PT100298A - NON-IONIC SOIL RELEASE AGENTS CONTAINING OXY-ETHYLENE AND OXY-ISOPROPYLENOXI UNITS - Google Patents

Description

Y # ^ 64.47.8 " NON-IONIC SOIL RELEASING AGENTS "

TECHNICAL FIELD

This invention relates to nonionic oligomers which function as improved soil release agents (a.l.s.), and which are useful in laundry compositions, especially fabric softening compositions and the like.

BACKGROUND OF THE INVENTION 10 15

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An effect of " releasing dirt " is produced when especially woven fabrics containing a synthetic fiber component are immersed in an aqueous wash or rinsing bath in a domestic or institutional setting wherein the aqueous bath includes various polymeric ester or oligomeric (als) typically at low levels, such as five to a few tens of parts per million. The deposition of oligomers or polymers on the surface of the fabrics also yields one. from dirt. The effect of releasing dirt is different from the usual effect; cleaning detergents and laundry detergent activators, in that an effect of multiple washes is ensured, for example, fabrics washed repeatedly, tend to be progressively easier to clean after two, three or four cycles of "; wash and use, and some anti-fouling benefits are also ensured. The release of dirt is especially marked on the polyester fabrics but good results are also assured on polyester / cotton blends. There are also soil-release benefits in nylons and acrylics. The release of dirt in a context of aqueous washes is very different from the industrial finish of yarns and fibers, warp sizing and the like, 2 30 1 5

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25 30 35 64,478

in terms of the general molds of the ALS compositions which work best. This may be a consequence of some substantial difficulties in processing conditions. In any case, laundry ALS of this type is typically applied to fabrics in washing machines or in the presence of non-interfering detersive surfactants or, preferably, in the presence of softening agents. The ALS deposits only to a limited extent fabrics. In contrast, industrial finishing is often done by equipment and / or by controllably controllable processes such as fabrics. Typically, the fabric is cleaned, and the concentration of cleaning agents or softening agents (if any) tends to be low at least to the level desired for the exhaustion of the textile release substrate treatment. It is precisely here that technical differences arise between the laundry and the industrial finish, so there are also differences laundry detergents, laundry conditioners, vandal bleaches, and the like. Such laundry compositions are also prepared in various forms, such as granular, liquid, gel, paste, and dry-added products. laundry facilities are keenly aware that the various forms of laundry compositions have inherent constrictions to the formulation. For example, solid formulated compositions require ingredients generally capable of dispersing or dissolving laundry laundry, while the liquid formula generally requires ingredients that are freely miscible without a chemical or physical interaction excessive, such as phase changes or precipitation.

Particularly, the compositions of the - = 3 = 10

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Ikã

modern vandaria are now becoming available in the popular form of " concentrated ". For example, fabric softeners, which have now been commercially available, contain cationic softening ingredients at concentrations on the order of three times that of fabric softeners formerly available. It is to be understood that the formulation of such compositions in shelf-stable form and with reasonable viscosity variations can be difficult. The difficulties of formulation and execution are certainly emphasized when attempts are made to incorporate additional functional ingredients, such as ALS, into such compositions. Accordingly, a continuous process for effective, compatible and easy-to-form ALS for use in the laundry compositions is maintained. The present invention provides nonionic, effective ALS which are suitable for use in the laundry compositions. The invention also provides nonionic ALS which are particularly useful in combination with cationic fabric softeners. Moreover, many of the ALS do not excessively increase the viscosity of the liquid fabric softener compositions, even when formulated as " concentrated " softeners. PREVIOUS TECHNIQUES US Patent 4,711,730 to Gosselink and Diehl, Dec. 8, 1987, refers to coated, polypropylene polyoxyethylene-1,2-propylene-polyester polyesters, useful as laundry-releasing agents in laundry tergents and compositions fabric softeners, including concentrates. Additional references in the field, such as those cited in Gosselink and Diehl, include the following: = 4 = 35 10 0 15

