprise at least 50% by weight of the total
polymer;
wherein the weight ratio of the aluminosilicate
material to the polyacetal carboxylate material is
from about 1:10 to about 10:1.
2. The composition of Claim 1 comprising from about 20%
to about 60% by weight of the builder mixture.

- 24 -
3. The composition of Claim 1 wherein the weight ratio of
the aluminosilicate material to the polyacetal carboxylate
material is from about 1:4 to about 4:1.
4. The composition of Claim 3 wherein the weight ratio is
from about 1:2 to about 2:1.
5. The composition of Claim 1 wherein the aluminosilicate
material is hydrated zeolite A, X, or P (B).
6. The composition of Claim 5 wherein the aluminosilicate
material has a particle size diameter of from about 0.1
microns to about 10 microns.
7. The composition of Claim 6 wherein n averages between
10 and 200.
8. The composition of Claim 7 wherein M is an alkali metal.
9. The composition of Claim 1 wherein n averages between
10 and about 200.
10. The composition of Claim 9 wherein n averages between
about 50 and about 100.
11. The composition of Claim 1 wherein M is an alkali metal.
12. The composition of Claim 11 wherein M is sodium.
13. The composition of Claim 1 wherein the polymer comprises
polyacetal carboxylate segments having the general formula:
<IMG>
wherein Y is a chain extending agent, p averages at least 4,
q is at least 1, and M is as defined above.

- 25 -
14. The composition of Claim 13 wherein the polyacetal
carboxylate segments in the polymer comprise at least 80%
by weight of the total polymer.
15. The composition of Claim 13 wherein the chain extending
agent is an oxyalkyl group having from 1 to about 4 carbon
atoms.
16. The composition of Claim 13 wherein the chain extending
agent is at least one ?CH2CH2O?.
17. The composition of Claim 13 wherein the chain extending
agent is at least one ?CH2CH(CH3)O?.
18. The composition of Claim 1 wherein the polymer is a
water-soluble polyacetal carboxylate having the structure
<IMG>
wherein M is selected from the group consisting of alkali
metal, ammonium, tetralkyl ammonium groups and alkanol
amine groups having from 1 to about 4 carbon atoms in the
alkyl chain; n averages at least 4; R1 and R2 are individ-
ually any chemically stable group which stabilize the poly-
acetal carboxylate against rapid depolymerization in alka-
line solution; and the total number of polyacetal carboxy-
late segments comprise at least 50% by weight of the total
polymer.
19. The composition of Claim 18 wherein R1 and R2 are
individually selected from the group consisting of alkyl
and cyclic alkyl groups containing oxygen.
20. The composition of Claim 18 wherein R1 is selected
from the group consisting of -OCH3, -OC2H5, HO(CH2CH2O?1-4,

- 26 -
<IMG> ,
<IMG> ,
and mixtures thereof, and R2 is selected from the group
consisting of -CH3, -C2H5, ?CH2CH2O?1-4H,
<IMG> ,
<IMG> ,
and mixtures thereof, where R is hydrogen or alkyl having
1 to 8 carbon atoms.
21. The composition of Claim 18 wherein n is a number
between 4 and about 400.
22. The composition of Claim 21 wherein n is a number
between about 50 to about 200.
23. The composition of Claim 18 wherein M is sodium, R1
is <IMG>, <IMG>
or mixtures thereof, R2 is <IMG>,
and n averages between about 50 and about 200.

- 27 -
24. The composition of claim 18 wherein R1 is
HO(CH2CH2O)1-4, R2 is ?CH2CH2O?1-4H, M is sodium and n
averages between about 50 and about 200.
25. The composition of Claim 1 comprising from about 10% to
about 50% by weight of the surfactant.
26. The composition of claim 1 wherein the surfactant is
selected from the group consisting of anionic, cationic,
nonionic, ampholytic, and zwitterionic surfactants, and
mixtures thereof.
27. The composition of Claim 26 wherein the surfactant is
a nonionic surfactant.
28. The composition of Claim 27 wherein the surfactant
is a biodegradable nonionic surfactant having the formula
R(OC2H4)nOH wherein R is a primary or secondary alkyl
chain of from about 8 to about 22 carbon atoms and n is an
average of from about 2 to about 12, having an HLB of from
about 5 to about 17.
29. The composition of Claim 26 wherein the surfactant is
selected from the group consisting of cationic and nonionic
surfactants, and mixtures thereof.
30. The composition of Claim 29 wherein the surfactant is
a mixture consisting essentially of:
(a) a biodegradable nonionic surfactant having the
formula R(OC2H4)nOH wherein R is a primary or
secondary alkyl chain of from about 8 to about 22
carbon atoms and n is an average of from about 2
to about 12, having an HLB of from about 5 to
about 17; and
(b) a cationic surfactant, free of hydrazinium groups,
having the formula
<IMG>

