CA1148831A

CA1148831A - Detergent compositions

Info

Publication number: CA1148831A
Application number: CA000345728A
Authority: CA
Inventors: Victor F. Rodriguez; Brandon H. Wiers
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1979-02-16
Filing date: 1980-02-15
Publication date: 1983-06-28
Also published as: JPS55147599A; EP0015024A1

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.

Description

33~

~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, ~.

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~

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.

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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 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

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(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.

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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.

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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.

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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, 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, -CH , -CH CH2, -OCH ~ CH

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 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.~

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~

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~

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~

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.

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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 :

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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~

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~

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~

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~

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 ;'~~

Claims

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 , 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.

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:
wherein Y is a chain extending agent, p averages at least 4, q is at least 1, and M is as defined above.

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 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, , , and mixtures thereof, and R2 is selected from the group consisting of -CH3, -C2H5, ?CH2CH2O?1-4H, , , 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 , or mixtures thereof, R2 is , and n averages between about 50 and about 200.

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 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 , , , , , , , -O-, , , , 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) , (2) , (3) , (4) , (5) , wherein p is from 1 to 12, (6) , wherein each p is from 1 to 12, (7) , (8) , 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.