US3870648A - Polyelectrolytes as detergent builders - Google Patents

Polyelectrolytes as detergent builders Download PDF

Info

Publication number
US3870648A
US3870648A US106549A US10654971A US3870648A US 3870648 A US3870648 A US 3870648A US 106549 A US106549 A US 106549A US 10654971 A US10654971 A US 10654971A US 3870648 A US3870648 A US 3870648A
Authority
US
United States
Prior art keywords
builder
alkali metal
detergent
composite
builders
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US106549A
Inventor
Richard Anthony Grifo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ISP Investments LLC
Original Assignee
GAF Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GAF Corp filed Critical GAF Corp
Priority to US106549A priority Critical patent/US3870648A/en
Priority to GB29672A priority patent/GB1363351A/en
Priority to DE2200779A priority patent/DE2200779B2/en
Priority to CH37972A priority patent/CH566392A5/xx
Priority to FR7200930A priority patent/FR2122212A5/fr
Priority to BE777980A priority patent/BE777980A/en
Priority to JP47006087A priority patent/JPS529681B1/ja
Priority to NL7200504.A priority patent/NL157650B/en
Priority to CA132,383A priority patent/CA993305A/en
Application granted granted Critical
Publication of US3870648A publication Critical patent/US3870648A/en
Assigned to CHASE MANHATTAN BANK, THE NATIONAL ASSOCIATION reassignment CHASE MANHATTAN BANK, THE NATIONAL ASSOCIATION SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DORSET INC. A CORP OF DELAWARE
Assigned to GAF CHEMICALS CORPORATION reassignment GAF CHEMICALS CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE ON 04/11/1989 Assignors: DORSET INC.
Assigned to DORSET INC., A DE CORP. reassignment DORSET INC., A DE CORP. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE APRIL 10, 1989 Assignors: GAF CORPORATION, A DE CORP.
Assigned to CHASE MANHATTAN BANK (NATIONAL ASSOCIATION), THE reassignment CHASE MANHATTAN BANK (NATIONAL ASSOCIATION), THE SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GAF CHEMICALS CORPORATION, A CORP. OF DE
Assigned to ISP 3 CORP reassignment ISP 3 CORP ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GAF CHEMICALS CORPORATION
Assigned to ISP INVESTMENTS INC. reassignment ISP INVESTMENTS INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE ON 06/06/1991 Assignors: ISP 3 CORP.
Anticipated expiration legal-status Critical
Assigned to GAF BUILDING MATERIALS CORPORATION, SUTTON LABORATORIES, INC., GAF CHEMICALS CORPORATION reassignment GAF BUILDING MATERIALS CORPORATION RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: CHASE MANHATTAN BANK, THE (NATIONAL ASSOCIATION)
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/10Carbonates ; Bicarbonates