- 28 -
wherein each R1 is an organic group containing a
straight or branched alkyl or alkenyl group optionally
substituted with up to 3 phenyl or hydroxy groups and
optionally interrupted by up to 4 structures selected
from the group consisting of
, <IMG> , <IMG> , <IMG> , <IMG> ,
<IMG> , <IMG> , -O-, <IMG> , <IMG> , <IMG> ,
and mixtures thereof, each R1 containing from about
8 to about 22 carbon atoms, and which may additionally
contain up to about 12 ethylene oxide groups; m is a
number from 1 to 3; each R2 is an alkyl or hydroxy
alkyl group containing from 1 to 4 carbon atoms or a
benzyl group, with no more than one R2 in a molecule
being benzyl; x is from 0 to 11, the remainder of any
carbon atom positions being filled by hydrogens; Y is
selected from the group consisting of
(1) <IMG> ,
(2) <IMG> ,
(3) <IMG>,
(4) <IMG> ,
(5) <IMG> , wherein p is from 1 to 12,

- 29 -
(6) <IMG>, wherein each p is from 1 to 12,
(7) <IMG> ,
(8) <IMG>
, and
(9) mixtures thereof;
L is 1 or 2, the Y groups being separated by a moiety
selected from the group consisting of R1 and R2
analogs having from one to above twenty-two carbon
atoms and 2 free carbon single bonds when L is 2; Z
is an anion in a number sufficient to give electrical
neutrality to the molecule; said cationic surfactant
being at least water-dispersible in admixture with
said nonionic surfactant;
the ratio of said nonionic surfactant to said cationic
surfactant being in the range of from 2:1 to about 100:1,
and said mixture having a cloud point of from about 0 to
about 95°C.
31. The composition of Claim 28 or 30 wherein the
alumino-silicate material is hydrated zeolite A or X and
has a particle size diameter of from about 0.1 microns to
about 10 microns.
32. The composition of Claim 30 wherein n averages
between about 50 and about 100 and M is sodium.

Description

33~
-- 1 --
~ETER~ENT COMPOSITIONS
Technical Field
This invention relates to detergent compositions
containing, as an improved builder system, a combination
of polyacetal carboxylate builder materials and alumino-
silicate materials. These compositions deliver excellent
particulate soil removal performance and greasy/oily soil
removal benefits. Preferably, this builder system is
incorporated into detergent compositions containing non-
ionic, and more preferably cationic/nonionic, surfactants
Background Art
The property possessed by some materials of improving
detergency levels of soaps and synthetic detergents and
the use of such materials in detergent compositions is
known. Such cleaning boosters are called "builders" and
such builders permit the attainment of better cleaning
performance than is possible when so-called unbuilt com-
positions are used. The behavior and mechanisms by which
builders perform their function are only partially under-
stood. It is known that good builders must be able to
sequester most of the calcium and/or magnesium ions in
the wash water since these ions are detrimental to the
detergency process. However, it is difficult to predict
which compounds possess useful combinations of builder
properties and which compounds do not because of the com-
plex nature of detergency and the countless factors which
contribute both to overall performance results and the
requirements of environmental acceptability.
Sodium tripolyphosphate (STP) has been found to be a
highly efficient cleaning and detergent builder and this
compound has been widely used for decades in cleaning and
detergent formulations. However, because of the recent
emphasis on removing phosphates from detergent and clean-
ing compositions for environmental reasons, the detergent
and cleaning industry is now looking for materials suit-
able for use as builders which do not contain phosphorus,
~.

-- 2 --
and which are environmentally acceptable. It is difficult,
however, to simultaneously deliver effective cleaning
performance and biodegradability. Inorganic builders
other than STP are generally not satisfactory for use as
a builder in detergent formulatio~s because of their poor
builder properties. Sodium aluminosilicates, commonly
known as zeolites, have been proposed for use in detergent
formulations since they are able to soften water by
removing calcium ions; however, they are not very
effective in removing magnesium ions from water.
Thus, it can be seen that there is a need for a new
material wi~h builder properties equivalent to STP, which
does not contain phosphorus, which is water-soluble, and
which achieves environmental acceptability by being
readily biodegradable. Now, according to the present
invention, there is provided a new builder mixture which
is equal to, if not superior to, STP and the organic
portion of which will depolymerize rapidly in a non-
alkaline medium to form low molecular weight components
which are readily biodegradable.
Summary of the Invention
The present invention encompasses a detergent
composition, which contains from 0 to about 25% phosphate
. materials, comprising:
(a) from about 1% to about 95% by weight of
surfactant;
(b) from about 5~ to about 99~ of a detergency
builder mixture consisting essentially of:
(i) a water-insoluble sodium aluminosilicate
material, having the formula
Naz(Alo2)z(sio2)y-xH2o~
wherein z and y are integers equal to at
least 6, the molar ratio of z to y is from
about 1.0:1 to about 0.5:1, and x is an
integer from about 15 to about 264, said
material having a calcium ion exchange
capacity of at least 200 milligrams

