|Publication number||US3691107 A|
|Publication date||Sep 12, 1972|
|Filing date||Aug 28, 1970|
|Priority date||Aug 28, 1970|
|Publication number||US 3691107 A, US 3691107A, US-A-3691107, US3691107 A, US3691107A|
|Inventors||Erdy Nicholas Z, Yu Arthur J|
|Original Assignee||Stauffer Chemical Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (10), Referenced by (6), Classifications (11)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent Erdy et al.
[ NOVEL DETERGENT COMPOSITIONS  Inventors: Nicholas Z. Erdy, New York, N.Y.;
Arthur J. Yu, Stamford, Conn.
 Assignee: Stauiier Chemical Company, New
 Filed: Aug. 28, 1970  App1.No.: 68,016
 US. Cl. ..252/544, 252/89, 252/132, 252/140, 252/155, 252/523, 252/525,
 Int. Cl. ..Clld 3/30  Field of Search ..252/89, 135, 525, 527, 544, 252/546, 140, 155; 260/785 R  References Cited UNITED STATES PATENTS 2,264,103 11/1941 Tucker ..210/23 2,31 1,008 2/1943 Tucker ..210/23 3,060,124 10/1962 Ginn ..252/135 3,060,155 10/1962 Reinhard ..260/78.5 R
1 51 Sept. 12, 1972' Primary Examiner-Leon D. Rosdol Assistant Examiner-1-larris A. Pitlick Attorney-Wayne C. Jaeschke, Martin Goldwasser and Daniel S. Ortiz [5 7] ABSTRACT There are disclosed novel detergent compositions comprising a mixture of one or more surfactants with a unique builder for said compositions which comprises a cross linked, water-insoluble copolymer of at least one C C olefin and at least one polycarboxyl vinyl monomer; said crosslinked, water-insoluble copolymer being a water-swellable, gel-forming material.
16 Claims, No Drawings NOVELDETERGENT COMPOSITIONS BACKGROUND OF THE INVENTION Detergent compositions for use in both home and industrial cleaning operations generally comprise a mixture of one or more surfactants along with a substance which is commonly referred to as a builder." Builders, which generally are present in detergent compositions in concentrations of from about -50 percent, by weight, serve to substantially enhance the cleaning ability of the detergent composition by means of various mechanisms such, for example, as by providing it with the ability to sequester metallic ions thereby softening the wash water in situ. Commonly utilized builders include the alkali metal carbonates, borates, bicarbonates, silicates and especially the inorganic phosphates and polyphosphates such as sodium tripolyphosphate (S TPP).
Although these, inorganic phosphates provide efficient re'sults'a's detergentbuil'ders, their use is presently being curtailed since it is believed, by some, that the presence of their residues may, in some manner, facilitate the occurrence of eutrophication. The latter phenomenon involves the rapid growth of algae in ponds, lakes and streams whereupon during their subsequent decompositionessentially all of the dissolved oxygen in the water is consumed thereby making it uninhabitable by fish and other forms of aquatic life.
Another class of materials which has been considered for use as detergent builders is the organic polyelectrolytes comprising salts of carboxylated polymers. In particular, the prior art has stressed that water soluble polymersor polymer salts, which may be either linear or crosslinked, are suitable for such usage. However, the performance of detergent compositions containing such water soluble polymeric builders has not been found to be appreciably better than the results obtainable with compositions containing phosphate builders although the former are not considered to be a source of algal growth.
Y Thus, itis the prime object of this invention to provide detergent compositions containing builders which will have no discernible effect upon algal growth while nonetheless providing a degree of cleaning efficiency which is at least equivalent to that attainable with inorganic phosphates. Various other objects and advantages will be apparent from a reading of the disclosure which follows hereinafter.
TECHNICAL DISCLOSURE OF THE INVENTION cleaning efficiency which equals and, in many cases,
surpasses the results obtained with detergents which contain phosphate builders. Moreover, the polymeric builders of these detergent compositions are not known to promote eutrophication.
The C.,-C olefins applicable for use in preparing the water-insoluble, crosslinked copolymer detergent builders suitable for use in the compositions of this invention include l-butene, isobutylene, l-pentene, l-hexene, diisobutylene, l-octene, l-nonene and l-decene and their mixtures. From this group, the use of isobutylene is preferred. As for the applicable polycarboxyl vinyl comonomers, these may include any ethylenically unsaturated monomer, or a mixture of such monomers, which contain at least two carboxyl groups which may be in either the free acid, anhydride or salt form. Thus, for this purpose, one may use one or more of such polycarboxyl monomers as maleic, fumaric, itaconic, aconitic, methylene malonic, mesaconic, citraconic and 3-butene-l,2,3-tricarboxylic acids as well as their polymerizable salts and anhydrides. In effect, it is possible to employ any vinyl monomer, such as a nitrile, amide or ester, whose polymerized moieties will yield at least two carboxyl groups upon introducing the copolymer into an aqueous system. From the above group, it is preferred to use maleic anhydride as the polycarboxyl comonomer. The final copolymer should contain from about 20 to 80, and preferably from about 40 to 60 mole percent of moieties derived from one or more of the above listed C.,-C olefins with the balance of the copolymer comprising moieties derived from one or more of the above noted polycarboxyl monomers. These proportions may also be expressed in terms of the fact that the mole ratio of the polycarboxyl monomer to the olefin monomer in these copolymers ranges from about 1:4 to about 4:1.
The preparation of these copolymers ordinarily involves a polymerization process wherein the selected monomers are dissolved in an inert diluent which may be a solvent for one or more of the monomers but which may or may not be a solvent for the resulting copolymer. Suitable diluents include heptane, benzene, toluene, the xylenes, I ethyl acetate, acetone, tetrahydrofuran, dimethyl sulfoxide and dimethyl formamide. And, in some cases, an excess of one of the monomers may also be used as the diluent. The monomer solution is heated at a temperature of from about 30 to 200 C., and preferably between about 60 to C. for a period of from about 0.5 to 10 hours at pressures which may range from ambient up to about 1,000 psi, and preferably at autogenous pressure, during the polymerization; the amount of pressure being dependent upon the monomers being polymerized, the choice of diluent and the reaction temperature. The reaction is conducted in the presence of from about 0.01 to 10 percent, by weight of the monomer charge, of a solvent soluble free radical initiating catalyst which may include peroxide compounds such as peracetic acid, benzoyl peroxide, caprylyl peroxide, cumene hydroperoxide, isopropyl peroxydicarbonate and azo compounds such as azobisisobutyronitrile. The precise combination of temperature and pressure utilized will, of course, be dependent upon the particular diluent, monomers and catalyst which are being utilized. Subsequent to the completion of the polymerization, the resulting copolymer, if insoluble, may be conveniently separated from its solvent medium by a simple filtration process or, if soluble, it may be recovered by being precipitated with a liquid in which it is insoluble such, for example, as ethyl ether.