Definitions

  • ABSTRACT A non-polluting builder composition for cleansing purposes is described consisting of composite of a polyelectrolyte and the alkali metal salt of a weak acid.
  • Such builder compositions can replace the phosphorous and nitrogen-containing builders previously used in cleansing and laundry detergents with regard to effectiveness in hard water at one-tenth and one-fifth the concentrations of such previously used builders.
  • composite builders prevent the precipitation of insoluble calcium soaps which occurs in household and laundry detergent compositions utilizing either component alone as a builder.
  • the previously noted stabilizing effects of the polyelectrolyte with regard to enzymes and bleaches is not decreased by the added components of these composite builders.
  • This invention relates to detergent compositions useful for household and laundry service and particularly relates to builders for such compositions that are devoid of pollutant or toxic potentials.
  • builders refers to the class of compounds and compositions which improve detergency levels of synthetic detergents and soaps. By utilizing builders, it is possible to prepare detergent compositions having superior detergency as measured by removal of dirt and superior qualities with regard to the redeposition of the dirt that is loosened during the washing process. Additionally, by utilizing builders, it is possible to reduce the final cost of the detergent compositions.
  • the phosphate ion is a nutrient for algae which are a prime cause of eutrification of our lakes and waterways.
  • the phosphate ion from laundry and household use of detergents appears to enhance the growth of algae and the sudden overgrowth of algae interferes with the ecological balance within the lakes and waterways into which such waste waters are discharged.
  • nitrolotriacetic acid A recently commercialized builder material, nitrolotriacetic acid, had been proposed as a replacement for phosphate builders such as the polyphosphates.
  • phosphate builders such as the polyphosphates.
  • recent research has indicated the possibility of birth defects in test animals after exposure to combinations of nitrilotriacetic acid, which is a nitrogencontaining chelating agent, with certain toxic salts. It appears that this builder molecule in some manner permits the transport of toxic cadmium and mercury through tissue membranes. Consequently, this material is less than desirable for utilization in and around the normal household and for discharge into our environmental waters.
  • the above objects are achieved by the utilization in cleansing compositions, comprising detergents and builders, a builder that is a composite of certain polyelcctrolytes and alkaline-reacting salts of alkali metals with weak acids.
  • the polyelectrolyte component of the composite builders of this invention are the copolymer of lower alkyl vinyl ethers with maleic acid or its anhydride.
  • PVM/MA of Polyvinyl methyl ether/Maleic Anhydride and its hydrolyzed product.
  • the anhydride copolymer has the configuration of:
  • Viscosity measurements are commonly used as an in dication of the average molecular weight of the polymeric composition.
  • the K value (Fikentscher) of any particular mixture of polymers is calculated from viscosity data and is useful as an indication of the average molecular weight of such mixtures. Its determination is fully described in MODERN PLASTICS 23 No. 3, 157-161, 212, 214, 216, 218, (1945) and is defined as 1,000 times k in the empirical relative viscosity equation:
  • C is the concentration in grams per hundred cc. of polymer solution and 1 re] is the ratio of the viscosity of the solution to that of pure solvent.
  • K values are reportedas 1,000 times the calculated viscosity coefficient in order to avoid the use of decimals.
  • the preferred interpolymers employed in the present invention have k values of from about 10 to about 200.
  • the two essential ingredients for cleansing compositions comprise the detergent compound itself and the builder.
  • detergent compositions useful in conjunction with the builders of this invention are any of the classes of detergents commonly used for laundry and household cleansers. These fall into the general classes of nonionic, anionic, cationic, and amphoteric detergents. Detergents from natural and synthetic sources falling within these classes are amply set forth in Detergents and Emulsifiers, J. W. McCutcheon, editor, published by J. W. McCutcheon, Inc., 236 Mount Kemble Ave., West Orange, NJ.
  • nonionic detergents are those which do not ionize in water solution.
  • nonionic synthetic detergents commonly used are those formed by the condensation reaction of ethylene oxide units with hydrophobic bases among which are ethylene oxide condensates with alkyl phenols wherein the alkyl group on the phenol contains from six to about 12 carbon atoms in either straight or branched-chain configuration and the ethylene oxide is present in amounts equal to 10 or 12 units of ethylene oxide per mole of alkyl phenol.
  • nonionic detergents are the group of aliphatic alcohols condensed with ethylene oxide, i.e., alcohols having eight to 18 carbon atoms condensed with 8 to 30 units of ethylene oxide among which may be mentioned the condensate of 10 to 30 moles of ethylene oxide with coconut alcohol fractions having 10 to 14 carbon atoms.
  • Other nonionic synthetic detergents include the condensation products of ethylene oxide with propylene oxide and diamines or phosphates and the long-chain tertiary amines, oxides and tcrtiaryphosphines oxides. These are eschewed for the purposes of this invention for reasons of their pollution proclivities.
  • the preferred nonionic detergents for the purposes of this invention are the condensates of nonylphenol with ethylene oxide offered commercially under the Igepal trademark by GAF Corporation, New York City.
  • anionic detergent compounds useful in the compositions of this invention there must be mentioned ordinary soap.
  • This is the alkali metal salts of long-chain fatty acids having at least 12 carbon atoms.
  • Suitable soaps are the sodium, potassium and ammonium salts of fatty acids, derived from oils and fats from vegetable and animal sources.
  • anionic synthetic detergent compounds are the water-soluble salts and particularly the alkali metal salts of organic sulfuric reaction products such as the sulfonates and sulfates of alkyl and alkaryl moieties containing from eight to about 22 carbon atoms in the alkyl portion of the radical.
  • organic sulfuric reaction products such as the sulfonates and sulfates of alkyl and alkaryl moieties containing from eight to about 22 carbon atoms in the alkyl portion of the radical.
  • linear alkyl sulfonate sodium salts such as sodium lauryl sulfonate and the sodium and potassium alkyl benzene sulfonates such as are described in U.S. Pat. Nos. 2,220,009 and 2,477,383.
  • amphoteric synthetic detergents While the builders of this invention may be utilized with the amphoteric synthetic detergents. it is preferred not to do so since they generally fall within the broad class of amine derivatives and due to the chclating nature of most of such amphoteric compounds with heavy metals, it is preferred to avoid solubitized forms of such toxic materials in household environments.
  • the cationic synthetic detergents are generally the quaternary ammonium salts.
  • the quaternary ammonium compounds i.e., their ready biodegradeability, an exception is made concerning the utilization of nitrogen-containing deterv gents for general household purposes.
  • These compounds are particularly useful due to their cold water detergency characteristics.
  • Particularly useful for cold water laundry detergents is Soromine CAZ (CAP Corporation) a cationic complex polyalkyl amido imidezolinium sulfate.