3~
-- 3 --
equivalent/gram, a calcium ion exchange rate
of at least about 2 grains/gallon/minute/
gram, and a particle size diameter of from
about 0.1 microns to about 100 microns; and
(ii) a stabilized water-soluble polymer compris-
ing polyacetal carboxylate segments having
the structure
~CHotn
COOM
wherein M is selected from the group consist-
ing of alkali metal, ammonium, tetraalkyl
ammonium and alkanol amine groups having
from 1 to about 4 carbon atoms in the alkyl
and alkanol ~hains; n averages at least 4;
and the total number o polyacetal carboxy-
late segments comprise at least 50% by
weight of the total polymer;
wherein the weight ratio of the aluminosilicate
material to the polyacetal carboxylate material
is from about 1:10 to about 10:1.
As a particularly preferred embodiment of the present
invention, the above-described builder mixture is incorp-
orated into a detergent composition containing a nonionic
surfactant, and, more preferably, a cationic~nonionic
surfactant mixture, as hereinafter described.
Disclosure of the Invention
This invention comprises the discovery of an improved
builder system for use in detergent compositions. The
builder system, a combination of polyacetal carboxylate
builder materials and aluminosilicate materials, delivers
excellent particulate soil removal performance and greasy/
oily soil removal benefits. The detergent compositions
are especially good in 10-40C water, especially when the
particle size diameter of the aluminosilicate material is
from about 0.5 to about 2 microns.

3~
-- 4 --
The essential elements in the detergent composition of
this invention are: a detergent surfactant, a polyacetal
carboxylate builder material, and an aluminosilicate
material.
Surfactant
The detergent surfactant represents from about 1~
to about 95%, preferably from about 10% to about 50%, by
weight of the detergent composition. Suitable surfactants
are any of those generally known in the art. More specif-
ically, the surfactant can be selected from the group
consisting of anionic, cationic, nonionic~ ampholytic, and
zwitterionic surfactants, and mixtures thereof.
Suitable surfactants for use herein are described in
U. S. Patent 3,936,537, Baskerville et al, issued February
3, 1976, and in Canadian Patent Application Serial No.
341,900, Jones et al, filed December 13, 1979~
As a preferred embodiment of the present invention,
the detergent surfactant is selected from the group
consisting of cationic and nonionic surfactants, and
~ mixtures thereof, particularly those described in Canadian
Patent Applications Serial No. 306,456,.Cockrell, filed
June 29, 1978; Serial No. 306,474, Murphy, filed June 29,
1978; Serial No. 325,240, Murphy, filed March 12, 1979.
A particularly preferred surfactant mixture consists
essentially of:
(a) a biodegradable nonionic surfactant having the
formula R(OC2H4)nOH wherein R is a primary
or secondary alkyl chain of from about 8 to about
22 carbon atoms and n is an average of from about
2 to about 12, having an HLB of from about 5 to
about 17; and
(b) a cationic surfactant, free of hydrazinium groups,
having the formula
m x LZ
. . ~

~18B~1
-- 5 --
wherein each Rl is an organic group containing a
straight or branched alkyl or alkenyl group optionally
substitu~ed with up to 3 phenyl or hydroxy groups and
optionally interrupted by up to 4 structures selected
from the group consisting of
O O O R R O
C-O-, -O-C-, -C-N-, -N-C-,
o H H o o O H H o
Il l l 11 11 11 1 1 11
-C-N-, -N-C-, -O-, -O-C-O-, -O-C-N-, -N-C-O--,
and mixtures thereof, each Rl containing from about
8 to about 22 carbon atoms, and which may additionally
contain up to about 12 ethylene oxide groups; m is a
number from 1 to 3; each R2 is an alkyl or hydroxy
alkyl group containing from 1 to 4 carbon atoms or a
benzyl group, with no more than one R2 in a molecule
being benzyl; x is from O to 11, the remainder of any
carbon atom positions being filled by hydroyens; Y is
selected from the group consisting of
(1) -N-
;
I
N - C -
/+
(2) -C~ I
N - C -
l+
(3) _p_
(4) -S-
I
(5) -N- , wherein p is from 1 to 12,
(C2H4)pH

B~3~
(lC2 4 )p
(6) -Ni , wherein each p is from 1 to 12,
I
~ 2 4 )p
I
(7)\ ~ C ~
C +N
C C
~ C~
(8) ~ C~
N +N
~C C ~ , and
N ~
(9) mixtures thereof;
L is 1 or 2, the Y groups being separated by a moiety
selected from the group consisting of R and R
analogs having from one to above twenty-two carbon
atoms and 2 free carbon single bonds when L is 2; Z
is an anion in a number sufficient to give electrical
neutrality to the molecule; said cationic surfactant
being at least water-dispersible in admixture with
said nonionic surfactant;
the ratio of said nonionic surfactant to said cationic
surfactant being in the range of from 2:1 to about 100:1,
and said mixture having a cloud point of from about O to
about 95C.
As another preferred embodiment of the present
invention, the surfactant for use herein is a nonionic
lS surfactant, and preerably is a biodegradable nonionic
surfactant having the formula R(OC2H~)nOH wherein R is a
primary or secondary alkyl chain of from about 8 to about
22 carbon atoms and n is an average of from about 2 to
about 12, having an HLB of from about 5 to about 17.
'~3;,.