It is essential that the copolymers used for the preparation of the detergent builders of this invention should have a molecular weight prior to crosslinking, as expressed in terms of their relative viscosity as determined, at 25 C., with a 1 percent solution of the copolymer in N-methyl-pyrrolidone, of at least about 1.05. Thus, the use of copolymers having a substantially lower molecular weight is undesirable inasmuch as large quantities of crosslinking agent will be required in order to convert them into their required water-insoluble albeit water-swellable, gel forming form. Those skilled in the polymer art will have little or no difficulty in adjusting the process variables of the polymerization reaction in order to be able to prepare the resulting copolymers so that their molecular weights are greater than the above stated minimum limit.
Since the polymeric detergent builders of this invention are most conveniently utilized in the form of their salts, such salts including their alkali metal and ammonium salts, may be readily prepared either prior or subsequent to the crosslinking of these copolymers. Thus, it is merely necessary to react the solid copolymer at ambient temperatures with about a percent, by weight, aqueous solution of sodium, potassium, lithium or ammonium hydroxide for a sufficient period until a swollen structure is obtained. The latter product is then added to an alcohol in order to precipitate out the desired copolymer salt.
As has previously been noted, the polymeric detergent builders of this invention must be in a water-insoluble, gel-forming crosslinked form. Thus, crosslinking of these copolymers is usually carried out as a distinct and separate step which is conducted subsequent to their polymerization.
More particularly, the post-polymerization, crosslinking of these copolymers, or their salts, involves their reaction with an effective concentration of one or more reagents capable of transforming their essentially linear configuration into a three-dimensional, water-insoluble network. Preferred for this purpose are the compounds having the structure:
wherein R represents an aliphatic or aromatic hydrocarbon group having from about two to 30 carbon atoms and which may contain one or more hetero atoms such, for example, as an oxygen, sulfur or nitrogen atom; X represents a primary or secondary OH group; and isocyanate, i.e. -N C 0, group; an epoxy group; an ethyleneimine group; a primary or secondary Sl-l, NHR group wherein R represents hydrogen, an alkyl or a substituted alkyl group having from one to 12 carbon atoms which may be linear or branched and wherein suitable substituent groups for said alkyl groups may comprise halo, nitro, alkoxy, cyano, acyl and the like and n represents an integer having a value of from about 2 to 100.
Exemplary of the applicable crosslinking agents conforming to the above formula are: glycols such as ethylene glycol, the propane glycols, the butane glycols, the pentane glycols, the hexane glycols, the cyclohexane glycols, the heptane glycols, the octane glycols, the nonane glycols, the decane glycols, the undecane glycols, the dodecane glycols and the xylene glycols; the triols such as glycerol, trimethylolpropane,
the butane triols, the pentane triols, the hexane triols, the cyclohexane triols, the heptane triols, the octane triols, the nonane triols, the decane triols, the undecane triols, the dodecane triols, the tetrols such as the butane tetrols, the pentane tetrols including pentaerythritol, the hexane tetrols, the cyclohexane tetrols, the heptane tetrols, the octane tetrols, the nonane tetrols, the decane tetrols and, the undecane tetrols; the pentitols such as arabitol, adonitol, xylitol and rhamitol; the hexitols such as glucose, mannitol, sorbitol and dulcitol; and the heptitols such as pereseitol and volemitol.
Also applicable are the higher polyhydric alcohols of the saccharide types such as raffinose, sucrose, galactose, mannose, gulose, idose, tolose, allose, fructose, sorbose and the acetylenic and olefinic unsaturated glycols such as 2-butyne-l, 4-diol, 3,6-dihydroxycyclohexene and dipropenylglycol; polyhydric amines such as ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine and hexamethylene diamine; the cyclohexane diamines, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, ophenylene diamine, m-phenylene diamine, p-phenylene diamine, diethylene triamine, triethylene tetraamine, ethanol-amine, tetraethylene pentamine, pentaethylene hexamine, polyethyleneimine, the N,N'dialkyl or diaryl ethylene diamines where the alkyl or the aryl groups have a combined value of from two to 12 carbon atoms and nitrilo bis-propylamine polyhydric thioglycols such as ethylene dithioglycol, propylene dithioglycol, trimethylene dithioglycol, tetramethylene dithioglycol, pentamethylene dithioglycol and the like; polyhydric amino alcohols such as diethanolamine, 2,3- dihydroxy propylamine, N-alkyl or N-aryl ethanolamines wherein the alkyl group has from one to 12 carbon atoms; thio amines such as beta-mercapto ethyl amine, beta-mercapto-N-alkyl or N-aryl ethyl amines wherein diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, methylene, bis- (p-phenyl isocyanate) and the like; and, unsaturated organic alcohols such as allyl alcohol and l-dodecene- 10-0] and the like. In addition, certain hydroxyl containing polymeric materials, such as polyvinyl alcohol, may also be used as crosslinking agents.
From the above listed group of crosslinking agents, it is preferred to employ (l) alkylene polyamines such, for example as diethylene triamine, triethylene triamine, triethylene tetramine and tetraethylene pentamine; or (2) alpha, omega-polymethylene diamines such, for example, as ethylene diamine, hexamethylene diamine, octamethylene diamine and o-phenylene diamine. The actual crosslinking reaction may be conducted by admixing a solution of the copolymer, which may be in its anhydride, acid.or salt form or as a copolymer salt mixture thereof, with a solution containing an effective concentration of the selected crosslinking agent and thereupon heating the resulting mixture, with agitation, at a temperature of from about 25 to C. and for a period of from about 5 minutes to 24 hours. The precise details of time, temperature and concentration of crosslinking agent will, of course, be dependent upon such factors as the particular copolymer and crosslinking agent which are being reacted. However, in most instances the weight ratio of the copolymer to the crosslinking agent will range from about :1 to about 500:1.
Regardless of the manner in which the crosslinking of the polymer is achieved, it is essential that the crosslinking reaction should proceed to a degree which is sufficient to result in the preparation of an essentially water-insoluble rather than a water soluble material. Accordingly, the crosslinkingreaction should yield a product characterized by its ability to form a threedimensional, water-soluble, gel-network when introduced into an aqueous medium wherein it will appear as'a translucent or transparent suspension which may or may not .be in the colloidal form. This threedimensional gel networkis highly swellable under the alkaline conditions encountered when it is used as part of a detergentcomposition but it does not, however, go into solution since its gel-network remains insoluble.