  • the cationic detergents are unstable in the presence of alkaline pH solutions but the cationic detergents are fully compatible with the polyelectrolyte/alkaline salts composite builder of this invention.
  • the particular composition composite builders of this invention possibly due to the presence of the polyelectrolyte appear not to have this adverse effect.
  • detergent and builder composite of the present invention are utilized according to the following proportions:
  • composite builder parts by weight 5 to 70 surfactant parts by weight 5 to The above tabulation is a representation of the proportions of the active detergent to the composite builder in detergent cleansing compositions according to this invention.
  • Complete detergent compositions contain many ancillary ingredients useful for other purposes but having little to do directly with the problem of soil removal and the prevention of soil redeposition which combined indicate the cleansing effectiveness of the cleansing compositions.
  • lary agents which may be included in complete detergent eleansing and/or laundry compositions to adapt to certain specific applications, there may be mentioned the optical brighteners, anti-corrosives, foam stabilizers, defoaming agents, soil-suspending agents, enzymes, bleaches and the like.
  • the composite builder of this invention does not interfere with most of these ancillary materials.
  • the final detergent cleansers of this invention may be compounded as liquids or solids.
  • the detergent cleansing concentrates in the proportions tabulated above, plus any ancillary agents are then diluted with water to the extent ofSOO to 20,000 parts by weight of water.
  • Water presents its own problems depending on the degree of hardness and the presence of unwanted ions. Hardness is measured by the amount of calcium and magnesium ions. Such ions form insoluble non-detergent curds with long-chain fatty acids thereby preventing full utilization of the detergent compounds.
  • Other deleterious ions include iron which inalkaline solution tends to deposit as iron hydroxide, which upon drying and oxidizing leaves unsightly stains (rust spots) on laundered materials.
  • the ratio of polyelectrolytes to alkaline salts in the composite builder should range from 1 to l00 to l to 2 parts by weight.
  • the ratio of the detergent compound in the cleanser to the builder should be in the range of 8 parts by weight of the detergent to one part by weight of the builder.
  • To the other end of the range one part by tion is commercially marketed in various molecular weight ranges.
  • the various grades of polyelectrolyte are soluble in water and within the concentration and pH ranges set forth, the molecular weight has little or no effect upon the efficiacy of the builder compositions of-this invention.
  • the Terg-O-Tometer Detergency Test as described weight of the detergent to 100 parts by weight of the in Detergency Evaluation and Testing (J. C. Harris, composite builder of this invention. They may be forlnterscience Publishers, N.Y.) was utilized. Standard mulated as solid compositions in powder or shaped soiled cotton cloth was purchased from Test Fabrics. form or In llquld COnCentrlC 0rm- Inc.
  • Table 1 is a tabulation of concentration ranges pr p rties, of h preferred p ly r ly of this n n i n,
  • the formula used to calculate percent detergency is PVM/MA, the preferred alkaline salts, and commercial given in Detergency Evaluation and Testing" (p. 105) detergent compounds to be formulated into a condenand is: sate so that as diluted, the concentrate is equivalent to industrial household and laundry products used at 1.0 grams/liter: [(A E) B/(C B)] X 100 Detergency TABLE 1 Detergent Use Range Preferred 71 by Weight of Solution 7:
  • PVM/MA is the preferred polwhere yelectrolyte but that mixtures of the alkaline salts may also be used in combination with sodium carbonate for there is a synergism between the polyelectrolyte and the sodium carbonate or silicate or borate as regards the measurement of detergency at the various degrees of water hardness commonly encountered in the.
  • Examples 1 and 7 show the detergency as a function of water hardness for soda ash and sodium silicate polyelectrolyte (PVM/MA) and the synergism found in the salts with this polyelectrolyte as measured in the Tcrg-OTometer Detergency Test as as described in Detergency Evaluation and Testing" (J. C. Harris, lnterscience Publishers, N.Y.).
  • PVM/MA sodium silicate polyelectrolyte
  • Whiteness is calculated according to a formula published in Measurements of the Appearance of Paint Finishes by R. S. Hunter (Official Digest, Vol. 35, No. 459, p. 250-365) where G green filter reflectance B blue filter reflectance Standard soiled swatches together with unsoiled swatches were washed in the Terg-O-Tometer using a solution of the product in the designated water hardness. After washing 20 minutes, the swatches were rinsed and iron dried and then measured for reflectance using the Hunter D40 reflectometer. The data was then subjected to the whiteness formula and the detergency formula. The results are given in the tables with each example.
  • composition Gantrez AN 119 .017r .0171
  • EXAMPLE 2 This example illustrates the detergency improvement of a complete detergent composition including a non- EXAMPLE 4 surfactant GAFAC RA600 (TM) marketed by SAP Corporation and which is a complex organic phosphate ester based on linear alcohols.
  • GAFAC RA600 TM
  • EXAMPLE 5 ionic synthetic detergent lgepal C0630 (TM) mar- 55 keted by GAF Corporation and which is generically described as a nonylphenol-ethylcne oxide condensation product according to US. Pat. Nos. 1,970,578 and This example illustrates the effectiveness of the builder composite of this invention with sodium oleatc or soap as the anionic detergent.
  • EXAMPLE 7 such as the sole preferred modes and compositions as This example illustrates the effectiveness of the builder composite of this invention utilizing sodium meta silicates as the alkaline salt instead of sodium carbonate.
  • the detergency effect of the polyelectrolyte and the Na SiO of the components ofthe builder com- 3 positc is synergistic.
  • Example 1 and 7 the combination of the poly (vinyl methyl/maleie anhydride with sodium carbonate or sodium metasilicate is more effective than either component alone. This performance is more noticeable as the water hardness increases.
  • the prime purpose of the builder composite of this invention is to provide non-polluting builders for household. industrial and laundry purposes, the novel builders may also serve not only to completely replace the phosphate and nitrogen-containing builders previously used but may also partially replace them during interim periods of product change-over.
  • Example 8 below is a comparison of detergency and redeposition data of the commonly used builders with the composite builder of this invention and its components:
  • a detergent selected from the group consisting of nonionic, anionic, cationic and amphoteric detergents, together with a composite builder, as sole builder, consisting of a member selected from the group consisting of polyvinyl methyl ether/maleic anhydride, salts and hydrolysis products thereof having a K value of from 10 to about 200 and at least one alkali metal salt selected from the group consisting of alkali metal carbonates, alkali metal silicates, and alkali metal borates wherein the ratio of polyvinyl methyl ether/maleic anhydride group member to alkali metal salt group member is, in parts by weight, from 1:100 to l:2, the ratio of the detergent to the composite builder being, in parts by weight, 8:] to 1:100, whereby to produce an ecologically desirable detergent composition at least substantially devoid of non-polluting nitrogen and phosphorus.