3~
-- 7 --
Builder Mixture
The detergent compositions herein contain from about 5%
to about 99~, preferably from about 20% to about 60%, by
weight of a detergency builder mixture. The builder
mixture consists essentially of:
(i) a water-insoluble sodium aluminosilicate
material, having the formula
Naz(Alo2)z(sio2)y-xH2o~
wherein z and y are integers equal to at least
6, the molar ratio of z to y is from about
1.0:1 to about 0.5:1, and x is an integer
from about 15 to about 264, said material
having a calcium ion exchange capacity of
at least 200 milligrams equivalent/gram, a
calcium ion exchange rate of at least about
2 grains/gallon/minute/gram, and a particle
size diameter of ~rom about 0.1 microns to
about 100 microns; and
(ii) a stabilized water~soluble polymer compris-
ing polyacetal carboxylate segments having
the structure
~CHotn
COOM
. wherein M is selected from the group consist-
ing of alkali metal, ammonium, tetraalkyl,
ammonium and alkanol amine groups having from
1 to about 4 carbon atoms in the alkyl and
alkanol chains; n averages at least 4; and
the total number of polyacetal carboxylate
segments comprise at least 50% by weight of
the total polymer;
wherein the weight ratio of the aluminosilicate
material to the polyacetal carboxylate material
is from about 1:10 to about 10:1.
Preferably, the weight ratio of the aluminosilicate mater-
ial to the polyacetal carboxylate material is from about
1:4 to about 4:1, more preferably from about 1:2 to about
2:1.
` ` ~

383~
The aluminosilicate materials for use herein are those
commonly known as hydrated zeolites A, X, and P(B). The
zeolites should have a particle size diameter of from about
0.1 microns to about 100 microns, preferably from about 0.1
microns to about 10 microns. Aluminosilicate materials are
more fully described in U.S. Patent 4,096,081, Phenicie et
al, issued June 20, 1978; and Canadian Patent 1,035,234
issued July 25~ 1978.
The polyacetal carboxylates for use herein are more
fully described in U.S. Patents 4,144,226 issued March 13,
1979 and 4,146,495 issued March 27, 1979.
These polyacetal carboxylates can be prepared by bring-
ing together under polymerization conditions an ester of
glyoxylic acid and a polymerization initiator. The result-
ing polyacetal carboxylate ester is then attached to
chemically stable end groups to stabilize the polyacetal
carboxylate against rapid depolymerization in alkaline
solution, converted to the corresponding salt, and added
to a surfactant.
For the purposes of this invention, the term "rapid
depolymerization in alkaline solution" as it is used in
the specification and claims, shall mean that in an aqueous
solution of 0.5 molar sodium hydroxide containing 10 grams
per liter of polyacetal carboxylate, the average chain
length of the polyacetal carboxylate will be reduced bymore than 50~, as determined by Proton Magnetic Resonance,
after 1 hour at 20C.
Any number of esters of glyoxylic acid can be used to
prepare the polyacetal carboxylates of the present inven-
tion. Such esters can be made by the reaction of an alcohol

3~
g
containing from 1 to 4 carbon atoms with glyoxylic acid
hydrate under conditions known to those skilled in the art.
Thereafter, the ester hemiacetal can be converted to the
corresponding aldehyde ester by any number of techniques
known to those skilled in the art, such as the reaction of
the ester hemiacetal with phosphorus pentoxide. The pro-
duct of the above reaction is then polymerized by tech-
niques known to those skilled in the art using an initiator
in accordance with the following general equation:
HC = O ~CHOt
I - Initiator I n
C = O -~ C = O (I)
OR OR
The resulting polyacetal carboxylate ester is then
reacted at its termini with a reagent which produces a
chemically stable end group to stabilize the polyacetal
carboxylate against rapid depolymerization in alkaline
solution. The stabilized polyacetal carboxylate is then
reacted with a base, such as lithium hydroxide, sodium
hydroxide, potassium hydroxide, ammonium hydroxide,
alkanolammonium hydroxide, and the like to make the
polyacetal carboxylate salt suitable for use as a builder
and as a sequestrant.
The glyoxylic acid can be converted to the ester by
reaction with any number of alcohols, such as methanol,
ethanol, propanol, isopropanol, and the like. It is only
necessary that the ester group does not interfere with the
subsequent polymerization. Methanol is preferred.
Any number of initiators can be used for the polymer-
ization. Nonionic or ionic initiators provide satisfac-
tory results. Suitable initiators include 2-hydroxy
pyridine -H20 complex; triethyl amine; ethylvinyl ether-
trifluoroacetic acid, and the like. Even traces of hydroxy
ion or cyanide ion will trigger the polymerization under
nonaqueous conditions. Compounds such as diethylsodium-
alonate or sodiomethylmalonate esters have been used withgood results.