Thus, it is to be stressed at this point, that the novel detergent builders of this invention must be both crosslinked and "yield water-insoluble gel structures in an aqueous medium. As will be seen, it is this uniquecombination of properties which serves to distinguish these novel builders from the polymeric detergent builders of the priorart which, ashas been noted, were in all cases dispersed particles are coalesced as, for example, by.
centrifugation, or if there is a sufficient concentration present to pervade the entire available liquid. As is true of other gels, the detergent builders of this invention may be rheologically characterized by the absence of steady flow upon being subjected to slight stresses. Such behavior in binary systems, even where a very high content of a liquid solvent is present, is accounted for by the presence in a gel of a three-dimensional network formed by the solute which thus serves to hold the liquid solvent entrapped therein.
While detergent builders comprising essentially water-soluble, linear polymers or essentially water soluble polymers containing branches formed by means of partial crosslinking, or other means, may provide results equivalent to inorganic phosphates such as sodium tripolyphosphate, the novel crosslinked, water-insoluble detergent builders of this invention will, on the other hand, generally provide results which are significantly better than those attainable with the inorganic phosphates. These superior results have been found to be directly attributable to the water-insoluble, three dimensional gel structure which they provide upon introduction into an aqueous medium.
lnsome cases, the gel structure of the detergent builtiers of this invention, when dispersed in an aqueous medium, will pervade 100 percent of the liquid volume whereas in other casesit will pervade only part of it. This factor, known as the gel volume percent, provides a convenient means for further characterizing these novel detergent builders. Thus, the gel volume percent of these builders may vary as a result of the influence of such factors as the individual swelling characteristics of the particular crosslinked copolymer or the absolute amount of gel that is present. Moreover, there is a definite and highly significant correlation between the gel volume percent of these builders and their efficiency as detergent builders. This relates to thefact that the efficiency of these polymeric detergent builders is proportional to the amount of gel which they yield in an aqueous medium, i.e., the gel volume percent of these polymeric builders is related to their detergency or cleaning power.
In determining gel volume percent, the following procedure is used: Test No. l
A 1 percent, by weight, aqueous suspension of the detergent builder is prepared by mixing 1 gram of the solid detergent builder and 99 grams of distilled water which has been pre-heated to about 60 C. in some cases, as when the crosslinked polymeric detergent builder is in its anhydride form, the anhydride linkages must be hydrolyzed prior to determining the gel volume percent and this may be accomplished by warming the anhydride copolymer, with agitation, in an alkaline, aqueous medium having a pH of about ll until full swelling is attained. In general, the process takes from 2 to 24 hours and during this period care must be exercised in order to prevent loss of water through evapo ration.
The pH of the resulting suspension is then adjusted to a level of about 1110.5 with a 20 percent, by weight, solution of sodium hydroxide whereupon it is cooled to room temperature, homogenized by agitation and poured into a 50 milliliter graduated centrifuge tube. The fluid is centrifuged at 2,500 rpm in a centrifuge in which the horizontal distance between the end of the centrifuge tube and its rotating center axis is no more than 19 centimeters. After 30 minutes, the line of demarcation separating the gel and the soluble phases is read and the gel-volume percent is calculated according to the following formula:
Gel volume percent Volume of gel Total volume of aqueous mixture X 100 A gel volume of at least 5 volume-percent indicates that a crosslinked, water-insoluble, but water-swellable copolymer gel is present. However, the best crosslinked copolymers for use as detergent builders in the compositions of this invention are those which have a gel volume greater than 50 volume-percent with optimum gel volume of percent, all of these gel volumes being determined at a pH of about 1 1.
In those cases where there is no visible line of demarcation separating the gel and soluble phases, whether this is due to the presence of 100 percent gel volume or to the complete absence of any gel, a second test must be performed on the same aqueous system in order to determine the gel volume percent of the polymeric builder dispersed therein.
Test No. 2
Under agitation, the same gel suspension, while still in the graduated centrifuge tube as used in Test No. l, is acidified by the dropwise addition of an approximately 37 percent, by weight, aqueous solution of HCI. Acidification and agitation are continued until the first sign of permanent turbidity is observed thereby signalling incipient coagulation. Additional HCl solution is then added dropwise with agitation being applied after adding each drop so as to reach coagulation of the gel. The recognition of the onset of coagulation may be facilitated by the observation of the movement of the air bubbles formed during the mixing of the gel suspension which is accomplished by shaking. Small bubbles do not rise in the gelled medium, they rise only after the onset of the coagulation. The commencement of the rising of the bubbles is, therefore, the endpoint of the test, at which time centrifugation may now be begun. It is to be noted, that the addition of l-lCl should not exceed the endpoint because the gel volume percent decreases as the pl-l is lowered. The centrifugation is then repeated at 2,500 rpm for 30 minutes as described above in Test No. l. The gel volume within the tube and the pH of the supernatant are then recorded and the gel volume percent of the total solution is calculated by means of the formula set forth, in Test 1.
In the event that the addition, in Test No. 2, of the HCl solution to the gel suspension does not produce any permanent turbidity, it may be concluded that the sample is not a crosslinked material or, if crosslinked, that it is water soluble and is, therefore, not advantageous for use as a detergent builder in the compositions of the present invention. Moreover, as has been noted, only those crosslinked water insoluble polymeric builders capable of exhibiting a gel volume of at least about and, preferably, at least about 50 percent, as determined by Test No. l or Test No. 2, are preferred for use in the detergent compositions of this invention. Optimum results are, however, obtained by the use of detergent builders having a gel volume of I00 percent, as determined by Test No. 1.
In using the above described builders to prepare detergent compositions, it is merely necessary to intimately admix one or more of these builders with one or more surfactants, i.e., surface active agents. The selected surfactant may be an anionic, nonionic, zwitterionic or an ampholytic, i.e., amphoteric, surfactant or one may employ a mixture of any two or more surfactants which may be of the same or of two or more different types, e.g., a blend of an anionic and nonionic surfactant.