Abstract

A non-polluting builder composition for cleansing purposes is described consisting of composite of a polyelectrolyte and the alkali metal salt of a weak acid. Such builder compositions can replace the phosphorous and nitrogen-containing builders previously used in cleansing and laundry detergents with regard to effectiveness in hard water at one-tenth and one-fifth the concentrations of such previously used builders. In hard water, such composite builders prevent the precipitation of insoluble calcium soaps which occurs in household and laundry detergent compositions utilizing either component alone as a builder. The previously noted stabilizing effects of the polyelectrolyte with regard to enzymes and bleaches is not decreased by the added components of these composite builders.

Description

States Patent 1 Grifo I POLYELECTROLYTES AS DETERGENT BUILDERS [52] US. Cl 252/135, 252/89, 252/137, 252/DIG. 15, 252/99 [51] Int. Cl. Clld 3/04, Cl 1d 11/00 [58] Field of Search 252/135, 137,89, DIG. 15
[56] References Cited UNITED STATES PATENTS 3,156,655 ll/1964 Bright 252/DIG. 15 3,284,364 ll/1966 Siegele 252/89 X 3,308,067 3/1967 Diehl 252/DIG. 15 3,535,258 10/1970 Sabatelli et a1. 252/105 3,623,991 l l/l971 Sabatelli et al, 252/99 X 3,700,599 10/1972 Mizuno et al 202/137 X 451 Mar. 11, 1975 Primary Examiner-Mayer Weinblatt Attorney, Agent, or FirmWalter C. Kehm; Samson B. Leavitt; James N. Blauvelt [57] ABSTRACT A non-polluting builder composition for cleansing purposes is described consisting of composite of a polyelectrolyte and the alkali metal salt of a weak acid. Such builder compositions can replace the phosphorous and nitrogen-containing builders previously used in cleansing and laundry detergents with regard to effectiveness in hard water at one-tenth and one-fifth the concentrations of such previously used builders. In hard water, such composite builders prevent the precipitation of insoluble calcium soaps which occurs in household and laundry detergent compositions utilizing either component alone as a builder. The previously noted stabilizing effects of the polyelectrolyte with regard to enzymes and bleaches is not decreased by the added components of these composite builders.
2 Claims, N0 Drawings 1 POLYELECTROLYTES AS DETERGENT BUILDERS FIELD OF THE INVENTION This invention relates to detergent compositions useful for household and laundry service and particularly relates to builders for such compositions that are devoid of pollutant or toxic potentials. The term builders refers to the class of compounds and compositions which improve detergency levels of synthetic detergents and soaps. By utilizing builders, it is possible to prepare detergent compositions having superior detergency as measured by removal of dirt and superior qualities with regard to the redeposition of the dirt that is loosened during the washing process. Additionally, by utilizing builders, it is possible to reduce the final cost of the detergent compositions.
The exact mechanism by which builders achieve their function in detergent compositions is not well understood. Consequently, it is not possible to predict classes of compounds or compositions which would tend to function as builders. Presently, two criteria are used for evaluating the effectiveness of builder compositions; detergency and anti-soild redeposition. Convenient objective means for measuring and evaluating these qualities will be describedbelow.
In the recent past, the most commonly used builder materials have been the water-soluble inorganic alakaline phosphates and polyphosphates. At present, their usage is being interdicted. The phosphate ion is a nutrient for algae which are a prime cause of eutrification of our lakes and waterways. The phosphate ion from laundry and household use of detergents appears to enhance the growth of algae and the sudden overgrowth of algae interferes with the ecological balance within the lakes and waterways into which such waste waters are discharged.
A recently commercialized builder material, nitrolotriacetic acid, had been proposed as a replacement for phosphate builders such as the polyphosphates. However, recent research has indicated the possibility of birth defects in test animals after exposure to combinations of nitrilotriacetic acid, which is a nitrogencontaining chelating agent, with certain toxic salts. It appears that this builder molecule in some manner permits the transport of toxic cadmium and mercury through tissue membranes. Consequently, this material is less than desirable for utilization in and around the normal household and for discharge into our environmental waters.
It is consequently an object of this invention to furnish a builder which is at least as effective as phosphates for use in detergent compositions.
It is a further object of this invention to provide a builder which is non-toxic and contains neither nitrogen phosphorus as readily available nutrient elements for the overgrowth of algae or other undesirable aquatic plants.
It is a further object of this invention to provide a builder which can be utilized for the preparation of ecologically balanced detergent products.
The above objects are achieved by the utilization in cleansing compositions, comprising detergents and builders, a builder that is a composite of certain polyelcctrolytes and alkaline-reacting salts of alkali metals with weak acids. The polyelectrolyte component of the composite builders of this invention are the copolymer of lower alkyl vinyl ethers with maleic acid or its anhydride. Preferred is PVM/MA of Polyvinyl methyl ether/Maleic Anhydride and its hydrolyzed product. The anhydride copolymer has the configuration of:
OR "I where R is lower alkyl up to 6 carbon atoms. .r is greater than 10, indicating polymers of molecule weight ranging from about 1,500 to in excess of 2,500,000. The anhydride copolymer is also useful in its hydrolyzed form and its salts. The hydrolyzed form, polyvinyl methyl ether/maleic acid has the following configuration:
l r1]. i. l
where R and x are as indicated above.
Viscosity measurements are commonly used as an in dication of the average molecular weight of the polymeric composition. The K value (Fikentscher) of any particular mixture of polymers is calculated from viscosity data and is useful as an indication of the average molecular weight of such mixtures. Its determination is fully described in MODERN PLASTICS 23 No. 3, 157-161, 212, 214, 216, 218, (1945) and is defined as 1,000 times k in the empirical relative viscosity equation:
wherein C is the concentration in grams per hundred cc. of polymer solution and 1 re] is the ratio of the viscosity of the solution to that of pure solvent. The K values are reportedas 1,000 times the calculated viscosity coefficient in order to avoid the use of decimals. The preferred interpolymers employed in the present invention have k values of from about 10 to about 200.
K values and specific viscosities (1 sp) are interconvertible and are related through relative viscosity (n0 rel). Thus, when viscosity measurements are taken on solutions which have a concentration of 1.00 gram of polymer per deciliter of solution at 25C (C l), the relationships are as follows:
(log e nrel)/C and intrinsic viscosity (the limit of inherent viscosity as C approaches 0 have the dimensions of dilution, i.e., the reciprocal of concentration. Intrinsic viscosity and Viscosity Average Molecular Gantrez 17 sp.* Weight AN-l l9 O.l 0.5 250,000 AN-l39 1.0 1.4 500,000 AN-l49 l.5 2.0 750,000 AN-l69 2.6 3.5 1,250,000 AN-l 79 3.6 4.5 2,250,000
as determined on a solution of 1.0 gm. of the copelymcr in l ml of methyl ethyl ketene at 25C.
The two essential ingredients for cleansing compositions comprise the detergent compound itself and the builder. Among the detergent compositions useful in conjunction with the builders of this invention are any of the classes of detergents commonly used for laundry and household cleansers. These fall into the general classes of nonionic, anionic, cationic, and amphoteric detergents. Detergents from natural and synthetic sources falling within these classes are amply set forth in Detergents and Emulsifiers, J. W. McCutcheon, editor, published by J. W. McCutcheon, Inc., 236 Mount Kemble Ave., West Orange, NJ.