8~
-- 10 --
Any number of chemically reactive groups can be added
to the polyacetal carboxylate termini to stabilize the
polyacetal carboxylate against rapid depolymerization in
an alkaline solution. It is only necessary that the chem-
ically reactive group stabilizes the polyacetal carboxy-
late against rapid depolymerization in an alkaline
solution, and the specific nature of the chemically
reactive group is not important in the proper function
of the polyacetal carboxylate in its intended use. As
an example, suitable chemically stable end groups include
stable substituent moieties derived from otherwise stable
compounds, such as alkanes, such as methane, ethane, pro-
pane, butane and higher alkanes such as decane, dodecane,
octadecane and the like; alkenes such as ethylene, propyl-
ene, butylene, decene, dodecene and the like; branched
chain hydrocarbons, both saturated and unsaturated, such
as 2-methyl butane, 2-methyl butene, 4-butyl-2,3-dimethyl
octane and the like; aromatic hydrocarbons such as benzene,
toluene, xylene and the like, cycloalkanes and cycloalkenes
such as cyclohexane and cyclohexene and the like; halo-
alkanes such as chlorobutane, dichloropentane and the
like; alcohols such as methanol, ethanol, 2-propanol,
cyclohexanol, sodium phenate and the like; polyhydric
alcohols such as 1,2-ethane diol, 1,4-benzene diol and the
like; mercaptans such as methane thiol, 1,2-ethanedithiol
and the like; ethers such as methoxyethane methyl ether,
ethyl ether, ethoxypropane and cyclic ethers such as
ethylene oxide, epichlorohydrin, tetramethylene oxide and
the like; aldehydes and ketones such as ethanal, acetone,
propanal, methylethyl ketone and the like; and carboxylate-
containing compounds such as the alkali metal salts o~
carboxylic acids, the esters of carboxylic acids and the
anhydrides. The abo~e listing is intended to be instruc-
tive and is not intended to be limited since chemically
stable end groups that stabilize the polyacetal carboxy-
late against rapid depolymerization in alkaline solution
include nitrilo groups and halides such as chlorides,
bromides and the like. Particularly suitable end groups

33~
include alkyl groups and cyclic alkyl groups containing
oxygen: such as oxyalkyl groups like methoxy, ethoxy and
the like; carboxylic acids such as -CH2COOM,
COOM H OCH2C 3
S -CR , -COOM , -CH
COOM COOM CH
OH (~OOM)2
and the like; aldehydes, ethers and other oxygen-containing
alkyl groups such as -OCHCH3OC2H5, ~OCH2CH2tl_4OH~
tCH2CH2tl 4H,
CH3 CH CH CH2 - CH2
-CH , -CH CH2, -OCH ~ CH
OCH2CH3 O - CH2 CH2
and the like. In the above examples of suitable end
groups, M is alkali metal, ammonium, alkanol amine, alkyl
groups having 1 to 4 carbon atoms, tetraalkyl ammonium
groups and alkanol amine groups having from 1 to about 4
carbon atoms in the alkyl chain, and R is hydrogen or
alkyl group of 1 to 8 carbon atoms. As will occur to those
skilled in the art in light of the present disclosure, the
, chemically stable end groups at the polyacetal carboxylate
termini can be alike or unlike.
As a further example of the polyacetal carboxylates of
the present invention wherein the end groups can be dif~er-
ent, one end group can be a polymer, and particularly a
polymer with an anionic charge, which permits one or more
of the polyacetal carboxylates of the present inven-tion to
be appended to the polymer, or on the other hand, the poly-
acetal carboxylates of the present invention can be the
part of a block copolymer having a polymer chain at each
of the polyacetal carbo~ylate termini. Preferred polymers
that are anionic or can be made anionic include: polymers
of cellulose acetate, cellulose propionate, cellulose
acetate butyrate, polyvinyl acetate, polyvinyl alcohol and
the like. In the case of an anionic polymer, the polymer

- 12 -
can be used to ~nitiate the polymerization to form the
polyacetal carboxylates wherein the polymer adds to the
termini as one of the chemically stable end groups to
stabilize that end of the polyacetal carboxylate against
rapid depolymerization in an alkaline solution, and there-
after the other end of the polyacetal carboxylate can be
stabilized with a compound such as ethylene oxide or the
like, as described above.
In one embodiment of this invention, diethylsodio~
malonate or sodiomethylmalonate is used as an initiator
to form the polymer. These compounds not only serve to
initiate the polymerization, but also the ester adds to
the termini as one of the chemically stable end groups to
stabilize that end of the polyacetal carboxylate against
rapid hydrolysis in an alkaline solution. These compounds
can be prepared from the corresponding esters using sodium
hydride in a solvent, such as tetrahydrofuran, by tech-
niques known to those skilled in the art.
Accordingly, it can be seen that in one embodiment of
this invention the builder mixture contains a water-soluble
polyacetal carboxylate having the structure:
RltCHO t- R2
COOM /n
wherein M is selected from the group consisting of alkali
metal, ammonium, tetraalkyl ammonium groups and alkanol
amine groups having from 1 to about 4 carbon atoms in the
alkyl chain; n averages at least 4; and Rl and R2 are
individually any chemically stable group which stabilizes
the polyacetal carboxylate against rapid depolymerization
in alkaline solution.
The number of repeating units, i.e., the value of n,
in the polyacetal carboxylate is important since the effec-
tiveness of the polyacetal carboxylate salt as a detergency
builder is affected by the chain length. Even when there
are as few as four repeating units (i.e., n averages 4),
the polyacetal carboxylate salt shows some effectiveness as
a sequestrant, chelating agent and builder. Although there
.~ .

