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WO1992017523A1 - Agents antisouillure non ioniques - Google Patents

Agents antisouillure non ioniques Download PDF

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Publication number
WO1992017523A1
WO1992017523A1 PCT/US1992/002256 US9202256W WO9217523A1 WO 1992017523 A1 WO1992017523 A1 WO 1992017523A1 US 9202256 W US9202256 W US 9202256W WO 9217523 A1 WO9217523 A1 WO 9217523A1
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WIPO (PCT)
Prior art keywords
soil release
units
weight
sra
compositions
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.)
Ceased
Application number
PCT/US1992/002256
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English (en)
Inventor
Robert Ya Lin Pan
Eugene Paul Gosselink
Sandra Louise Honsa
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Procter and Gamble Co
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Procter and Gamble Co
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Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to JP4509434A priority Critical patent/JPH06506251A/ja
Publication of WO1992017523A1 publication Critical patent/WO1992017523A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents

Definitions

  • This invention relates to nonionic oligomers which function as improved soil release agents (sra's), and which are useful in laundry compositions, especially fabric softener compositions, and the like.
  • a "soil release" effect is produced when fabrics, especially fabrics having a synthetic fiber component, are immersed in an aqueous laundry or rinse bath in a domestic or institutional setting wherein the aqueous bath comprises various polymeric or oligomeric ester soil release agents (sra's), typically at low levels such as five to a few tens of parts per million.
  • the polymers or oligomers deposit onto the fabric surface to provide a soil-release finish thereto.
  • Soil release is distinct from the usual cleaning effect of laundry detergent surfactants and builders, in that a multi-wash effect is secured, e.g., fabrics repetitively laundered tend to be cleaned progressively more easily over two, three or four wash-wear cycles, and some soil antiredeposition benefit is also often secured. Soil release is especially pronounced on polyester fabrics, but good results are also secured on polyester/cotton blends. Soil release benefits are also seen on nylons and acrylics.
  • Soil release in an aqueous laundry context is rather differ ⁇ ent from industrial finishing of yarns and fibers, warp-sizing and the like, in terms of the general kinds of sra compositions which work best. This may be a consequence of some substantial differ ⁇ ences in processing conditions.
  • laundry sra's of the type herein are typically applied to fabrics in washing machines, either in the presence of noninterfering detersive surfactants, or, more preferably, in the presence of cationic fabric softening agents.
  • the sra typically deposits to only a limited extent on the fabrics.
  • industrial finishing is commonly done in highly controllable process equipment, such as padders.
  • the textile is clean, and the concentration of cleaning agents or softening agents (if any) tends to be low, at least at the stage at which it is desired to exhaust a soil release treatment onto the textile substrate.
  • laundry compositions such as laundry deter ⁇ gents, laundry softeners, laundry bleaches, and the like.
  • Such laundry compositions are also prepared in various forms, such as granular, liquid, gel, paste-form, and dryer-added products.
  • Formulators in the laundry arts are acutely aware that various forms of laundry compositions have inherent formulation con ⁇ straints.
  • solid-formulated compositions need ingred ⁇ ients generally capable of dispersing or dissolving in aqueous laundry baths, while liquid formulae commonly need ingredients which are freely mixable without excessive chemical or physical interaction such as phase changes or precipitation.
  • the present invention provides effective nonionic sra's which are suitable for use in laundry compositions.
  • the invention also provides nonionic sra's which are particularly useful in combina ⁇ tion with cationic fabric softeners.
  • many of the sra's herein do not excessively increase the viscosity of liquid fabric softener compositions, even when formulated as softener "concentrates”.
  • U.S. Patent 4,116,885 to Derstadt et al discloses laundry detergent compositions containing 0.15% to 25% (most preferably 0.5% to 10%) of an ethylene terephthalate/PEG terephthalate soil release polyester, such as MILEASE T, having an average molecular weight of 5,000 to 200,000 (preferably 10,000 to 50,000).
  • These detergent compositions further contain 5% to 95% (most preferably 10% to 25%) of certain compatible alcohol sulfate and alkylethyoxy sulfate detergent surfactants and no more than 10% of other incompatible anionic surfactants such as the linear alkyl benzene sulfonates.
  • U.S. Patent 4,132,680 to Nicol also discloses laundry detergent compositions having soil release properties which contain 2% to 95% (preferably 10% to 60%) of a detergent surfactant and 0.15% to 25% (most preferably 1% to 10%) of an ethylene terephthalate/PEG terephthalate (mole ratio of 65:35 to 80:20) soil release polyester having a molecular weight of 10,000 to 50,000, e.g., MILEASE T.
  • These compositions further comprise 0.05% to 15% (most preferably 0.1% to 5%) of a component which disassociates in aqueous solution to yield quaternary ammonium cations having one to three C 8 -C 24 alkyl groups. These cations are taught by Nicol to improve the deposition of the soil release polyester on the laundered fabric. See column 11, lines 14-21.
  • Patent 3,893,929 to Basadur discloses rinse-added acidic solutions containing a soil release agent made from a dibasic carboxylic acid (preferably terephthalic acid), a polyalkylene glycol (preferably a PEG having a molecular weight of 1,300 to 1,800) and an alkylene glycol (ethylene, propylene or butylene glycol).
  • Preferred soil release agents have a molecular weight of from 3,000 to 5,000.
  • Cationic fabric softeners such as ditallow dimethyl ammonium chloride can be included in these compositions, but are said to be not preferred "since they tend to retard the deposition of the soil release agent on the polyester fibers at acidic pH.” See column 7, lines 54-59.