The nonionic detergents as the name implies, are those which do not ionize in water solution. Among the nonionic synthetic detergents commonly used are those formed by the condensation reaction of ethylene oxide units with hydrophobic bases among which are ethylene oxide condensates with alkyl phenols wherein the alkyl group on the phenol contains from six to about 12 carbon atoms in either straight or branched-chain configuration and the ethylene oxide is present in amounts equal to 10 or 12 units of ethylene oxide per mole of alkyl phenol. Further nonionic detergents are the group of aliphatic alcohols condensed with ethylene oxide, i.e., alcohols having eight to 18 carbon atoms condensed with 8 to 30 units of ethylene oxide among which may be mentioned the condensate of 10 to 30 moles of ethylene oxide with coconut alcohol fractions having 10 to 14 carbon atoms. Other nonionic synthetic detergents include the condensation products of ethylene oxide with propylene oxide and diamines or phosphates and the long-chain tertiary amines, oxides and tcrtiaryphosphines oxides. These are eschewed for the purposes of this invention for reasons of their pollution proclivities.
The preferred nonionic detergents for the purposes of this invention are the condensates of nonylphenol with ethylene oxide offered commercially under the Igepal trademark by GAF Corporation, New York City.
Among the anionic detergent compounds useful in the compositions of this invention, there must be mentioned ordinary soap. This is the alkali metal salts of long-chain fatty acids having at least 12 carbon atoms. Suitable soaps are the sodium, potassium and ammonium salts of fatty acids, derived from oils and fats from vegetable and animal sources.
Among the anionic synthetic detergent compounds are the water-soluble salts and particularly the alkali metal salts of organic sulfuric reaction products such as the sulfonates and sulfates of alkyl and alkaryl moieties containing from eight to about 22 carbon atoms in the alkyl portion of the radical. Commercially important are the linear alkyl sulfonate sodium salts such as sodium lauryl sulfonate and the sodium and potassium alkyl benzene sulfonates such as are described in U.S. Pat. Nos. 2,220,009 and 2,477,383.
While the builders of this invention may be utilized with the amphoteric synthetic detergents. it is preferred not to do so since they generally fall within the broad class of amine derivatives and due to the chclating nature of most of such amphoteric compounds with heavy metals, it is preferred to avoid solubitized forms of such toxic materials in household environments.
The cationic synthetic detergents are generally the quaternary ammonium salts. Here due to the particular nature of the quaternary ammonium compounds. i.e., their ready biodegradeability, an exception is made concerning the utilization of nitrogen-containing deterv gents for general household purposes. These compounds are particularly useful due to their cold water detergency characteristics. Particularly useful for cold water laundry detergents is Soromine CAZ (CAP Corporation) a cationic complex polyalkyl amido imidezolinium sulfate. Usually the cationic detergents are unstable in the presence of alkaline pH solutions but the cationic detergents are fully compatible with the polyelectrolyte/alkaline salts composite builder of this invention. The particular composition composite builders of this invention possibly due to the presence of the polyelectrolyte appear not to have this adverse effect.
In general, the detergent and builder composite of the present invention are utilized according to the following proportions:
composite builder parts by weight 5 to 70 surfactant parts by weight 5 to The above tabulation is a representation of the proportions of the active detergent to the composite builder in detergent cleansing compositions according to this invention. Complete detergent compositions, of course, contain many ancillary ingredients useful for other purposes but having little to do directly with the problem of soil removal and the prevention of soil redeposition which combined indicate the cleansing effectiveness of the cleansing compositions. Among aneil-, lary agents which may be included in complete detergent eleansing and/or laundry compositions to adapt to certain specific applications, there may be mentioned the optical brighteners, anti-corrosives, foam stabilizers, defoaming agents, soil-suspending agents, enzymes, bleaches and the like. The composite builder of this invention does not interfere with most of these ancillary materials.
The final detergent cleansers of this invention may be compounded as liquids or solids.
Additionally, there may be employed coloring materials, perfumes and corrosion inhibitors. In general, the detergent cleansing concentrates in the proportions tabulated above, plus any ancillary agents are then diluted with water to the extent ofSOO to 20,000 parts by weight of water. Water presents its own problems depending on the degree of hardness and the presence of unwanted ions. Hardness is measured by the amount of calcium and magnesium ions. Such ions form insoluble non-detergent curds with long-chain fatty acids thereby preventing full utilization of the detergent compounds. Other deleterious ions include iron which inalkaline solution tends to deposit as iron hydroxide, which upon drying and oxidizing leaves unsightly stains (rust spots) on laundered materials.
For general commercial practical use, it is preferred that the ratio of polyelectrolytes to alkaline salts in the composite builder, according to this invention, should range from 1 to l00 to l to 2 parts by weight. When the builder is used in ecologically desirable detergentcompositions, the ratio of the detergent compound in the cleanser to the builder should be in the range of 8 parts by weight of the detergent to one part by weight of the builder. To the other end of the range one part by tion is commercially marketed in various molecular weight ranges. The various grades of polyelectrolyte are soluble in water and within the concentration and pH ranges set forth, the molecular weight has little or no effect upon the efficiacy of the builder compositions of-this invention. I
In order to exemplify the present invention and to comparatively demonstrate the advantages thereof, a series of formulations were prepared and standardized samples were washed in these formulations in order to evaluate their detergency and antisoil redeposition properties. The procedure used to evaluate the detergency properties of the product tested was as follows:
The Terg-O-Tometer Detergency Test as described weight of the detergent to 100 parts by weight of the in Detergency Evaluation and Testing (J. C. Harris, composite builder of this invention. They may be forlnterscience Publishers, N.Y.) was utilized. Standard mulated as solid compositions in powder or shaped soiled cotton cloth was purchased from Test Fabrics. form or In llquld COnCentrlC 0rm- Inc. and used as a means of measuring detergency Table 1 below is a tabulation of concentration ranges pr p rties, of h preferred p ly r ly of this n n i n, The formula used to calculate percent detergency is PVM/MA, the preferred alkaline salts, and commercial given in Detergency Evaluation and Testing" (p. 105) detergent compounds to be formulated into a condenand is: sate so that as diluted, the concentrate is equivalent to industrial household and laundry products used at 1.0 grams/liter: [(A E) B/(C B)] X 100 Detergency TABLE 1 Detergent Use Range Preferred 71 by Weight of Solution 7:
Poly (vinyl methyl ether/ maleic anhydride or Poly (vinyl methyl ether/ maleic acid .001 5.0 .005 Alkali metal salts of weak acids NHL-CO" .001 10.0 .050 Na sio, .00l 10.0 .005 Borax .00l l().() .005 Detergent .005 5.0 .0100 Optional Additives (MC 0.0 L0 .0005 Optical Brightener 0.0 0.5 .0003 Na -S() 0.0 10.0 .0292 Sodium bicarbonate 0.0 l0.0