8.~
- 13 -
is no upper limit to the desired number of repeating units,
which may be as high as 400, or even higher, there does
not seem to be an advantage to having more than about 200
repeating units. When the number of repeating units
exceeds about 100, significant improvement in seques-
tration, chelation and builder properties is not observed.
Thus, it is preferred that the polyacetal carboxylate
contain between about 10 and about 200 units, and even
more preferred that the polyacetal carboxylate contains
between about 50 and about 100 repeating units.
The most important factors believed to control the
chain length include (1) the initiator concentration, (2)
the temperature of the polymerization, ~3) the purity of
the starting materials, and (4) the presence of solvents
and their levels. AS will occur to those skilled in the
art, the concentration of the initiator, solvents and
their levels, and the temperature of the polymerization
reaction are all interrelated and the desired chain length
can easily be controlled by simple experimentation by con-
trolling these variables. Generally speaking, the lower
the temperature at the beginning of the polymerization, the
higher the chain length. For example, when polymerization
was initiated with one mole percent 2-hydroxy pyridine
-H2O complex at a temperature of -70C., the resulting
polyacetal carboxylate contained 60 repeating units as
determined by Proton Magnetic Resonance (PMR). On the
other hand, when one mole percent 2-hydroxy pyridine -H2O
complex was used at about 20C, the resulting polyacetal
carboxylate had only about 20 repeating units.
The polyacetal carboxylate can also contain other
polymer fragments, and accordingly, the polymer can be a
linear homopolymer or copolymer, or it can be branched.
To form a copolymer, the polyacetal carboxylate segments
are polymerized with any number of chain extending agents
known to those skilled in the art. It is only necessary
that the chain extending agent does not cause the poly-
acetal carboxylate to rapidly depolymerize in alkaline
.

~B~3~
- 14 -
solution, or become insoluble in water. Rither aliphatic
or aromatic chain extending agents can be used, but ali-
phatic chain extending agents are pre~erred to make the
polymer more environmentally acceptable, and aliphatic
chain extending agents having from 1 to 4 carbon atoms,
such as ethylene oxide or propylene oxide, are especially
preferred.
It is important that a copolymer contains at least 4
repeating units (i.e., n averages at least 4) of the acetal
carboxylate to insure that the copolymer will effectively
sequester calcium and magnesium ions and provide builder
properties. It is preferred that the copolymer contain at
least 10 repeating units of acetal carboxylate, or more,
say 50 or 100 repeating units, for the reasons described
above. As will occur to those skilled in the art in light
of the present disclosure, having at least 4 acetal car-
boxylate units in a copolymer prepared by block or graft
polymerization techniques should not present a problem,
but when acetal carboxylate esters are copolymerized with
a chain extending agent, the amount of acetal carboxylate
should be at least about 50% by weight, based on the total
weight of the polymer, to insure that the polymer will
effectively sequester calcium and magnesium ions and retain
its builder properties. It is preferred that the amount
of acetal carboxylate is 80~ by weight, based on the total
weight of the polymer, or even higher.
As will occur to those skilled in the art, any number
of chain extending agents can be copolymerized with the
polyacetal carboxylates of the present invention. It is
only necessary that the chain extending agent will provide
at least two reactive sites and does not cause the poly-
acetal carboxylates to depolymerize in alkaline solution.
Suitable chain extending agents include: polyhydric alco-
hols, such as ethylene glycol, propylene glycol and the
like; epoxy compounds, such as ethylene oxide, propylene
oxide, epihalohydrin epoxysuccinates and the like alde-
hydes, such as formaldehyde, acetaldehyde, and the like.

3~
- 15 -
It is particularly beneficial when the chain extending
agent contains substituent carboxy groups.
Thus, it can be seen that in one embodiment of this
invention the builder mixture contains a stabilized water-
soluble polymer comprising polyacetal carboxylate segments
having the general formula:
[ Y(CHO)p
COOM
where Y is at least one chain extend~ng agent, preferably
alkyl or oxyalkyl having 1 to 4 carbon atoms, p averages
at least 4, q is at least 1, and M is selected from the
group consisting of alkali metal, ammonium, tetraalkyl
ammonium groups and alkanol amine groups having from 1 to
about 4 carbon atoms in the alkyl chain. Furthermore, the
lS polyacetal carboxyla~es having a chain extending agent can
be stabilized against rapid depolymerization in alkaline
solution by the same techniques used above using suitable
reagents or polymers as described above.
The polyacetal carboxylate ester can be converted to
the corresponding alkali metal, ammonium, tetraalkyl ammon-
ium or alkanol amine salts by conventional saponification
techniques, and such salts are especially useful as a
builder in detergent formulations. Since the pH of a
detergent solution is usually between pH 9 and pH 10, the
polyacetal carboxylate salt will not depolymerize rapidly
when used as a detergent builder in aqueous solution at
normal use concentrations (1 cup/washer), temperatures
~10-60C), and times (i.e., about 15 minutes) typical of
United States home laundry practices. Generally, the use
of the alkali metal salts, particularly the sodium salt,
is preferred. However, in some formulations where greater
builder solubility is required, the use of ammonium or
alkanol ammonium salts may be desirable.
It is to be noted that when the alkali, ammonium, or
alkanol ammonium salts of the present invention are used
as builders, they will be used generally in an alkaline
medium. When the compositions of the present invention