Anionic surface active compounds can be broadly described as compounds which contain hydrophilic and lipophilic groups with the hydrophilic group containing at least one negatively charged moiety. These compounds include sulfated or sulfonated alkyl, aryl and alkyl aryl hydrocarbons and alkali metal and ammonium salts thereof, for example, sodium salts of long chain alkyl sulfates, sodium salts of alkyl naphthalene sulfonic acids, sodium salts of sulfonated abietenes, sodium salts of alkyl benzene sulfonic acids particularly those in which the alkyl group contains from eight to 24 carbon atoms; sodium salts of sulfonated mineral oils and sodium salts of sulfosuccinic acid esters such as sodium dioctyl sulfosuccinate.
Advantageous anionic surfactants include the higher alkyl aryl sulfonic acids and their alkali metal, ammonium and alkaline earth metal salts such as for example sodium dodecyl benzene sulfonate, sodium tridecyl sulfonate, magnesium dodecyl benzene sulfonate, potassium tetradecyl benzene sulfonate, ammonium dodecyl toluene sulfonate, lithium pentadecyl benzene sulfonate, sodium dioctyl benzene sulfonate, disodium dodecyl benzene disulfonate, disodium di-isopropyl naphthalene disulfonate and the like as well as the alkali metal salts of alkyl aryl (sulfothioic acid) ethers and the alkyl thiosulfuric acid, etc. Preferred anionic organic surface active agents are, as noted hereinbefore, sodium salts of alkyl benzene sulfonic acids and particularly preferred sodium salts of alkyl benzene sulfonic acids are those in which the alkyl group or radical contains 10 to 18 carbon atoms in a straight (i.e., unbranched) chain.
Nonionic surface active compounds can be broadly described as compounds which do not ionize but usually acquire hydrophilic characteristics from an oxygenated side chain, such as polyoxyethylene, while the lipophilic part of the molecule may come from fatty acids, phenols, alcohols, amides or amines. Examples of nonionic surfactants include products formed by condensing one or more alkylene oxides of two to four carbon atoms, such as ethylene oxide or propylene oxide, preferably ethylene oxide alone or with other alkylene oxides, with a relatively hydrophobic or lipophilic compound such as a fatty alcohol, fatty acid, sterol, a fatty glyceride, a fatty amine, an aryl amine, a fatty mercaptan, tall oil, etc. Nonionic surface active agents also include those products produced by condensing one or more relatively lower alkyl alcohol amines (such as methanolamine, ethanolamine, propanolamine, etc.) with a fatty acid such as lauric acid, cetyl acid, tall oil fatty acid, abietic acid, etc.
Still other nonionic surface active compounds include the amine oxides and phosphine oxides and preferably the unsymmetrical trialkyl amine oxides and phosphine oxides wherein two of the alkyl groups are lower alkyl groups (one to four carbon atoms) and the other alkyl group is a higher alkyl group (eight to l8 carbon atoms). Examples include dimethyldodecylamine oxide, dimethyl dodecylphosphine oxide, dimethyl tetradecyl amine oxide, dimethyltetradecyl phosphine oxide, diethylhexadecylamine oxide, diethylhexadecylphosphine oxide and the like.
Particularly advantageous nonionic surface active agents are condensation products of a hydrophobic compound having at least one active hydrogen atom and a lower alkylene oxide (for example the condensation product of an aliphatic alcohol containing from about eight to about 18 carbon atoms) and from about 3 to about 30 mols of ethylene oxide per mol of the alcohol, or the condensation product of an alkyl phenol containing from about eight to about 18 carbon atoms in the alkyl group and from about 3 to about 30 mols of ethylene oxide per mol of alkyl phenol. Other advantageous nonionic detergents include condensation products of ethylene oxide with a hydrophobic compound formed by condensing propylene oxide with propylene glycol.
Amphoteric or ampholytic surface active compounds can be broadly described as compounds which have both anionic and cationic groups in the same molecule. Such compounds may be grouped into classes corresponding to the nature of the anionicforming group, which is usually carboxy, sulfoor sulfato. Examples of such compounds include sodium N-coco beta amino propionate, sodium N-tallow beta amino dipropionate, sodium iminodipropionate and the like.
Zwitterionic surfactants can be broadly described as derivatives of aliphatic quarternary ammonium compounds in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about eight to 18 carbon atoms and one contains an anionic water solubilizing group. Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexaclecylammonio) propane-l-sulfonate and 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropanel -sulfonate which are especially preferred for their excellent cool water detergency characteristics.
Additional representatives of compounds exemplary of each of the above described types of surfactants are given on pages 33-269 of McCutcheons Detergents and Emulsifiers, 1969 Annual published in 1969 by John W. McCutcheon, Inc. Morristown, New Jersey which is here incorporated by reference.
With respect to proportions, the concentration of the builders of this invention which is required to be blended with one or more surfactants in order to prepare an operable detergent composition will vary depending upon such factors as the end use, type of surfactants utilized, pH conditions and the like. Thus, these novel builders can be employed in detergent compositions in any desired proportions which are effective, i.e., any concentration which enhances the detergency characteristics of the selected surfactants. In general, however, the ratio of builder to surfactant will vary from about 1:10 to about 10:1 with optimum results being obtained 'with a ratio of builder to surfactants of from about 1:2 to about 5:1; the latter proportions being designed for the use of the resulting detergent compositions at a pH of from about 9 to 12 and preferably at from about 9.5 to 1 1.5.
The detergent compositions of this invention may be prepared in any of the commercially desirable forms including in the bar, granular, flake, liquid and tablet forms.
If desired, the novel polymeric detergent builders of this invention may be advantageously combined with other detergent builders which will function as supplementary builders. Such supplementary builders include the conventional alkali metal polyphosphates, i.e., the tripolyphosphates and pyrophosphates such as sodium tripolyphosphate, tetrasodium pyrophosphate, tetrapotassium phosphate, disodium pyrophosphate and the like; the amino polycarboxylic acids and salts such as the sodium, potassium and ammonium salts of nitrilotriacetic acid, the sodium, potassium ammonium salts of amino tri(methylenephosphonic acid), as well as the free acid; and, the diphosphonic acids and salts such as methylene diphosphonic acid and l-hydroxy, ethylidene diphosphonic acid. In addition, the detergent compositions of this invention may also contain various optional adjuncts such as foam boosters, dedusting agents, soil anti-redeposition agents, anticorrosion agents, anti-tarnishing agents, perfumes, germicidal agents and optical brighteners.
In actual use, it is suggested that the detergent compositions of this invention be dispersed in water so that the resulting aqueous dispersion will contain an effective concentration of the novel crosslinked, water in N-lauryl beta soluble, gel-forming copolymer builder in the range of from about 0.01 to 1.0 percent, by weight. For best results, the water should be at a temperature in the range of from about 20 to C.