lt should be noted that PVM/MA is the preferred polwhere yelectrolyte but that mixtures of the alkaline salts may also be used in combination with sodium carbonate for there is a synergism between the polyelectrolyte and the sodium carbonate or silicate or borate as regards the measurement of detergency at the various degrees of water hardness commonly encountered in the.
United States. In the Examples, Examples 1 and 7 show the detergency as a function of water hardness for soda ash and sodium silicate polyelectrolyte (PVM/MA) and the synergism found in the salts with this polyelectrolyte as measured in the Tcrg-OTometer Detergency Test as as described in Detergency Evaluation and Testing" (J. C. Harris, lnterscience Publishers, N.Y.).
With the other commonly used polyelectrolytes, it has been found that the detergency effect with alkaline salts is merely additive. While such other polyelectrolyte/alkaline salts composites are useful, they are not as commercially attractive or as competitively attractive or as competitively cleansing or ecologically desirable as the composites of this invention.
As noted. the preferred polyelectrolyte of this inven-,
A reflectance of soiled swatch after washing B reflectance of soiled swatch before washing C= reflectance of redeposition swatch before washing E net reduction in reflectance of redeposition swatch (before washing minus after washing) Whiteness is calculated according to a formula published in Measurements of the Appearance of Paint Finishes by R. S. Hunter (Official Digest, Vol. 35, No. 459, p. 250-365) where G green filter reflectance B blue filter reflectance Standard soiled swatches together with unsoiled swatches were washed in the Terg-O-Tometer using a solution of the product in the designated water hardness. After washing 20 minutes, the swatches were rinsed and iron dried and then measured for reflectance using the Hunter D40 reflectometer. The data was then subjected to the whiteness formula and the detergency formula. The results are given in the tables with each example.
EXAMPLE 1 The detergency of the preferred components of the composite according to this invention, i.e poly (vinyl EXAMPLE 3 This example illustrates a composition containing the anionic detergent dodecyl benzene sulfonate marketed water hardness. The results clearly illustrate the deter- 5 by Arco Chemical Co. under the name Ultrawet 60K.
Composition: Gantrez AN 119 .017r .0171
Na. CO;, .0571 .0571
Conditions Dist. Water Plus Composition (Without Surfactant) B. 25 ppm CuC1 .5 ppm FeCl 21.1 25.8 6.8 34.3
C. 100 ppm CaCl 5 ppm FeCl 7.4 7.9 13.5 25.0
D. 200 ppm CaCl- 5 ppm FeCL, 25.0 5.8 7.0 25.6
E. 300 ppm CaCI 5 ppm FeCl 35.0 4.7 16.2 34.2
F. 1000 ppm CaCl 5 ppm FeCL, -48.0 2l.7 -3.5 16.8
Composition Ultrawet 60K .03371 .03371 .03371 .03371 Gantrez AN] 19 .0171 .0171 Na CO .0571 .0571
Conditions Dist. Water Plus 71 Dctergency With Ultrawet 60K A. 25 ppm CaCL 5 ppm FeCl B. 100 ppm CaCl:. 5 ppm FeCl; C. 300 ppm CiiCl-g. 5 ppm FeCL,
gency synergism resulting from the preferred builder composites of this invention.
EXAMPLE 2 This example illustrates the detergency improvement of a complete detergent composition including a non- EXAMPLE 4 surfactant GAFAC RA600 (TM) marketed by SAP Corporation and which is a complex organic phosphate ester based on linear alcohols.
Composition GAFAC RA600 .0271 .0271 .0271 .0271 Gantrez AN119 .0171 .0171 Na CO .0571 .0571
Conditions Dist. Water Plus 71 Detergency with GAFAC A. 25 ppm CaCl- 5 ppm FeCL, 32.7 31.6 37.4 37.2 B. 100 ppm CaCl- 5 ppm FeCl 28.1 25.1 42.3 39.8 C. 300 ppm CZlCl-g, 5 ppm FeCl;, 10.7 11.5 26.6 39.8
Composition 1gepa1 C0630 02% .02% .02% .02% Gantrez AN] 19 .0171 .0171 Na CQ, .0571 .0571 Conditions Dist. Water Plus Detergency With Igepal C0630 A. 25 ppm CaCL. 5 ppm FeCL 24.7 40.2 19.2 53.6 B. 100 ppm CaCl 5 ppm FeCl 28.3 4.8 21.1 51.1
EXAMPLE 5 ionic synthetic detergent lgepal C0630 (TM) mar- 55 keted by GAF Corporation and which is generically described as a nonylphenol-ethylcne oxide condensation product according to US. Pat. Nos. 1,970,578 and This example illustrates the effectiveness of the builder composite of this invention with sodium oleatc or soap as the anionic detergent.
Conditions Dist. Water Plus Composition Na+ Oleate Gantrez ANl19 Na CO A 25 ppm B. 100 ppm C. 300 ppm CaCl 5 ppm FeCl CaCl 5 ppm FeCL, CaC1 5 ppm FeCl EXAMPLE 8 I Use Detergency Builder Compounds Concentration/7r Water Hardness(ppm) Average Redeposition Sodium Tripolyphosphate (STPP) 0.2 100 36.8 60.5 NTA 0.] 100 40.6 63.3 Sodium Carbonate 0.05 l00 33.5 60.2 Sodium Sulfate 0.2 100 3!.5 04.3 Poly (vinyl methyl/maleic anhydride) (Gantrez AN-l49 pH 7.0) 0.02 100 33.5 67.l Poly (vinyl methyl/maleic anhydride) (Gantrez AN-l49 NaCO EXAMPLE 6 This example illustrates the effectiveness of the builder composite of this invention with the cationic detergent Soromine CAZ-75(TM) marketed by GAF Corporation and which is a complex polyalkyl amido imidazolinium sulfate.
Wherever parts or percentages are mentioned, they are to be construed. as parts and percentages by weight. While the invention has been demonstrated in the examples by certain specific formulations, such examples merely indicate exemplary modes and compositions but the invention is not to be construed as limited to Composition Soromine CAZ'-75 0.026671 0.02667: 0.02667: v 0.026671 Oantrez ABl l9 .Ol7z .017: Nil co 05% 05% Conditions I Dist. Water Plus 7! Detergeney with Soromine CAZ'75 A. ppm CaCl- 5 ppm FeCL, 52.8 18.3 86.3 24.1
EXAMPLE 7 such as the sole preferred modes and compositions as This example illustrates the effectiveness of the builder composite of this invention utilizing sodium meta silicates as the alkaline salt instead of sodium carbonate. The detergency effect of the polyelectrolyte and the Na SiO of the components ofthe builder com- 3 positc is synergistic.
all equivalents thereto are intended.
What is claimed is:
l. A process for producing an ecologically desirable detergent composition suitable for washing textiles,
Igepal C0630 Conditions Dist. Water Plus Detergency with Sodium Metasilicate 100 ppm CaCl 5 ppm FeCl 14.2
As can be seen from Example 1 and 7, the combination of the poly (vinyl methyl/maleie anhydride with sodium carbonate or sodium metasilicate is more effective than either component alone. This performance is more noticeable as the water hardness increases. Examples 2. 3. 4, 5 and 6, aside from their demonstration ofthe effectiveness and utility of the composite builder of this invention with nonionic. anionic and cationic detergents. also demonstrate the synergistic performance of the preferred polyelectrolyte of this invention with soda ash in total formulation.
While the prime purpose of the builder composite of this invention is to provide non-polluting builders for household. industrial and laundry purposes, the novel builders may also serve not only to completely replace the phosphate and nitrogen-containing builders previously used but may also partially replace them during interim periods of product change-over. Example 8 below is a comparison of detergency and redeposition data of the commonly used builders with the composite builder of this invention and its components:
comprising admixing, as essential ingredients, a detergent selected from the group consisting of nonionic, anionic, cationic and amphoteric detergents, together with a composite builder, as sole builder, consisting of a member selected from the group consisting of polyvinyl methyl ether/maleic anhydride, salts and hydrolysis products thereof having a K value of from 10 to about 200 and at least one alkali metal salt selected from the group consisting of alkali metal carbonates, alkali metal silicates, and alkali metal borates wherein the ratio of polyvinyl methyl ether/maleic anhydride group member to alkali metal salt group member is, in parts by weight, from 1:100 to l:2, the ratio of the detergent to the composite builder being, in parts by weight, 8:] to 1:100, whereby to produce an ecologically desirable detergent composition at least substantially devoid of non-polluting nitrogen and phosphorus.
2. A process according to claim 1 wherein said alkali metal salt is sodium carbonate.