3~
- 16 -
are used at a pH of 7 or below, some of the preferred of
the polymer salts wll depolymerize. Thus, it can be seen
that the compositions of the present invention are effec-
tive cleaning agen~s, but when an aqueous solution contain-
ing the composition is discharged into a sewer or otherwaste water system, these preferred polyacetal carboxylate
salts will soon depolymerize into small fragments which
are readily biodegradable
Other Optional In~edients
Other ingredients which are conventionally used in
detergent compositions can be included in the detergent
compositions of the present invention. These components
include other detergency builders, antistatic and fabric-
softening agents, color speckles, bleaching agents and
bleach activators, suds boosters or suds suppressors,
anti-tarnish and anti-corrosion agents, soil suspending
agents, soil release agents, dyes, fillers, optical
brighteners~ germicides, pH adjusting agents, alkalinity
sources, hydrotropes, enzymes, enzyme-stabilizing agents,
perfumes, alkyl polyethoxylate nonionic surfactants, and
other optional detergent compounds.
As used herein, all percentages, parts and ratios given
are "by weight", unless otherwise specified.
The following nonlimiting examples illustrate the
additives and compositions of the present invention.
..,~

3~
- 17 -
EXAMPLE I
The following detergent composition was produced:
Composition A
Component Wt./%
Dihydrogenated tallowalkyl 7.65
dimethylammonium chloride
C12-13 E6 5 34.45
Monoethanol amine 7.3
Polyacetal carboxylate2 25.25
Sodium aluminosilicate3 25.25
Condensation product of C12 13 alcohol with 6.5
moles of ethylene oxide, commercially available as
Neodol 23-6.5 from Shell Chemical Company.
r l 1
CH3CH2-O-CH-O- - C - O - ICH-OCH2CH3, n = 86 (average)
3 CH3 COONa n CH3
12[(A102)l2(sio2)l2].27H2o
This composition delivered excellent particulate soil
removal performance, as demonstrated hereinafter in Example
III. Further, the composition provided greasy/oily soil
removal benefits.
EXAMPLE II
The following detergent compositions ~ere produced:
Composition B
Component Wt./~
~5 Dihydrogenated tallowalkyl7.65
dimethylammonium chloride
C12-13 E6 5 34.45
Monoethanol amine 7.3
Polyacetal carboxylate2 50.5
Composition C
Component Wt./%
Dihydrogenated tallowalkyl7.65
dimethylammonium chloride
C12-13 E6 5 34.45
Monoethanol amine 7.3 ~'
Sodium aluminosilicate3 50.5 :

~ L~B~3~
-- 18 --
EXAMPLE I I I
The detergent compositions described in Examples I and
II were tested as follows.
Identical clay-soiled cotton, polyester/cotton, and
polyester swatches were washed in aqueous solutions having
dissolved therein 500 parts per million of the detergent
compositions described in Examples I and II. The swatches
were washed for 10 minutes in a miniature agikator contain~
ing 1-1~2 gallons of washing liquor at 100F and artific-
ial water hardness (2 parts Ca++ to 1 part Mg+~) at levelsof 2, 7 and 12 grains per gallon. The swatches comprised
approximately 4~ by weight of the washing liquor. Aft~r
washing, the swatches were spun dry and rinsed with 1-1/2
gallons of water, at 100F, having the same water hardness
as that of the water they were washed in. The swatches
were then dried in a miniature electric dryer. A Hunter
Reflectometer was used to obtain a reflectance reading (in
Hunter Whlteness Units) for each of the laundered swatches.
A higher reflectance reading indicates greater cleaning
effectiveness. The results were as follows:
Fabric Water Harness Hunter Whiteness
Units
Swatches Washed with Composition A
Cotton2 gr./gal. 37.57 + 1.30
"7 gr./gal. 33.48 ~ 0.55
"12 gr./gal. 25.66 + 1.37
Polycotton2 gr./gal. 67.09 ~ 1.20
7 gr./gal. 63.54 + 0.44
"12 gr./gal. 58.37 + 0.80
30Polyester2 gr./gal. 70.09 + 1.52
"7 gr./gal. 68.89 + 1.32
"12 gr./gal. 64.87 + 1.23
Swatches Washed with Composition B
Cotton 2 gr./gal. 28.60 + 0.30
~l 7 gr./gal. 24.98 + 0.69
"12 gr./gal. 15.94 + 0.96