The following examples will further illustrate the embodiments of this invention. In these examples all parts given are by weight unless otherwise noted.
EXAMPLE I This example provides a comparison between a number of the crosslinked, water-insoluble, gel-forming detergent builders of this invention and: (l) a polyphosphate detergent builder, i.e., sodium tripolyphosphate (STPP) and (2) several uncrosslinked, i.e., linear, water soluble C -C olefinzmaleic anhydride copolymers.
The various builders are compared with respect to the gel volume percent, as determined by means of the above described procedure, as well as with respect to their actual cleaning efficiency as expressed in terms of the results obtained in the change in whiteness, i.e., the (A W), test. This washing test is conducted by comparing the whiteness of a standard 5 X 5 inches soiled cloth, sold by the American Conditioning House as ACH-1l5A, both before and after being washed with the particular detergent composition which is being evaluated. In order to provide uniform conditions the cloths are washed with a standard detergent formulation, as described below, in a standard washer, such as the Tergetometer sold by the United States Testing Co., Inc., at an initial pH of about 10-11, a rate of agitation of 145 rpm and a temperature of C. for a period of 15 minutes. A 5 minute rinse cycle, at ambient temperature, is provided for the cloths whereupon they are squeezed water free, air dried and ironed. The reflectance or whiteness of the cloth samples is measured, both before and after the washing procedure, on a color difference meter such as a D-25 Hunter color Difference Meter, sold by Hunter Associates Laboratory, Inc. Thus, the efficacy of the detergent builder is correlated to the absolute value of the change in whiteness or (A W) which is calculated as follows:
Parts Orvus AB"(anionic surfactant) 45 .0 Na SO (ionic strength control and filler) 8.5 Na Si0 (corrosion inhibitor) 5.0 Na P ll (threshold agent) 0.8 Carboxymethyl cellulose (soil anti-redeposition agent) 0.7 Detergent builder 40.0
"A mixture'containing 43%, by weight, Na so 15%, by weight, NaCl; 1%, by weight, water; and, 40%, by weight, of sodium dodecylbenzenesulfonate.
In this washing test, the concentration of the above described detergent composition is at 2.5 g. per liter of water containing 175 ppm of hardness as CaCo The detergent builders which are evaluated in this manner are described in Table l, hereinbelow.
TABLE I Builder No. Composition Control No detergent builder present 1 STPP 2 A water-soluble, uncrosslinked, i.e. linear,
sodium salt ofa 1:1, by mole, diisobutylenezmaleic anhydride copolymer.
3 A water-soluble, uncrosslinked 1:1, by mole, l-octenezmaleic acid copolymer.
4 A water-soluble, uncrosslinked sodium salt of a 1:1, by mole, l-butene:maleic anhydride copolymer.
5 A water-soluble, uncrosslinked sodium salt of a 1:1, by mole, l-hexenezmaleic anhydride copolymer.
6 A water-soluble, uncrosslinked sodium salt of a 1:1, by mole, isobutylene:maleic anhydride copolymer.
7 A water-insoluble, sodium salt of a l :1 by
mole, isobutylenezmaleic anhydride copolymer crosslinked with 30%, by weight, of Deta, i.e. diethylenetriamine.
8 A water-insoluble, sodium salt of a 1:1, by
mole, l-hexenezmaleic anhydride copolymer crosslinked with 5%, by weight, of tetraethylene pentamine.
9 A water-insoluble, sodium salt ofa 1:1, by
mole, l-butenezmaleic anhydride copolymer crosslinked with 5%, by weight, of DETA.
A water-insoluble, sodium salt ofa z 1:1, by
mole, isobutylene:maleic anhydride copolymer crosslinked with 0.5%, by weight, of DETA.
A water-insoluble =l:1, by mole, 1-
octene:maleic anhydride copolymer crosslinked with 0.5%, by weight, of tetraethylene pentamine.
Table 11, hereinbelow, provides the results of the change in whiteness test A W) for the standard detergent compositions containing each of the above described builders as well as for a control composition which does not contain any builders. The table also provides the gel volume percent value for each of the various builders.
With respect to the A W) values, the above given data shows that the value for this factor which is obtained for the builder-free control was 37.4. Accordingly, any detergent composition whose A W) value is greater than 37.4 would be considered efficacious. In this respect, the data reveal that the use of linear copolymers, i.e., Nos. 2-6 provides detergency results which, at best, are approximately equal to those attained with STPP whereas all of the crosslinked copolymers with a gel volume greater than 5, i.e., Nos. 8-11 displayed excellent results as detergent builders. On the other hand, Builder No. 7 while crosslinked, had a gel volume percent of only 1.5 and was, therefore, no better than either STPP or the linear copolymers represented by Builders Nos. 2-6.
The data also reveal the existence of an inverse relationship between the A W) value of a particular detergent composition and the extent to which its polymeric detergent builder has been crosslinked. Thus, where a builder such as No. 11 has been crosslinked with only 0.5 percent of DETA, it has the rather high A W) value of 57.5. On the other hand, when the identical copolymer is crosslinked with 30 percent of DETA, i.e., Builder No. 8, its A W) value is reduced to only 48.2. From the latter results, it is apparent that neither inadequate nor excessive crosslinking will yield products which provide A W) values superior to those attainable with STPP. Thus, superior washing action on the part of these crosslinked copolymers can only be obtained with an optimum degree of crosslinking as is found, for example, in builder No. 10 which has been crosslinked only to the extend necessary to provide it with an insoluble but highly swellable gel structure upon being introduced into an aqueous, alkaline medi- EXAMPLE 11 This example provides another demonstration of the advantage inherent in using, as detergent builders, only those C -C olefinzpolycarboxyl vinyl comonomer copolymers which have been crosslinked so that they have a gel volume of at least about 5 percent.
The following table sets forth the evaluation data obtained upon utilizing a number of different copolymers as the detergent builder in the standard detergent composition described in Example I.
Extra" Builder A W) Quality Sodium salt ofa 1:1, by mole,
diisobutylenezmaleic anhydride copolymer cross-linked with 5%, by wt., of DETA and having a gel volume of 52.7 +5.0 Sodium salt ofa linear =l:1, by mole,
diisobutylenezmaleic anhydride copolymer and having a gel volume of O.% 46.8 0.8 Sodium salt ofa =1:l, by mole, l-
hexenezmaleic anhydride copolymer crosslinked with 5%, by wt., of BETA and having a gel volume of 100% 53.0 +5.9
"Extra Builder Quality an evaluation factor relating to the effect of STPP in the same detergent composition. Its value is obtained by substracting the A W) value for the STPP control, i.e. 47, from the A W) value ofthe copolymer detergent builder.
pH of the aqueous system adjusted to 10.0 from an initial value of 8.3.