  • U.S. Patent 3,712,873 to Zenk discloses textile treating compositions applied by spraying or padding which comprise 1% to 5% of a soil release polyester of the type disclosed in the Basadur patent. These compositions can additionally contain up to 4% of a quaternary ammonium compound having one C 16 -C 22 alkyl group. The combination of this quaternary ammonium compound with the polyester is described as improving the soil-release characteristic of the treated fabric. Zenk also states that other quaternary ammonium compounds, such as ditallow dimethyl ammonium chloride, did not give the same superior performance. See column 3, lines 57-61.
  • U.S. Patent 3,512,920 to Dunlap discloses low molecular weight alkylene glycol/polyalkylene glycol terephthalic acid polyesters which are used in resin treating baths containing starch or cellulose derivatives to impart soil release properties to cotton/polyester fabrics after heat curing.
  • the alkylene glycols which can be used to make these polyesters include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butylene glycol and mixtures thereof.
  • the polyalkylene glycols which can be used include PEG, polybutylene glycol and mixtures thereof which have an average molecular weight of 200 to 20,000 (preferably 1,000 to 5,000).
  • polyester antistatic agents which can contain a water-solvatable polymeric group such as a polyoxyalkylene group having an average molecular weight of from 300 to 6,000.
  • Preferred polyoxyalkylene groups are the PEG'S having an average molecular weight of from 1,000 to 4,000.
  • Treatment is carried out by applying an aqueous dispersion of the polyester in the presence of an antioxidant, followed by heating to a temperature above 90'C to obtain a durable coating of the polyester on the treated article.
  • Example 6 discloses one such polyester formed by the catalyzed reaction of dimethyl terephthalate, ethylene glycol and an 0-methyl poly(oxyethylene)glycol having an average molecular weight of 350. A 20% solution of this polyester in benzyl alcohol was used to impart antistatic properties to a polyester fabric.
  • Example 7 discloses a 20% aqueous solution of a similar polyester used to impart antistatic properties to a polyester fabric.
  • U.S. Patent 4,427,557 to Stockburger discloses low molecular weight copolyesters (2,000 to 10,000) formed by the reaction of ethylene glycol, a PEG having an average molecular weight of 200 to 1,000, an aromatic dicarboxylic acid (e.g., dimethyl terephthalate), and a sulfonated aromatic dicarboxylic acid (e.g., dimethyl 5-sulfoisophthalate).
  • the PEG can be replaced, in part, with monoalkylethers of PEG such as the methyl, ethyl and butyl ethers.
  • a dispersion or solution of the copolyester is applied to the textile material and then heat set at elevated temperatures (90 * C to 150'C) to impart durable soil release properties.
  • Example 2 discloses a random copolyester used to impart antistatic properties which is formed by reacting dimethyl terephthalate, sodium dimethyl sulfoisophthalate, ethylene glycol and a PEG having an average molecular weight of 1,540.
  • polyesters More particularly their lower molecular weight oligomers, capable of acting as sra's in laundry products.
  • the earlier disclosures relate to modified polyester-type materials which are not necessarily oligomeric and which contain segments without particular end-caps. They derive from ethylene glycol/ dimethyl terephthalate randomly interspersed with polyether segments deriving from polyethylene glycol. See, for example, U.S. Patent 3,962,152, Nicol et al , issued June 8, 1976, U.S. Patent 4,116,885, Derstadt et al, issued September 7, 1978, Canadian Patent 1,100,262, Becker et al, issued May 5, 1981, U.S. Patent 4,238,531, Rudy et al, issued December 9, 1980, and British Patent Application 2,172,608, Crossin, published September 24, 1986.
  • the present invention encompasses soil release agents which comprise the oligomeric esterification product of a reaction mixture which comprises:
  • soil release agents being further characterized by having a mole ratio of oxyethyleneoxy units:oxyiso-propyleneoxy units of at least about 0.5:1.
  • the soil release agents herein comprise, for example, the esterification reaction product of a reaction mixture comprising: (a) CH 3 (0CH 2 CH 2 ) 16 0H;
  • Such soil release agents differ from the sra's disclosed by Gosselink and Diehl, U.S. Patent 4,711,730, cited above, in that they contain oxyethyleneoxy units.
  • the sra's of this invention unexpectedly exhibit better performance than those of the '730 patent.
  • R 2 is a mixture of both H and CH 3 (i.e., both ethylene and isopropylene moieties are present in the molecular structure) to provide a mole ratio of oxyethyleneox :oxyisopropyleneoxy of at least about 0.5:1, preferably at least about 1.25:1.
  • x, y, m and n are integers within the following ranges: n+1 *This term indicates the average number of adjacent terephthalate units before interruption by a PEG unit. It is to be understood that the mole ratio of oxyethyleneoxy: oxypropyleneoxy units can be varied to meet the needs of the formulator.
  • this ratio is preferably at least about 0.75:1, more preferably at least about 1.25:1.
  • some product haziness may occur at these ratios, so the formulator may elect to select a somewhat lower ratio, e.g., 0.5:1.
  • the invention also encompasses laundry compositions such as detergents, softeners, rinse aids, and the like, comprising at least about 0.1%, preferably from about 0.2% to about 10% by weight, of the foregoing sra's.
  • Preferred fabric softener compositions herein typically comprise from about 0.3% to about 3% by weight of the sra and from about 3% to about 25% by weight of a fabric softener component.
  • a dilutable liquid fabric softener composition concentrate comprises:
  • Typical laundry detergent compositions herein comprise conventional detersive surfactants, optional builders, optional carriers, and from about 0.1% to about 10% by weight of the sra.
  • Preferred laundry detergents comprise from about 0.3% to about 3% by weight of said soil release agent and at least about 3%, preferably from about 3% to about 20% by weight of a fatty acid polyhydroxy amide surfactant, especially C 12 -C 18 fatty acid N-methylglucamide.
  • the invention also encompasses a method for providing a soil release finish on fabrics by contacting said fabrics with an aqueous medium containing at least about 2 ppm of the foregoing sra's.