3~
-- 19 --
Polycotton 2 gr./gal. 59.86 + 1.34
" 7 gr./gal. 56.52 ~ 3.07
" 1~ gr./gal. 50.08 + 3.12
Polyester 2 gr./gal. 70.06 + 0.83
" 7 gr./gal. 61.55 + 0.81
" 12 gr./gal. 46.45 + 2.04
Swatches Washed_with Composition C
Cotton 2 gr./gal. 17.~5 + 2.51
" 7 gr./gal. 11.43 + 1.37
ll 12 gr./gal. 7.57 + 1.90
Polycotton 2 gr./gal. 55.54 ~ 1.34
" 7 gr./gal. 48.37 ~ 1.43
" 12 gr./gal. 57.94 + 0.75
Polyester 2 gr./gal. 71.65 + 0.86
~ 7 gr./gal. 71.20 + 0.76
" 12 gr./gal. ~9.17 + 1.53
These results clearly deomonstrate that synergistic
cleaning performance was provided by the combination of
the polyacetal carboxylate builder and the aluminosilicate
material. Substantially better overall cleaning was pro-
vided, at the same total builder level in otherwise ident-
ical compositions, by the detergent composition containing
the builder mixture than was provided by the detergent
compositions containing only the individual builders.
Substantially similar cleaning performance is obtained
when the surfactant for use in Composition A is selected
from the group consisting of anionic, cationic, nonionic,
ampholytic, and zwitterionic surfactants, and mixtures
thereof; and especially when the surfactant is selected
from the group consisting of cationic and nonionic surfac-
tants, and mixtures thereof. Similar cleaning is obtained ~'
when the surfactant is a biodegradable nonionic surfactant
having the formula R~OC2H4)nOH wherein R is a primary or
secondary alkyl chain of from about 8 to about 22 carbon
atoms and n is an average of from about 2 to about 12,
having an HLB of from about 5 to about 17. Similar

~B~3~
- 20 -
cleaning is obtained when the surfactant is any mixture
consisting essentially of a biodegradable nonionic sur-
factant having the formula R(OC2H4)nOH wherein R is
a primary or secondary alkyl chain of from about 8 to
about 22 carbon atoms and n is an average of from about 2
to about 12, having an HLB of from about 5 to about 17,
and a cationic surfactant, free of hydrazinium
groups, having the formula RmRxYLZ as defined herein.
Substantially similar cleaning benefits are obtained
when the weight ratio of the aluminosilicate material to
the polyacetal carboxylate material is from about l:10 to
about 10:1, especially when from about 1:4 to about 4:1.
Similar cleaning is obtained when the aluminosilicate
material is any hydrated zeolite A, X or P(B), having a
particle size diameter of from about 0.1 microns to about
100 microns, especially from about 0.1 microns to about 10
microns, especially about 1 micron.
Substantially similar cleaning performance is obtained
when the number of polyacetal carboxylate segments aver-
ages at least 4 r but especially when n averages between 10and 200.
EXAMPLE IV
The following detergent composition is produced:
Component Wt./~
Tallowalkyl sulfate 5.5
Tallowethoxylate sulfate 5.5
Sodium (C12) linear al~yl-
benzene sulfonate (C12LAS) 3.5
Sodium silicate 2.0
Sodium tripolyphosphate 12.5
Polyacetal carboxylate 12.5
Sodium aluminosilicate 18.0
(hydrated Zeolite ~, particle
diameter 1-10 microns)
Sodium carbonate 10.0
Sodium sulfate 28.5
Miscellaneous 2.0
100.O

8~3~
- 21 -
EXAMPLE V
The following detergent composition is produced:
Component Wt,/~
Tallowalkyl sulfate 5.5
Tallowethoxylate sulfate 5.5
Sodium (C12) linear alkyl-
benzene sulfonate (C12LAS) 3.5
Sodium silicate 2.0
Polyacetal carboxylate220.0
Sodium aluminosilicate18.0
(hydrated Zeolite A, particle
diameter 1-10 microns)
Sodium carbonate 10.0
Sodium sulfate 33.5
Miscellaneous 2.0
100.O
EXAMPLE VI
The following detergent composition is produced:
Component Wt./%
Sodium tetrapropylene 20
benzene sulfonate
Sodium pyrophosphate 10
Sodium orthophosphate 5
~ Sodium hydrated Zeolite A 10
(3 micron diameter)
Polyacetal carboxylate210
Sodium sulfate 20
Sodium carbonate 10 '
H2O and minors Balance
EXAMPLE VII
The following detergent composition is produced:
Component Wt./~
Sodium tetrapropylene benzene 25
sulfonate
Sodium carbonate S
Sodium bicarbonate 10
Sodium pyrophosphate 15
Polyacetal carboxylate15
'`Y;~
.~

~1 383~
- 22 -
Hydrated sodium Zeolite X 10
(3 micron diameter)
Sodium sulfate, H2O, and minors Balance
EXAMPLE VI I I
The followir.g detergent composition is produced:
Component Wt./%
Sodium coconut alkyl poly- 14
ethoxylate (3) sulfate
Coconut alkyl dimethyl amine 8
oxide
Polyacetal carboxylate2 5
Hydrated sodium Zeolite P 5
(2 micron diameter)
Water and ethanol Balance
EXAMPLE IX
The following detergent composition is produced:
Component Wt./%
Sodium C13 alkylbenzene 15
sulfonate
C12_15 alkyl polyethoxylate (6.5) 25
Polyacetal carboxylate 20
Hydrated sodium Zeolite A 15
(-0.8 micron diameter)
H2O Balance
2~ EXAMPLE X
The following detergent composition is produced:
Component Wt./%
C12_13(E)6 5 12.0
C14-15(E)7 0 12.0
Ditallow dimethylammonium 4.8
chloride
Ethanol 10.0
Polyacetal carboxylate2 10.0
Sodium aluminosilicate3 10.0
Sodium citrate 0.5
Miscellaneous (includes perfume,0.37
brightener, dye)
Water Balance
;'~~