Claims (2)

1. A process for producing an ecologically desirable detergent composition suitable for washing textiles, comprising admixing, as essential ingredients, a detergent selected from the group consisting of nonionic, anionic, cationic and amphoteric detergents, together with a composite builder, as sole builder, consisting of a member selected from the group consisting of polyvinyl methyl ether/maleic anhydride, salts and hydrolysis products thereof having a K value of from 10 to about 200 and at least one alkali metal salt selected from the group consisting of alkali metal carbonates, alkali metal silicates, and alkali metal borates wherein the ratio of polyvinyl methyl ether/maleic anhydride group member to alkali metal salt group member is, in parts by weight, from 1:100 to 1:2, the ratio of the detergent to the composite builder being, in parts by weight, 8:1 to 1:100, whereby to produce an ecologically desirable detergent composition at least substantially devoid of non-polluting nitrogen and phosphorus.
1. A PROCESS FOR PRODUCING AN ECOLOGICALLY DESIRABLE DETERGENT COMPOSITION SUITABLE FOR WASHING TEXTILES, COMPRISING ADMIXING, AS ESSENTIAL INGREDIENTS, A DETERGENT SELECTED FROM THE GROUP CONSISTING OF NONIONIC, ANIONIC, CATIONIC AND AMPHOTERIC DETERGENTS, TOGETHER WITH A COMPOSITE BUILDER, AS SOLE BUILDER, CONSISTING OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF POLYVINYL METHYL ETHER/MALEIC ANHYDRIDE, SALTS AND HYDROLYSIS PRODUCTS THEREOF HAVING A K VALUE OF FROM 10 TO ABOUT 200 AND AT LEAST ONE ALKALI METAL SALT SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL CARBONATES, ALKALI METAL SILICATES, AND ALKALI METAL BORATES WHEREIN THE RATIO OF POLYVINYL METHYL ETHER/MALEIC ANHYDRIDE GROUP MEMBER TO ALKALI METAL SALT GROUP MEMBER IS, IN PARTS BY WEIGHT, FROM 1:100 TO 1:2, THE RATIO OF THE DETERGENT TO THE COMPOSITE BUILDER BEING, IN PARTS BY WEIGHT, 8:1 TO 1:100. WHEREBY TO PRODUCE AN ECOLOGICALLY DESIRABLE DETERGENT COMPOSITION AT LEAST SUBSTANTIALLY DEVOID OF NON-POLLUTING NITROGEN AND PHOSPHORUS.
US106549A 1971-01-14 1971-01-14 Polyelectrolytes as detergent builders Expired - Lifetime US3870648A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US106549A US3870648A (en) 1971-01-14 1971-01-14 Polyelectrolytes as detergent builders
GB29672A GB1363351A (en) 1971-01-14 1972-01-04 Detergent compositions
DE2200779A DE2200779B2 (en) 1971-01-14 1972-01-08 Detergent composition
CH37972A CH566392A5 (en) 1971-01-14 1972-01-11
FR7200930A FR2122212A5 (en) 1971-01-14 1972-01-12
JP47006087A JPS529681B1 (en) 1971-01-14 1972-01-13
NL7200504.A NL157650B (en) 1971-01-14 1972-01-13 PROCESS FOR PREPARING A TEXTILE DETERGENT.
CA132,383A CA993305A (en) 1971-01-14 1972-01-13 Polyelectrolytes as detergent builders
BE777980A BE777980A (en) 1971-01-14 1972-01-13 NEW POLYELECTROLYTES AS DETERGENT CHARGE

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US106549A US3870648A (en) 1971-01-14 1971-01-14 Polyelectrolytes as detergent builders

Publications (1)

Publication Number Publication Date
US3870648A true US3870648A (en) 1975-03-11

Family

ID=22312015

Family Applications (1)

Application Number Title Priority Date Filing Date
US106549A Expired - Lifetime US3870648A (en) 1971-01-14 1971-01-14 Polyelectrolytes as detergent builders

Country Status (9)

Country Link
US (1) US3870648A (en)
JP (1) JPS529681B1 (en)
BE (1) BE777980A (en)
CA (1) CA993305A (en)
CH (1) CH566392A5 (en)
DE (1) DE2200779B2 (en)
FR (1) FR2122212A5 (en)
GB (1) GB1363351A (en)
NL (1) NL157650B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4000080A (en) * 1974-10-11 1976-12-28 The Procter & Gamble Company Low phosphate content detergent composition
US4072621A (en) * 1974-11-13 1978-02-07 The Procter & Gamble Company Detergent composition
US4096084A (en) * 1973-06-04 1978-06-20 Tennant Company Surface cleaning method and machine
US4797223A (en) * 1988-01-11 1989-01-10 Rohm And Haas Company Water soluble polymers for detergent compositions
US4946627A (en) * 1989-07-19 1990-08-07 National Starch And Chemical Investment Holding Corporation Hydrophobically modified polycarboxylate polymers utilized as detergent builders
US20110124546A1 (en) * 2009-11-20 2011-05-26 Ecolab Inc. Solidification matrix using a maleic-containing terpolymer binding agent