  • the method comprises contacting the fabrics with an aqueous bath comprising at least 3 ppm (preferably from about 4 ppm to about 25 ppm) of the foregoing sra's and at least about 10 ppm (preferably from about 30 ppm to about 100 ppm) of a cationic fabric softener for a period of at least about 1 minute (preferably from about 1 minute to about 10 minutes) before separating the fabrics from the aqueous bath.
  • an aqueous bath comprising at least 3 ppm (preferably from about 4 ppm to about 25 ppm) of the foregoing sra's and at least about 10 ppm (preferably from about 30 ppm to about 100 ppm) of a cationic fabric softener for a period of at least about 1 minute (preferably from about 1 minute to about 10 minutes) before separating the fabrics from the aqueous bath.
  • the sra's of the present invention are prepared by esterifi- cation of the hydroxyl- and carboxylate-substituted reactants disclosed hereinabove.
  • the following Examples further illustrate the preparation of sra's according to this invention, but are not intended to be limiting thereof.
  • the material is transferred to a 1 liter, single neck, round bottom flask and heated gradually over about 20 minutes to 230 * C in a Kugelrohr apparatus (Aldrich) at about 1.5 mm Hg and maintained there for 1 hour. The flask is then allowed to air cool quite rapidly to near room temperature under vacuum (-30 min.). The reaction yields 124.1 g of soft brown solid.
  • the ⁇ -NMRfDMSO-de shows a very intense resonance at about 3.5 ppm for the poly(oxy- ethylene) segments, a resonance at about 8.0 ppm for the tere- phthalates, resonances at about 1.4 ppm for the methyl group of doubly esterified propylene glycol, and at about 4.7 ppm for doubly esterified ethylene glycol.
  • Comparison of the resonances at 1.4 and 4.7 ppm indicates that the mole ratio of ethylene glycol-derived units to propylene glycol-derived units is approxi- mately 2.2:1. This is referred to as the E/P ratio.
  • the 13 C-NMR(DMS0-d 6 ) is also consistent with the desired polymer structure, showing resonances at 70.2 (polyoxyethylene segments), 16.5 ppm (CH 3 of doubly esterified propylene glycol), 63.6 ppm (doubly esterified ethylene glycol), and 58.4 ppm (CH 3 0CH 2 CH 2 0-).
  • the absence of resonances at about 60 ppm for any monoesters of ethylene glycol (-C(0)0CH 2 CH 2 0H) or at about 20 ppm for the methyl group of one of the isomeric monoesters of propylene glycol (-C(0)0CH(CH 3 )CH 2 0H) indicates that the degree of polymerization is high.
  • An oligomer with a lower E/P ratio may be obtained using the same synthesis conditions except that the initial ratio of ethyl ⁇ ene glycol:propylene glycol is reduced. Typically, an initial glycol ratio of about 0.25:1 gives a final E/P ratio of about 0.5:1.
  • Dimethyl terephthalate Pol (ethylene glycol) methyl ether MW 750 Pol (ethylene glycol) of MW 1500
  • the 1 H-NMR(d6-DMS0) shows a very intense resonance at about 3.45 ppm for the polyoxyethylene segments, a complex resonance at about 8.05 ppm for the terephthalates, resonances at about 1.4 ppm for the methyl group of doubly esterified propylene glycol, and at about 4.7 ppm for doubly esterified ethylene glycol.
  • Comparison of the resonances at 1.4 and 4.7 ppm indicates that the mole ratio of ethylene glycol- derived units to propylene glycol-derived units is approximately 1.5:1. This is referred to as the E/P ratio.
  • the i3 C-NMR(d6- DMSO) is also consistent with the desired polymer structure, showing resonances at 70.2 ppm (polyoxyethylene segments), 16 ppm (CH 3 of doubly esterified propylene glycol), 63.6 ppm (doubly esterified ethylene glycol), and a very tiny peak at 58 ppm (CH 3 0CH 2 0-).
  • the virtual absence of resonances at about 60 ppm for any monoesters of ethylene glycol (-C(0)0CH 2 CH 2 0H) or at about 20 ppm for one of the iso eric monoesters of propylene glycol ((-C(0)0CH(CH 3 )CH 2 0H) indicates that the degree of polymerization is high.
  • the system is stirred as the temperature is gradually raised from 175 * C to 195 * C over a 36 hour period as 290 g of distillate (mostly methanol) is collected.
  • the temperature is then raised to 210"C for 18 hours as more distillate is collected.
  • a fritted glass inlet tube is inserted to near the bottom of the flask and inert gas is passed through at a high rate with the temperature maintained at 200'C. This is continued for approximately 4 days as a small amount of additional distillate collects.
  • the resulting polymer is allowed to cool to give about 3800 g of a soft solid which is about 65% soluble in water at room temperature when tested by stirring overnight at a 10% solids level.
  • the ⁇ -NMRfd ⁇ -DMSO shows a very intense resonance at about 3.45 ppm for the polyoxyethylene segments, a complex resonance at about 8.05 ppm for the tere- phthalates, resonances at about 1.4 ppm for the methyl group for doubly esterified propylene glycol, and at about 4.7 ppm for doubly esterified ethylene glycol.
  • Comparison of the resonances at 1.4 and 4.7 ppm indicates that the mole ratio of ethylene glycol-derived units to propylene glycol-derived units is approximately 2.6:1. This is referred to as the E/P ratio.
  • the 13 C-NMR(d6-DMS0) is also consistent with the desired polymer structure, showing resonances at 70.2 ppm (polyoxyethylene segments), 16 ppm (CH 3 of doubly esterified propylene glycol), 63.6 ppm (doubly esterified ethylene glycol), and a very tiny peak at 58 ppm (CH 3 0CH 2 CH 2 0-).