EXAMPLE 111 This example illustrates the preparation of a z 1:1 by mole, 1-butene:maleic anhydride copolymer suitable for use in preparing the novel detergent builders of this invention.
A mixture of 200 grams of maleic anhydride and 700 milliliters of acetone is charged into a three-liter Parr bomb equipped with a gas inlet valve, a valve for the introduction of initiator solution and a thermocouple well. After degassing in a dry-ice acetone bath, a total of 498 grams of l-butene is introduced into the Parr bomb. The Parr bomb is then heated to a temperature of about 84-85 C. and 166 milliliters of a 4 percent, by weight, solution of benzoyl peroxide in acetone is then introduced by means of a metering pump over a period of S 1% hours. The reaction mixture is heated at this temperature for an additional 4 9% hours and, after cooling to room temperature, the Parr bomb is vented and the reaction mixture precipitated, with agitation, into 8-liters of diethyl ether.'After drying, the above described copolymer is found to have a relative viscosity in excess of 1.05 as determined with a 1 percent, by weight, solution in N-methylpyrrolidone at 25 C.
EXAMPLE IV This example illustrates the conversion of the l-butene: maleic anhydride copolymer whose preparation was described I in Example III, hereinabove, into the form of its sodium salt.
A total of 5. grams of the copolymer of Example III is treated with an excess of a 10 percent, by weight, aqueous sodium hydroxide solution. After complete dissolution is achieved, the polymer solution is precipitated in methanol. The resultant sodium salt of the copolymer is then filtered and is finally obtained in a quantitative yield. It is to be noted that the sodium hydroxide solution converts the maleic anhydride moieties of the copolymer to the acid form and thereupon neutralizes these acid moieties to the sodium salt form.
EXAMPLE V This example illustrates the crosslinking and subsequent neutralization of the l-butenezmaleic anhydride copolymer whojse preparation is described in Example IIl hereinabove.
To a solutionof grams of the copolymer of Example III in 50 g of N-methylpyrrolidone, there is added to l0 milliliters of a solution containing 1 gram of diethylenetriamine (DETA) diluted to 100 milliliters with N-methylpyrrolidone. This mixture is heated and stirred for one hour at a temperature of about 80-90 C. yielding a viscous, opaque mixture. A drop of this mixturegives rise to swollen gel particles when introduced into a percent, by weight, aqueous sodium hydroxide solution thus indicating insolubility on the part of the crosslinked copolymer. With vigorous agitation, an excess of the sodium hydroxide solution is then added to the balance of the crosslinked copolymer in order to convert it into the salt form. The entire mixture is then poured into methanol yielding a white precipitate which is separated by filtration and is then dried. The yield of the sodium salt of this water-insoluble, crosslinked l-butenezmaleic anhydride copolymer is quantitative.
This product is found to have a gel volume about percent and provides excellent results as a detergent builder on being formulated into the standard detergent composition described in Example 1.
EXAMPLE VI This example illustrates the preparation of a l l, by
In preparing this polymer, the procedure of Example III is repeated with the exception, in this instance, that an equal amount, on a molar basis, of isobutylene is substituted for the l-butene. The resulting copolymer has a relative viscosity in excess of 1.05 as determined under the above described conditions.
EXAMPLE VII This example illustrates the conversion of the z 1 l, by mole, isobutylenezmaleic anhydride copolymer of Example VI into the form of its sodium salt.
The procedure of Example IV was repeated with the exception, in this instance, that the copolymer of Example VI was substituted for the l-butene:maleic anhydride copolymer of Example III. A quantitative yield of the copolymer salt was obtained in this manner.
EXAMPLE VIII This example illustrates the crosslinking of the isobutylenezmaleic anhydride copolymer of Example VI.
A sample of 12 grams of the copolymer of Example Vl is dissolved in 150 milliliters of N-methylpyrrolidone. To this solution there is added, with stirring, 6 milliliters of a solution containing 1 gram of DETA diluted to milliliters with N-methylpyrrolidone. The reaction mixture was precipitated into water providing a quantitative yield of the crosslinked copolymer which is found to have a gel volume of 100 percent, as determined by Test No. l, and a gel volume of 44 percent, as determined by Test No. 2. It provides excellent results as a detergent builder on being formulated into the standard detergent composition described in Example I.
EXAMPLE IX This example illustrates the preparation of a l-butenez3-butene-l,2,3-tricarboxylic acid copolymer suitable for use in preparing the novel detergent builders of this invention.
In preparing this copolymer, the procedure of Example III is repeated with the exception, in this instance, that an equal amount, on a molar basis, of 3-butene- 1,2,3-tricarboxylic acid is substituted for the maleic anhydride and dimethyl sulfoxide is substituted for acetone. The resulting copolymer has a relative viscosity in excess of 1.05 as determined under the above described conditions.
EXAMPLE x This example illustrates the crosslinking of the l-butenez3-butene-1,2,3-tricarboxylic acid copolymer whose preparation is described in Example IX hereinabove.
Thus, a quantitative yield of the crosslinked copolymer of Example IX, is obtained by subjecting this copolymer to the reaction procedure described in Example VIII with the exception, in this instance, that EPON 128, a di-epoxy compound sold by the Shell Chemical Company, rather than DETA is used as the crosslinking agent. This water insoluble product is found to have a gel volume in excess of 5 percent, as determined by Test No. l, and provides excellent results as a detergent builder on being formulated into the standard detergent composition described in Example I.
EXAMPLE Xl This example illustrates the preparation of another copolymer suitable for use in preparing the novel detergent builders of this invention.
Thus, a lzl, by mole, l-hexene:maleic anhydride copolymer is prepared utilizing the polymerization procedures of Example III with the exception, in this instance, that an equivalent amount, on a molar basis, of l-hexene is substituted for the l-butene. The resulting copolymer has a relative viscosity in excess of l.05 as determined under the above described conditions.
EXAMPLE Xll This example illustrates the crosslinking of the l-hexenezmaleic anhydride copolymer of Example XI. Thus, a sample of 100 grams of the copolymer of Example VIII is dissolved in 160 milliliters of acetone and the resulting solution is warmed to 4050 C. To this warmed solution is added 5 grams of tetraethylenepentamine in 100 milliliters of acetone. The reaction mixture gels within one minute and the acetone is then removed by evaporation. The residue is recovered and provides a quantitative yield of the crosslinked copolymer. This water-insoluble product is found to have a gel volume of greater than 5 percent and provides excellent results as a builder on being formulated into the standard detergent composition described in Example I.