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK333878A (en) * 1977-08-17 1979-02-18 Colgate Palmolive Co SOAP
DE3065073D1 (en) * 1979-11-09 1983-11-03 Unilever Nv Non-aqueous, built liquid detergent composition and method for preparing same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3156655A (en) * 1960-08-02 1964-11-10 Lever Brothers Ltd Heavy duty liquid detergent composition
US3284364A (en) * 1963-01-25 1966-11-08 American Cyanamid Co Soil anti-redeposition agents
US3308067A (en) * 1963-04-01 1967-03-07 Procter & Gamble Polyelectrolyte builders and detergent compositions
US3535258A (en) * 1967-12-04 1970-10-20 Grace W R & Co Machine dishwashing composition and process
US3623991A (en) * 1969-06-10 1971-11-30 Chemed Corp Descaling detergent composition
US3700599A (en) * 1970-09-25 1972-10-24 Economics Lab Composition for mechanically cleaning hard surfaces

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3156655A (en) * 1960-08-02 1964-11-10 Lever Brothers Ltd Heavy duty liquid detergent composition
US3284364A (en) * 1963-01-25 1966-11-08 American Cyanamid Co Soil anti-redeposition agents
US3308067A (en) * 1963-04-01 1967-03-07 Procter & Gamble Polyelectrolyte builders and detergent compositions
US3535258A (en) * 1967-12-04 1970-10-20 Grace W R & Co Machine dishwashing composition and process
US3623991A (en) * 1969-06-10 1971-11-30 Chemed Corp Descaling detergent composition
US3700599A (en) * 1970-09-25 1972-10-24 Economics Lab Composition for mechanically cleaning hard surfaces

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4096084A (en) * 1973-06-04 1978-06-20 Tennant Company Surface cleaning method and machine
US4000080A (en) * 1974-10-11 1976-12-28 The Procter & Gamble Company Low phosphate content detergent composition
US4072621A (en) * 1974-11-13 1978-02-07 The Procter & Gamble Company Detergent composition
US4303557A (en) * 1974-11-13 1981-12-01 The Procter & Gamble Company Abrasion resistant spray dried aluminosilicate detergent composition
US4797223A (en) * 1988-01-11 1989-01-10 Rohm And Haas Company Water soluble polymers for detergent compositions
US4946627A (en) * 1989-07-19 1990-08-07 National Starch And Chemical Investment Holding Corporation Hydrophobically modified polycarboxylate polymers utilized as detergent builders
US20110124546A1 (en) * 2009-11-20 2011-05-26 Ecolab Inc. Solidification matrix using a maleic-containing terpolymer binding agent

Also Published As

Publication number Publication date
GB1363351A (en) 1974-08-14
NL7200504A (en) 1972-07-18
CA993305A (en) 1976-07-20
BE777980A (en) 1972-07-13
JPS529681B1 (en) 1977-03-17
CH566392A5 (en) 1975-09-15
FR2122212A5 (en) 1972-08-25
DE2200779B2 (en) 1978-05-03
NL157650B (en) 1978-08-15
DE2200779A1 (en) 1972-07-20

Similar Documents

Publication Publication Date Title
US3904685A (en) Polyacrylic acid having high chelation value and its production
US4122043A (en) Amidobetaine containing detergent composition non-toxic to aquatic life
US3001945A (en) Liquid detergent composition
US3764559A (en) Detergent compositions
GB1600981A (en) Detergent composition
US3725290A (en) Oxyacetic acid compounds as builders for detergent compositions
US4532067A (en) Liquid detergent compositions containing hydroxypropyl methylcellulose
US3454500A (en) Soap compositions having improved curd-dispersing properties
US5507971A (en) Liquid cleaners for hard surfaces
US3870648A (en) Polyelectrolytes as detergent builders
US4612137A (en) Anti-yellowing detergent composition containing citrate and isocitrate
JP3927623B2 (en) Cleaning composition
US3925228A (en) Carbonate built detergents
US3776851A (en) Detergents containing tetrahydroxysuccinic acid and salts thereof
US3798183A (en) Detergent builder composition
DE1964024A1 (en) Detergents and cleaning agents
CA2012836C (en) Washing or detergent compositions
US4088610A (en) Detergent compositions
IE853191L (en) Detergent compositions
EP0913461A1 (en) Cleaning agent composition
CA1268682A (en) Detergent compositions using an aminocarboxylic acid as builder
JPH05171198A (en) Solid detergent
US5900396A (en) Carbonate built laundry detergent composition
US3335086A (en) Soil anti-redeposition agent
NO165772B (en) FITTINGS CALCULATED TO AA BE MOUNTED ON A VERSABLE DOOR SHEET.

Legal Events

Date Code Title Description
AS Assignment

Owner name: CHASE MANHATTAN BANK, THE NATIONAL ASSOCIATION

Free format text: SECURITY INTEREST;ASSIGNOR:DORSET INC. A CORP OF DELAWARE;REEL/FRAME:005122/0370

Effective date: 19890329

AS Assignment

Owner name: GAF CHEMICALS CORPORATION

Free format text: CHANGE OF NAME;ASSIGNOR:DORSET INC.;REEL/FRAME:005251/0071

Effective date: 19890411

AS Assignment

Owner name: DORSET INC., A DE CORP.

Free format text: CHANGE OF NAME;ASSIGNOR:GAF CORPORATION, A DE CORP.;REEL/FRAME:005250/0940

Effective date: 19890410

AS Assignment

Owner name: CHASE MANHATTAN BANK (NATIONAL ASSOCIATION), THE

Free format text: SECURITY INTEREST;ASSIGNOR:GAF CHEMICALS CORPORATION, A CORP. OF DE;REEL/FRAME:005604/0020

Effective date: 19900917

AS Assignment

Owner name: ISP INVESTMENTS INC.

Free format text: CHANGE OF NAME;ASSIGNOR:ISP 3 CORP.;REEL/FRAME:005949/0051

Effective date: 19910508

Owner name: ISP 3 CORP

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GAF CHEMICALS CORPORATION;REEL/FRAME:005949/0001

Effective date: 19910508

AS Assignment

Owner name: GAF CHEMICALS CORPORATION

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:CHASE MANHATTAN BANK, THE (NATIONAL ASSOCIATION);REEL/FRAME:006243/0208

Effective date: 19920804

Owner name: SUTTON LABORATORIES, INC.

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:CHASE MANHATTAN BANK, THE (NATIONAL ASSOCIATION);REEL/FRAME:006243/0208

Effective date: 19920804

Owner name: GAF BUILDING MATERIALS CORPORATION

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:CHASE MANHATTAN BANK, THE (NATIONAL ASSOCIATION);REEL/FRAME:006243/0208

Effective date: 19920804