  • the virtual absence of resonances at about 60 ppm for any monoesters of ethylene glycol (-C(0)0CH 2 CH 2 0H) or at about 20 ppm for one of the isomeric monoesters of propylene glycol (-C(0)0CH(CH 3 )CH 2 0H) indicates that the degree of polymerization is high.
  • the sra's according to this invention can be employed in a variety of circumstances where it is desired to impart a soil release finish to fabrics, especially in a laundering operation.
  • the sra's herein can be added directly to a laundry or rinse bath of an automatic washing machine.
  • the sra's can be sprayed onto fabrics during an ironing operation.
  • the sra's can be deposited onto fabrics during a laundry drying operation in an automatic clothes dryer.
  • the sra's herein are deposited onto fabrics from an aqueous bath containing a fabric softener, such as the cationic fabric softeners well-known in the art.
  • a fabric softener such as the cationic fabric softeners well-known in the art.
  • various sra's can be selected from those disclosed herein which are quite compatible with cationics and do not disadvantageously increase the viscosities of even the "triple-concentrate" liquid fabric softener products that have recently come onto the market.
  • the lower molecular weight sra's will result in lesser increases in viscosities.
  • preferred compositions herein provide both a fabric softener component and an sra component, and are designed to provide a fabric softening (and antistatic) benefit concurrently with a soil release conditioning. The following is intended to assist the formulator in the manufacture of combined fabric softener/soil release compositions, but is not intended to be limiting thereof.
  • the liquid fabric softener composi ⁇ tions of the present invention comprise an effective amount of the sra's hereinabove defined. What is an "effective amount" will depend upon the particular sra's used, the particular type of fabric softener formulation and the benefits desired. Usually, the sra's are effective when included in an amount from about 0.01 to about 10% by weight of the composition. In terms of soil release benefits, preferred fabric softener compositions can comprise from about 0.1 to about 5% by weight of the sra's, but typically comprise from about 0.3 to about 3% by weight of these compounds.
  • the fabric softener compositions of the present invention further comprise from about 2 to about 50% (preferably from about 3 to about 25%) by weight fabric softener components.
  • the fabric softener component typically comprises from about 3 to about 10% by weight of the composition.
  • the fabric softener component typically comprises from about 15 to about 25% by weight of the composition.
  • the fabric softener component typically comprises a mono- or di(higher alkyl) quaternary ammonium salt or mixtures of such salts.
  • a mono- or di(higher alkyl) quaternary ammonium salt or mixtures of such salts See U.S. Patent 3,928,213 to Temple et al, issued December 23, 1975, especially column 2, line 57 to column 4, line 34, and U.S. Patent 4,399,045 to Burns, issued August 16, 1983, especially column 4, line 23 to column 7, line 2 (herein incorporated by reference), which disclose suitable quaternary ammonium salts.
  • “higher alkyl” as used in the context of the quaternary ammonium salts herein is meant alkyl groups having from 8 to 30 carbon atoms, preferably from 12 to 22 carbon atoms. Examples of such conventional quaternary ammonium salts include:
  • Rj is an aliphatic C 12 -C 22 hydrocarbon group
  • R 2 is a Cj-C saturated alkyl or hydroxyalkyl group
  • R 3 is selected from R 1 (preferred) or R 2 groups and A is an anion such as chloride, bromide or methyl sulfate.
  • Suitable mononitrogen quaternary ammonium salts are mono tallowtrimethylammonium chloride (MTTMAC), ditallowdi- methylammonium chloride (DTDMAC), ditallowdimethylammonium methyl sulfate, di(hydrogenated tallow)dimethylammonium chloride, dibehenyldimethylammonium chloride, dihexadecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, dieicosyldimethyl- ammonium chloride, didocosyldimethylammonium chloride; di(hydrogenated tallow)dimethylammonium methyl sulfate; dihexadecyldiethylammonium chloride; ditallowdipropylammonium bromide; di(coconutalkyl)dimethylammonium chloride; and mixtures thereof; 2. diamide quaternary ammonium salts having the formula
  • R 7 wherein R 4 is an aliphatic C 12 -C 22 hydrocarbon group; R 3 and R 5 are each divalent alkylene group having 1 to 3 carbon atoms; R 6 is a C ⁇ -C 4 saturated alkyl or hydroxyalkyl group; R 7 is R 6 or the moiety (C a H 2a 0)bH, wherein a is 2 or 3 and b is from 1 to about 5; and A is an anion.
  • Suitable diamide quaternary ammonium salts are methylbis(tanowamidoethyl)(2-hydroxyethyl)ammonium methyl sul ⁇ fate, methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)- ammonium methyl sulfate, and bis(2-hydrogenated tallowamidoethyl)- ethoxylatedammonium methyl sulfate; these materials are available from Sherex Chemical Company under the trade names VARISOFT 222, VARISOFT 220 and VARISOFT 110;
  • quaternary imidazolinium salts such as 1-methyl-1- tallowamido-ethyl-2-tallowimidazolinium methyl sulfate (sold under the trade name VARISOFT 475), l-methyl-l-(hydrogenated tallow- amidoethyl)-2-tallowimidizolium methyl sulfate (sold under the trade name VARISOFT 445), 1-ethylene-bis(2-tallow-l-methyl- imidazolinium methylsulfate) (sold under the trade name VARISOFT 6112); and l-methyl-2-tallow-3[ta ⁇ owamidoethylta ⁇ owylamino)- ethyl]imidazolinium methylsulfate (sold under the trade name VARISOFT 3012).
  • a preferred fabric softener component comprises: (A) from about 2 to about 15% by weight mononitrogen quaternary ammonium salts; (B) from 0 to about 14% by weight diamide quaternary ammonium salts; (C) from about 2 to about 13% by weight quaternary imidazolinium salts; the total amount of salts A, B and C being from about 15 to about 22.5% by weight. See U.S. Patent 4,399,045 to Burns, issued August 16, 1983, which is incorporated by reference.