EXAMPLE Xlll This example illustrates the preparation of another of the copolymers suitable for use in preparing the novel detergent builders of this invention which, in this case, is a -"lzl, by mole, diisobutylene:fumaric acid copolymer.
A mixture of 40 grams of fumaric acid, grams of diisobutylene, and 200 milliliters of N-methyl pyrrolidone is heated to 60 C.. About 0.5 grams of benzoyl peroxide is then added and the mixture is vigorously stirred and maintained at 7585 C. for a total reaction time of 8 hours. After cooling, the viscous reaction product is precipitated into diethyl ether. The polymer thus obtained has a relative viscosity in excess of 1.05 as determined by means of the above described procedure.
EXAMPLE XIV This example illustrates the crosslinking of the diisobutylene:fumaric acid copolymer of Example Xlll.
A solution of the copolymer of Example Xlll in N- methyl pyrrolidone is heated at 60-70 C. for 24 hours in the presence of 5 percent, by weight, of EPON 128 and the resulting reaction product is precipitated into diethyl ether. This water-insoluble product is found to have a gel volume in excess of 5 percent and provides excellent results as a detergent builder on being formulated into the standard detergent composition described in Example I.
EXAMPLE XV This example illustrates the preparation of a ldecene:itaconic anhydride copolymer suitable for use in preparing the detergent builders of this invention.
A mixture of 22 grams of itaconic anhydride, 25 grams of l-decene and 0.60 grams of benzoyl peroxide is dissolved in 100 milliliters of p-xylene. The reaction mixture is heated at 85 C. for 2 hours, and an additional 0.4 grams of benzoyl peroxide is added. The heating is continued for an additional 18 hours. After cooling, the reaction mixture is precipitated into excess ether yielding the above described copolymer which is recovered by filtration and drying. The relative viscosity of the polymer is in excess of 1.05 as determined under the above described conditions.
EXAMPLE XVI This example illustrates the crosslinking of the ldecenezitaconic anhydride copolymer of Example XV.
Thus, a quantitative yield of the crosslinked copolymer of Example XV is obtained by subjecting this copolymer to the procedure of Example Xll with the exception, in this instance, that ethylenediamine is used as the crosslinking agent. This water-insoluble product is found to have a gel volume in excess of 5 percent as determined by Test No. l and provides excellent results as a detergent builder in the standard detergent builder described in Example I.
EXAMPLE XVlIl This example illustrates the preparation of a l-octenezmethylene malonic anhydride copolymer suitable for use in preparing the novel detergent builders of a mixture of this invention.
A mixture of 11 grams of methylene malonic anhydride, 12.2 grams of l-octene, and 0.28 grams of benzoyl peroxide is dissolved in 50 milliliters of pxylene. The reaction mixture is heated at 8085 C. for about 2 hours, and an additional 0.2 grams of benzoyl peroxide is added whereupon the heating is continued for an additional 18 hours. After cooling, the reaction mixture is precipitated into excess ether yielding the above described copolymer after filtration and drying. This copolymer has a relative viscosity in excess of 1.05 as determined by means of the above described procedure.
EXAMPLE XVlll This example illustrates the crosslinking of the l-octene:methylene malonic anhydride copolymer of Example XVll.
A 20 gram sample of the copolymer of Example XVll is dissolved in 50 milliliters of acetone and the resulting solution is warmed to about 45-5 5 C. To this warm solution is added 16 milliliters of acetone containing 1 gram of DETA. After gelation occurs, the acetone solvent is partially removed by blowing a stream of nitrogen over the mixture and the remaining solvent is removed under vacuum. The crosslinked copolymer is obtained in a quantitative yield. This water-soluble product is found to have a gel volume in excess of 5 percent, as determined by Test No. l, and provides excellent results as a detergent builder on being formulated into the standard detergent composition described in Example I.
Variations may be made in proportions, procedures and materials without departing from the scope of this invention as defined in the following claims.
What is claimed is:
1. A detergent composition consisting essentially of a mixture of:
a. From 1 to about 2 parts by weight of at least one surfactant selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic surfactant and mixtures thereof; and as a builder for said detergent composition;
. From about 5 to about 1 part by weight of an alkali metal or ammonium salt of a crosslinked, watersoluble copolymer of from about 20 to about 80 mole percent of at least one olefin having four to carbon atoms, or mixtures thereof, and from about 80 to about mole percent of at least one polycarboxyl vinyl monomer selected from the group consisting of maleic, fumaric, itaconic, aconitic, methylene malonic, mesaconic, 3-butene-l,2,3-tricarboxylic and citraconic acids, anhydrides, their alkali metal or ammonium salts or mixtures thereof; said crosslinked copolymer being water swellable and capable of forming a gel I when introduced into an aqueous medium and having a relative viscosity, prior to crosslinking, of t at least l.05 as a 1 percent solution in N-methylpyrrolidone at C, and wherein said copolymer is crosslinked with a crosslinking agent having the structure:
wherein R is an aliphatic or aromatic hydrocarbon having from about two to carbon atoms; X is selected from the group consisting of a primary and secondary hydroxyl, primary and secondary SH and NHR' groups, N C 0 groups, epoxy groups and ethyleneimine groups, and wherein R is selected from the group consisting of hydrogen, alkyl groups having from about one to 12 carbon atoms, and, wherein n is an integer having a value of from about 2 to 100, said crosslinking agent being employed in a weight ratio to said copolymer of from about 1:20 to about 1:500.
2. The detergent composition of claim 1, wherein said copolymer is crosslinked witha crosslinking agent selected from the group consisting of alkylene polyamines and alpha, omega-polymethylene diamines.
3. The detergent composition of Claim 2, wherein said copolymer is crosslinked with diethylenetriamine.
4. The detergent composition of claim 1, wherein said crosslinked copolymer has a gel volume of at least about 5 percent as a 1 percent by weight concentration in distilled water at a pH of l l-.
5. The detergent composition of claim 1, wherein said polycarboxyl vinyl comonomer is maleic anhydride.
6. The detergent composition of claim 1, wherein said olefin is isobutylene.
7. The detergent composition of claim 1, wherein said olefin is l-butene.
8. An aqueous dispersion of the detergent composition of claim 1.
9. The detergent composition of claim 1, wherein said crosslinked copolymer is selected from the group consisting of the copolymer of isobutylene and maleic anhydride and the copolymer of l-butene and maleic anhydride.