  • the fabric softener component can also comprise certain di(higher alkyl) cyclic amines, typically as a mixture with a quaternary ammonium salt(s). These cyclic amines have the formula:
  • R 8 and R 9 are, independently, a C 8 -C 30 alkyl or alkenyl group, preferably Cn-C 2Z alkyl, more preferably C 15 -C l ⁇ alkyl, or mixtures of such alkyl radicals, such as those obtained from coconut oil, "soft” (nonhardened) tallow, and hardened tallow;
  • Q is CH or N, preferably N;
  • Z is
  • T is 0 or NR n , R ⁇ being H or C j -C 4 alkyl, preferably H; and R 10 is a divalent Ci-C 3 alkylene or (C 2 H 4 0)d group, wherein d is a number of from 1 to 8, or Z is R 10 .
  • amines are as follows: 1-tallow- amidoethyl-2-tallowimidazoline; l-(2-C 14 - 18 -alkyl-amidoethyl)-2- Cj 3 -C 17 -alkyl-4,5-dihydro-imidazole; l-stearylamidopropyl-2- stearylimidazoline; and l-tallowamidobutyl-2-tallowpiperidine.
  • Acids and Bases When cyclic amines are present in the fabric softener component, the pH of the fabric softener composi ⁇ tion is important for proper dispersion of the amines. Moreover, a somewhat acidic pH is preferred for hydrolytic stability of the soil release compounds of the present invention. Therefore, acids and/or bases can be added to the composition to adjust its pH. The amount of acid or base should be such that the pH of the dispersion, after mixing, is in the range from about 2.5 to about 6.5. Examples of suitable acids include the inorganic mineral acids, carboxylic acids, in particular the low molecular weight carboxylic acids, and alkanesulfonic acids.
  • Suitable inorganic acids include HC1 , H 2 S0 4 , HN0 3 and H 3 P0 4 .
  • Suitable organic acids include formic, acetic, ethanesulfonic and ethanesulfonic acid.
  • Preferred acids are hydrochloric, phos ⁇ phoric, formic and methanesulfonic acid.
  • Suitable bases include NaOH and Na 2 C0 3 .
  • Organic solvent The fabric softener compositions of the present invention can be formulated without the use of any organic solvent. However, the presence of organic solvents (for example, low molecular weight, water miscible aliphatic alcohols) does not harm the storage stability, the viscosity, or the softening performance of the compositions. Examples of such solvents include ethanol and isopropanol.
  • the quaternary ammonium salt(s) (or cyclic amine) will be obtained from a supplier of bulk chemicals in solid form or as a solution in an organic solvent, e.g., isopropanol. There is no need to remove such a solvent in making the compositions. Indeed, additional solvent can be added, if this is deemed desirable.
  • the fabric softener compositions optionally contain nonionics as have been disclosed for use in softener compositions. Such nonionics and the usage levels have been disclosed in U.S. Patent 4,454,049, to MacGilp et al, issued
  • nonionics suitable for the fabric softener compositions herein include glycerol esters (e.g., glycerol onostearate), fatty alcohols (e.g., stearyl alcohol), and alkoxylated fatty alcohols.
  • glycerol esters e.g., glycerol onostearate
  • fatty alcohols e.g., stearyl alcohol
  • alkoxylated fatty alcohols e.g., stearyl alcohol
  • the nonionic if used, is typically used at a level in the range of from about 0.5 to about
  • the nonionics are not considered part of the fabric softening component for the purposes of calculating the amount of fabric softening component in the composition.
  • the fabric softening composition optionally contains an aqueous emulsion of a predomi ⁇ nantly linear polydialkyl or alkyl aryl siloxane in which the alkyl groups can have from one to five carbon atoms and can be wholly or partially fluorinated.
  • Suitable silicones are poly- dimethyl siloxanes having a viscosity at 25 * C in the range from about 100 to about 100,000 centistokes, preferably in the range from about 1,000 to about 12,000 centistokes.
  • the ionic charge characteristics of the silicone as used in the combination can be important in determining both the extent of deposition and the evenness of distribution of the silicone and hence the properties of a fabric treated therewith.
  • Sil cones having cationic character show an enhanced tendency to deposit.
  • Silicones found to be of value in providing fabric feel benefits have a predominantly linear character and are preferably polydialkylsiloxanes in which the alkyl group is most commonly methyl.
  • Such silicone polymers are frequently manufac- tured commercially by emulsion polymerization using a strong acid or strong alkali catalyst in the presence of a nonionic or mixed nonionic-anionic emulsifier system.
  • the optional silicone component also embraces a silicone of cationic character which is defined as being one of: (a) a predominantly linear poly di Ci-C 5 alkyl- or C x -alky1, aryl- polysiloxane, prepared by emulsion polymerization using a cationic surfactant as emulsifier; (b) an alpha-omega-di quaternized di C ⁇ -C 5 or C !
  • the fabric softening compositions herein can contain up to about 10%, preferably from about 0.1% to about 5%, of the silicone component.
  • these compositions can contain relatively small amounts of electrolytes (e.g., 0.1%-3%), such as
  • NaCl, KBr, LiCl, MgCl 2 or CaCl 2 NaCl, KBr, LiCl, MgCl 2 or CaCl 2 .
  • the fabric softener compositions can also optionally contain other ingredients known to be suitable for use in textile soften ⁇ ers.
  • Such adjuvants include perfumes, preservatives, germicides, colorants, dyes, fungicides, stabilizers, brighteners and opaci- fiers. These adjuvants, if used, are normally added at their conventional levels (ca. 0.1%-5%). However, in the case of composition ingredients utilized for a fabric treatment effect, e.g., perfumes, these materials can be added at higher than normal levels, corresponding to the degree of concentration of the product.
  • the balance of the liquid fabric softener compositions of the present invention is water.
  • a fabric softener base composition is prepared from the following ingredients: Ingredient Wt. %
  • Ditallowdimethylammonium chloride 4.33 1-methyl-1-tallowamidoethyl-2-tallow- imidazolinium methyl sulfate (VARISOFT 475) 1.0 Ethanol 0.7 Isopropanol 0.1
  • Dital1owdi ethylammonium chloride l-tallowamidoethyl-2-tallowimidazoline Tallowtrimethylammonium chloride
  • Polydimethylsiloxane (viscosity 5,000 centistokes) 0.2 0.6 1.33 4.0 Perfume Minors* HC1 Water *CaCl 2 , dye, bactericide
  • a concentrated fabric softener base composition is prepared from the following ingredients:
  • the Premix is blended with the Water Seat, then combined with the Post Addition mix.
  • compositions can be used as laundry detergents, laundry additives, and laundry pre-treatments.
  • the laundry detergent compositions of the present invention comprise a soil release component which contains an effective amount of the sra's previously defined. What is an "effective amount" will depend upon the particular sra's used, the particular type of detergent formulation (liquid, granular, etc.) and the benefits desired. Usually, the sra's are effective when included in an amount from about 0.01 to about 10% by weight of the composition. In terms of soil release benefits, preferred laundry detergent compositions can comprise from about 0.1 to about 5% by weight of the sra's, but typically comprise from about 0.3 to about 3% by weight of these compounds. For granular detergent formulations, the sra component typically comprises the sra compounds, plus any protective enrobing material.
  • the sra could be exposed to highly alkaline materials such as NaOH and KOH.
  • the sra's in particular those having shorter backbones, can be degraded by alkaline environments, especially those above a pH of about 8.5.
  • the sra's are preferably enrobed in a material which protects them from the alkaline environment of a granular detergent formulation yet permits the sra's to be dispersed in the laundering operation.
  • Suitable enrobing materials include the nonionic surfactants, polyethylene glycols (PEG), fatty acids, fatty acid esters of diols and polyols, anionic surfactants, film forming polymers and mixtures of these materials.
  • suitable nonionic surfactant enrobing materials include some of those described hereinafter as also being useful detersive surfactants in the compositions.
  • suitable PEG enrobing materials are those having an average M.W. of from about 2,000 to 15,000, preferably from about 3,000 to about 10,000 and most preferably from about 4,000 to about 8,000.
  • suitable fatty acid enrobing materials are the higher fatty acids having from 12 to 18 carbon atoms.
  • suitable fatty acid ester enrobing materials include the sorbitan fatty acid esters (e.g., sorbitan monolaurate).
  • suitable enrobing materials including anionic surfactants and film forming polymers, are disclosed in U.S. Patent 4,486,327 to Murphy et al, issued December 4, 1984, which is incorporated by reference. The sra's can be enrobed according to the methods disclosed in this Murphy et al patent.
  • the sra component can be comprised entirely of sra's or can further include a water-soluble organic solvent or a hydrotrope to aid in dissolving the sra's.
  • Suitable organic solvents are usually aromatic and can include ethyl benzoate, phenoxyethanol , methyl-o-to!uate, 2-methoxybenzyl alcohol and pyrrolidone.
  • Suitable hydrotropes include the methyl capped PEG's and shorter backbone polyesters. These short backbone polyesters are more water-soluble, and, accordingly, can function as hydrotropes for the longer backbone, less water-insoluble sra's.
  • liquid detergent formulations containing the sra's of the present invention will depend upon the sra's used, especially what fraction thereof is water-soluble, the ingredients present in the laundry detergent system, and whether an isotropic, homogeneous liquid is desired.
  • isotropic liquid detergent formulations the sra's need to be dissolved as much as possible which sometimes requires the use of organic solvents or hydrotropes.
  • dissolving the sra's in liquid detergent formulations can make them more effective as soil release agents by facilitating dissolution in the wash liquor and thereby the adsorption on target fabrics.
  • Laundry compositions of the present invention preferably comprise from about 5 to about 75% by weight of a noninterfering, preferably nonionic detersive surfactant.
  • the nonionic detersive surfactant comprises from about 10 to about 40% by weight of the composition, and most preferably from about 15 to about 30% by weight.
  • Suitable nonionic surfactants for use in laundry compositions of the present invention are generally disclosed in U.S. Patent 3,929,678 to Laughlin et al , issued December 30, 1975 at column 13, line 14 through column 16, line 6 (herein incorporated by reference). Classes of nonionic surfactants included are:
  • the polyethylene oxide condensates of alkyl phenols.
  • examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol.
  • Such materials are available as IGEPAL CO-630, marketed by the GAF Corporation, and Triton X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company.
  • the condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol, and the condensa- tion product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms).
  • nonionic surfactants of this type include TERGITOL 15-S-9, marketed by Union Carbide Corporation, NE0D0L 45-9, NE0D0L 23-6.5, NE0D0L 45-7, and NE0D0L 45-4, marketed by Shell Chemical Company, and KYRO EOB, marketed by The Procter & Gamble Company.
  • Semi-polar nonionic detergent surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides contain ⁇ ing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consist ⁇ ing of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
  • Preferred amine oxide detergent surfactants are C 10 -C 18 alkyl dimethyl amine oxide and C 8 -C 12 alkoxy ethyl dihydroxy ethyl amine oxide.
  • Fatty acid amide detergent surfactants see U.S. Patent 4,711,730, column 17, line 35, for a description of such surfactants).
  • Preferred nonionic detergent surfactants for use in laundry compositions of the present invention are the ethoxylated alcohols and alkylphenols, especially the condensation products of C 12 -C 1 alcohols with from about 3 to about 7 moles of ethylene oxide per mole of alcohol, e.g., C 12 -C 13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
  • N-alkyl glucamine- amide-type surfactants as described in U.S. Patent 2,965,576 and in British Patent 809,060, E. R. Wilson, constitute another class of preferred nonionic surfactants for use herein.