10. A detergent composition consisting essentially of a mixture of:
a. From about 1 to about 2 parts by weight of at least one surfactant selected from the group of anionic, nonionic, zwitterionic and ampholytic surfactants and mixtures thereof; and, as a builder for said detergent composition;
b. From about 5 to about 1 part by weight of a crosslinked, water insoluble copolymer of from about 20 to mole percent of isobutylene and from about 80 to 20 mole percent maleic anhydride; said crosslinked copolymer being water-swellable and capable of forming a gel when introduced into an aqueous medium, and having a relative viscosity, prior to crosslinking, of at least 1.05 as a l percent solution in N-methyl-pyrrolidone at 25 C, and wherein said copolymer is crosslinked with a crosslinking agent having the structure:
wherein R is an aliphatic or aromatic hydrocarbon having from about two to 30 carbon atoms; X is selected from the group consisting of a primary and secondary hydroxyl, primary and secondary SH and NHR' groups, N C 0 groups, epoxy groups and ethyleneimine groups, and wherein R is selected from the group consisting of hydrogen, alkyl groups having from about one to 12 carbon atoms, and, wherein nis an integer having a value of from about 2 to 100, said crosslinking agent being employed in a weight ratio to said copolymer of from about 1:20 to about 1:500.
11. The detergent composition of claim 10, wherein said copolymer is crosslinked with a crosslinking agent selected from the group consisting of alkylene polyamines and alpha, omega-polyethylene diamines.
12. The detergent composition of Claim 11, wherein said copolymer is crosslinked with diethylenetriamine.
13. The detergent composition of claim 10, wherein said crosslinked copolymer has a gel volume of at least about 5% as a 1 percent by weight concentration in distilled water at a pH of l l.
14. The detergent composition of Claim 10, wherein said crosslinked copolymer is in the form of an alkali metal or ammonium salt.
15. An aqueous dispersion of the detergent composition of claim 10.
16. A detergent composition consisting essentially of a mixture of:
a. From about 1 to about 2 parts by weight of at least one surfactant selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic surfactants and mixtures thereof; and, as a builder for said detergent composition;
b. From about 5 to about 1 part by weight of a crosslinked, water-insoluble copolymer consisting of a copolymer of 20 to 80 mole percent isobutylene and 80 to 20 mole percent maleic anhydride which has a relative viscosity; prior to crosslinking, of 1.05 as a 1 percent solution in N-methylpyrrolidone at 25 C., and which has been crosslinked with diethylenetriamine in a weight ratio of copolymer to crosslinking agent of about 20:1 to about 500:1; said copolymer being waterswellable and capable of forming a gel having a gel volume of at least 5 percent when introduced into distilled water in a 1 percent by weight concentration at a pH of about 1 l.
Nii cholas Z Erdy and Arthur J. Yu
It is; certified that error Lppt-ars in the above-identified patent and that Paidv Letters Iatent are hereby corrected as shown below Column 5, line t, the word polymer should read copolymer line 11, the word "water-soluble" should read Water-insoluble Column 9, line 10, the word 3-(N,N-dimethylN--he ;aclecyl ar'nmonio) should read 5- (N,N-dimethyl-N Q hexadecylammonio) Column 10, line 65, the formula wa so'fl should read Na S0 Column 11, line 45, the word "TABLE II iii. should read TABLE II Column 15, line #0, the word "to" should be deleted; line 58,
the word "about" should read above Column 16, line 26, the word "EXAMPLE XVIII" should read EXAMPLE XVII I Column 17, lines 9 8c 10, Claim 1, the word water-soluble" should read water-insoluble Signed and sealed this 13th day of Pefiruary 1973..
EDWARD M.FLETCHER,JR. ROBERT COTTSCHALK Attesting Officer Commissloner of Patents
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2264103 *||Jun 6, 1936||Nov 25, 1941||Procter & Gamble||Process and product for softening hard water|
|US2311008 *||Jun 12, 1939||Feb 16, 1943||Procter & Gamble||Process and composition for softening hard water|
|US3060124 *||Dec 28, 1956||Oct 23, 1962||Monsanto Chemicals||Liquid detergent gel compositions having stability against separation|
|US3060155 *||Dec 29, 1960||Oct 23, 1962||Monsanto Chemicals||Terpolymers of olefins, maleic anhydride and hexadiene-1, 5|
|US3073805 *||Nov 23, 1959||Jan 15, 1963||Monsanto Chemicals||Cross-linked olefin-maleic anhydride interpolymers|
|US3073806 *||Nov 23, 1959||Jan 15, 1963||Monsanto Chemicals||Cross-linked olefin-maleic anhydride interpolymers|
|US3208949 *||Oct 30, 1961||Sep 28, 1965||Lever Brothers Ltd||Liquid detergent composition|
|US3308067 *||Apr 1, 1963||Mar 7, 1967||Procter & Gamble||Polyelectrolyte builders and detergent compositions|
|US3346873 *||Apr 21, 1966||Oct 10, 1967||Procter & Gamble||Liquid detergent composition containing solubilizing electrolytes|
|AU227960A *||Title not available|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3975280 *||Mar 19, 1975||Aug 17, 1976||Henkel & Cie G.M.B.H.||Storage-stable, readily-soluble detergent additives, coating compositions and process|
|US4076643 *||Oct 9, 1974||Feb 28, 1978||Solvay & Cie.||Pre-mixes intended to be added to detergent powders by post-addition|
|US4481126 *||Jul 26, 1982||Nov 6, 1984||The Procter & Gamble Company||No rinse liquid car cleaner with solid polymers|
|US5205960 *||Mar 29, 1991||Apr 27, 1993||S. C. Johnson & Son, Inc.||Method of making clear, stable prespotter laundry detergent|
|US5520841 *||Jan 18, 1995||May 28, 1996||Henkel Kommanditgesellschaft Auf Aktien||Pumpable alkaline cleaning concentrates|
|US20030194492 *||Jun 4, 2003||Oct 16, 2003||Specialty Fertilizer Products, Llc||Anionic polymers composed of dicarboxylic acids and uses thereof|
|U.S. Classification||510/418, 510/337, 510/361, 510/476, 510/360|
|International Classification||C11D3/00, C11D3/37|
|Cooperative Classification||C11D3/3757, C11D3/3703|
|European Classification||C11D3/37C6, C11D3/37B|