  • Laundry compositions of the present invention can also comprise from 0 to about 15% by weight (preferably from 0 to about 10% by weight) synthetic anionic detergent surfactants.
  • synthetic anionic detergent surfactants include the water-soluble salts, typically the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid of sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • examples of this group of synthetic anionic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) and the sodium and potassium alkylbenzenesulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
  • C X1 -C 13 LAS linear straight chain alkylben- zenesulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C X1 -C 13 LAS.
  • Synthetic anionic surfactants also include: the C 10 -C 22 alkyl polyethoxylate sulfates; the sodium alkyl glyceryl ether sulfonates; the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkanesulfonates containing from about 1 to 3 carbon
  • Ampholytic surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic deriva- tives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water- solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent 3,929,678 to Laugh!in et al, issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants.
  • Zwitterionic surfactants can be broadly described as deriva ⁇ tives of secondary and tertiary amines, derivatives of hetero- cyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent 3,929,678 to Laugh!in et al, issued December 30, 1975 at column 19, line 38 through column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants.
  • Suitable cationic surfactants are disclosed in U.S. Patent 4,259,217 to Murphy, issued March 31, 1981, herein incorporated by reference.
  • the alkali metal soaps which are useful include the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms.
  • the laundry detergent compositions of the present invention can optionally comprise inorganic or organic detergent builders to assist in mineral hardness control.
  • Such builders will typically comprise up to about 60% by weight of the compositions; built liquid formulations generally comprise from about 1% to about 25% by weight detergency builder, most preferably from about 3% to about 20% by weight, while built granular formulations generally comprise from about 5% to about 50% by weight detergent builder, most preferably from about 10% to about 30% by weight.
  • Suitable detergent builders include the crystalline alumino- silicate ion exchange materials typically referred to as "Zeolite A”, “Zeolite P”, and “Zeolite X”, especially the zeolites having a particle size from about 0.1 to about 10 microns.
  • Optimum zeolites for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
  • Amorphous aluminosilicates, especially those having a magnesium ion exchange rate of at least about 1 grain/gallon/minute/gram/gallon are also useful.
  • a method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669.
  • An especially preferred hydrated aluminosilicate has the formula:
  • detergency builders include the water-soluble alkali metal (or ammonium) phosphates, polyphosphates, phosphonates, carbonates, silicates, acetates, polyhydroxysulfonates and, especially, polycarboxylates.
  • Various polycarboxylate builders are disclosed in U.S. Patents 3,308,067; 3,723,322; 4,144,226; and 4,246,495.
  • the oxydisuccinates aka “oxodisuccinates”
  • tartrate mono- and di-succinates, and citrate are specific examples of preferred polycarboxylate builders for use herein.
  • the laundry detergent compositions herein can also optionally include clay soil removal and/or antiredeposition agents, and such materials are usually employed in ranges from about 0.1% to about 10% by weight of the compositions.
  • Such materials include various ethoxylated amines, and the like, referred to in the above-cited U.S. Patent 4,711,730.
  • Another group of preferred clay soil removal/antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, published June 27, 1984. Such materials are also disclosed in considerable detail in U.S. Patent 4,711,730, cited above.
  • optional ingredients which can be included in laundry detergent compositions of the present invention in their conven- tional art-established levels for use include solvents, bleaching agents, bleach activators, corrosion inhibitors, dyes, fillers, optical brighten- ers, germicides, pH-adjusting agents, enzymes, enzyme stabilizers, perfumes, and the like.
  • Granular detergent compositions embodying the sra's of the present invention can be formed by dry-mixing the sra's into compositions formed by otherwise conventional techniques, conven- tional techniques, i.e., by slurrying the other individual compon ⁇ ents in water and then atomizing and spray-drying the resulting mixture, or by pan or drum granulation of the ingredients, or by fluidized bed processes.
  • Liquid formulations can be in the form of single phase (preferred) compositions or can be in multiphase or "dispersion" form.
  • Dispersions conventionally employ viscosity modifiers to produce systems having plastic shear characteristics to maintain stable dispersions and to prevent phase separation or solids settlement.
  • the laundry detergent compositions of the present invention are operative within a wide range of wash pH's, they are particularly suitable when formulated in liquids to provide a near neutral wash pH, i.e., an initial pH of from about 6.0 to about 8.5 at concentrations of from about 0.1% to about 2% by weight in water at 20 * C.
  • the near neutral pH of such formulations is also desirable to ensure long-term stability for the sra's.
  • the product pH is preferably from about 6.5 to about 8.5, and more preferably from about 7.0 to about 8.0.
  • the following illustrate specific embodiments of laundry detergent compositions employing the sra's of the present inven ⁇ tion, but are not intended to be limiting thereof.
  • a liquid detergent composition is as follows. Ingredient Wt. %
  • Example XIII The composition of Example XIII is prepared using standard admix procedures to incorporate the sra.
  • the sra's of the present invention can be employed in laundry and softening compositions of a type familiar to formulators of fabric care compositions.
  • the sra's herein can be directly added to, for example, aqueous laundry rinse baths in conjunction with fabrics.
  • the sra's herein can be releasably affixed to sheet substrates, or the like, designed for use in automatic clothes dryers.
  • Such sheet substrates can additionally have releasably affixed thereto various fabric softener and/or anti- static agents of types which are well-known in commercial prac ⁇ tice.
  • damp fabrics are tumbled with the sheet substrates, thereby causing the sra and, if present, optional fabric soften ⁇ ers/antistatic agents, to be transferred from the sheet substrate onto the fabric surfaces.
  • a 13 C-NMR(DMS0-d 6 ) shows a resonance for -C(0)0CH 2 CH 2 0C(0 ⁇ - at -63.2 ppm (diester), a resonance for -C(0)0CH 2 CH 2 0H at -59.4 ppm (monoester), and a large peak at -69.8 representing poly(oxyethylene) units.
  • the ratio of the diester peak height to the monoester peak height is about 5.8.
  • the appreciable concentration of end groups consisting of monoesters of ethylene glycol shows that the product is a low molecular weight polymer.
  • the 1 H-NMR(DMS0-d 6 ) spectrum is also consistent with the formation of a low molecular weight polymer.
  • Peaks in the 1.1-1.3 ppm region show an appreciable level of monoesters of propylene glycol are present.
  • the ratio of the area of the peak for the methylene groups of diesters of ethylene glycol at -4.7 ppm to the area of the peak for the methyl group of diesters of propylene glycol at -1.4 ppm is measured. From this, the molar ratio of incorporated ethylene/propylene glycols (E/P ratio) is calculated to be 2.2:1.
  • the solubility is tested by weighing a small amount of material into a vial, adding enough distilled water to make a 5% by weight solution, and agitating the vial vigorously. The material is soluble under these conditions.
  • compositions comprising from about 10% to about 32% by weight of cationic fabric softener (e.g., DTDMAC), from about 4% to about 20% by weight of imidazolinium fabric softener and from about 1% to about 5% by weight of the sra's herein are also encompassed by this invention.
  • cationic fabric softener e.g., DTDMAC
  • compositions comprise from about 0.3% to about 3% by weight of the sra's herein and, as the detersive surfactant, from about 3% to about 20% by weight of a fatty acid polyhydroxy amide surfactant (see U.S. Patent 2,965,576, corresponding to GB 809,060, cited above, incorporated herein by reference), preferably in combination with from about 5% to about 25% by weight of a sulfated or sulfonated anionic surfactant such as the C 12 -C 18 alkyl benzene sulfonates, C 12 -C 18 alkyl ethoxy sulfonates (avg. EO 3-10; preferred), along with conventional amounts (15%-50%) of conventional builders, including such preferred builders as Zeolite A, oxydisuccinates, and mixtures thereof, the balance of such compositions comprising conventional detergent ingredients at conventional levels.
  • a fatty acid polyhydroxy amide surfactant see U.S. Patent 2,965,576,

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Abstract

Agents antisouillure non ioniques possédant à la fois des unités oxyéthylène et oxyiso-propylèneoxy et utilisés dans les compositions de lessive, notamment les produits liquides assouplissant les tissus au rinçage, ainsi que dans les compositions détergentes. Ainsi, on ajoute à un produit assouplissant liquide comprenant du DTDMAC le produit réactionnel de CH3(OCH2CH2)16OH, de diméthyle-téréphtalate, de polyéthylène-glycol 1500, de 1,2-propylène-glycol et d'éthylène-glycol, de préférence sous forme de polymère/oligomère dans lequel le rapport éthylène-glycol:propylène-glycol est d'environ 1,5:1. Les tissus rincés dans un bain contenant cette composition sont à la fois assouplis et dotés d'un apprêt antisouillure.
PCT/US1992/002256 1991-03-28 1992-03-18 Agents antisouillure non ioniques Ceased WO1992017523A1 (fr)

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WO1995020640A1 (fr) * 1994-01-31 1995-08-03 Henkel Kommanditgesellschaft Auf Aktien Melanges detergents
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WO1999041348A1 (fr) * 1998-02-11 1999-08-19 Rhodia Chimie Compositions detergentes contenant un silicone amine et un glucamide
WO2000042139A1 (fr) * 1999-01-11 2000-07-20 The Procter & Gamble Company Composition d'entretien pour tissus, destinee a etre appliquee directement sur des tissus
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DE19811329C2 (de) * 1998-03-16 2001-11-22 Lifestyle Vertriebsgmbh Mittel zur Bekämpfung von Flöhen
WO2002002731A1 (fr) * 2000-06-29 2002-01-10 Colgate-Palmolive Company Composition adoucissante multiphase limpide pour tissus
US6489395B2 (en) 1999-12-08 2002-12-03 Clariant Gmbh Emulsions
WO2009138177A1 (fr) * 2008-05-15 2009-11-19 Clariant International Ltd Additifs pour détergents et agents de nettoyage
US7655609B2 (en) 2005-12-12 2010-02-02 Milliken & Company Soil release agent
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WO2011098355A1 (fr) 2010-02-09 2011-08-18 Unilever Plc Polymères colorants
EP2448992A4 (fr) * 2009-07-01 2013-01-09 Rhodia China Co Ltd Procédé de production d'un copolymère séquencé polyéther-polyester
WO2014029479A1 (fr) * 2012-08-18 2014-02-27 Clariant International Ltd Utilisation de polyesters dans des produits de lavage et de nettoyage
US20150141315A1 (en) * 2012-06-15 2015-05-21 Rhodia Operations Method to recover or increase water absorbency of polyester textile
US20180094220A1 (en) * 2016-10-03 2018-04-05 The Procter & Gamble Company Laundry detergent composition
WO2018085305A1 (fr) 2016-11-01 2018-05-11 The Procter & Gamble Company Leuco-polymères en tant qu'agents d'azurage dans des compositions d'entretien du linge
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WO1993023510A1 (fr) * 1992-05-12 1993-11-25 The Procter & Gamble Company Compositions concentrees assouplissantes contenant des produits assouplissants biodegradables
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CA2106217A1 (fr) 1992-09-29
AU1753292A (en) 1992-11-02
JPH06506251A (ja) 1994-07-14
NZ242150A (en) 1995-04-27
TW200550B (fr) 1993-02-21
CN1066680A (zh) 1992-12-02
MX9201415A (es) 1992-10-01
AR244788A1 (es) 1993-11-30
PT100298A (pt) 1993-07-30

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