Mod. 71-20,000 ex. - 70/08 20 25 30 64,478

Ethylene-terp- thalate / PEG-terptalate-releasing polyesters used in laundry detergent compositions US Pat. No. 4,166,885 to Dersadt et al., Issued September 26, 1978 discloses laundry compositions containing 0.15% to 25% (preferably 0.5% to 10%) of one. ethylene terp- thalate / PEG'teraphthalate, 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 from 5% to 95% (preferably from 10% to 25%) of alcoholsulfate and alkyl ethoxy sulfate compatible detergent surfactants and not more than 10% of other incompatible anionic surfactants such as linear alkyl sulfates benzene. US Patent 4,132,680 to Nicol, January 2, 1979, also discloses laundry detergent compositions having soil release properties containing from 2% to 95% (preferably from 10% to 60%) of a detergent surfactant and , 15? to 25% (preferably 1% to 10%) of an ethylene terpthalate / PEG terptalate (65:35 to 80:20 molecular weight) polyester with a molecular weight of 10,000 to 50,000 for example, MILEASE T These compositions further comprise from 0.05% to 15% (preferably from 0.1% to 5%) of a component which is dissociated in aqueous solution to give quaternary ammonium cations, having one to three alkyl groups C8 " C24 * These cations were instructed by Nicol to improve the deposition of the soil release polyesters in the washed fabrics. See column 11, lines 14-21. B. Use of polyesters in rinse additives to give soil release properties A Canadian Patent 1,100,262 Becker = 5 = 3515

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et al., May 5, 1981, discloses fabric softening compositions containing from 1% to 80% (preferably 5% to 50%) of a fabric softening agent such as di-tallow dimethyl chloride in combination with 0.5% to 25% (preferably 1% to 10%) of certain choline fatty acid esters. These softener compositions preferably include from 0.5% to 10% (preferably from 1% to 5%) of an ethylene terpthalate / PEG-terpthalate soil release polyester, such as PERMALOSE or ZELCON. Basadur US Pat. No. 3,893,929, issued July 8, 1975, discloses additive acid detergent solutions containing a soil release agent made from dibasic carboxylic acid (preferably tera-phthalic acid), a polyalkylene glycol ( preferably a PEG having a molecular weight of 1300 to 1800) and an alkylene glycol (ethylene, propylene or butylene glycol). Preferred soil-releasing agents have a molecular weight of 3,000 to 5,000. Cationic fabric softeners, such as di-tallow dimethyl ammonium chloride may be included in these compositions, but are referred to as not preferred " since they tend to retard the deposition of the soil release agent on the fibers of the polyester, at an acidic pH ". See column 7, lines 54-59. U.S. Patent 3,712,873 to Zenk, January 23, 1973, discloses spray applied or waterborne textile treatment compositions comprising from 1% to 5% of a soil release polyester of the type published in the Basadur patent. These compositions may additionally contain more than 4% of a quaternary ammonium compound having an alkyl group. The combination of this quaternary ammonium compound with the polyester is described as an improvement in the soil release characteristics of the treated tissue. Zenk, also states 6 64,478

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25

that quaternary ammonium compounds, such as di-tallow dimethyl ammonium chloride, do not give the same level of performance. See column 3, lines 57-61. C. Use of polyesters in dry-added products to provide soil release properties U.S. Patent 4,238,531 to Rudy et al., Issued December 9, 1980, discloses dry-added products which contain a " distributing agent " such as polyethylene glycol and an adjuvant, applied to the fabric, which may be a soil release agent. The soil release agents disclosed include polyacrylate resins, polyvinyl alcohol and PERMALOSE TG polyesters (see example 8). D. Use of polyesters in textile or textile treatment solutions which are heat-treated to provide release of dirt and / or anti-static properties US 3,512,920 Dunlap, issued May 9, 1970, discloses polyesters of tert- low molecular weight lenoglycols which are used in resin treatment baths containing starch derivatives or cellulose derivatives to give soil release properties to cotton / polyester fabrics after heat treatment. The alkylene glycols that can be used to produce such polyesters include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butylene glycol and mixtures thereof. Polyalkylene glycols which may be used include PEG, polybutylene glycol and their smells having an average molecular weight of 200 to 20,000 (preferably 1,000 to 5,000). = 7 = 35 1 5

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US Patent 3, 416,952 to McIntyre et al., Issued December 17, 1968, discloses antistatic agents, polyesters which may contain a water soluble polymer group, such as a polyoxyalkylene group, having an average molecular weight of about 300 to 6,000. Preferred polyoxyethylene groups are PEG, having an average molecular weight of from 1,000 to 4,000. The treatment is carried out by the application of an aqueous dispersion of the polyester in the presence of an antioxidant followed by heating to a temperature in excess of 90 ° C to obtain a durable coating of the polyester in the treated article. Example 6 shows one of these polyesters formed by the catalyzed reaction of dimethyl terafthalate, ethylene glycol and a 0-methyl poly (oxyethylene) glycol having an average molecular weight of 350. A 20% solution of this polyester in benzyl alcohol was used to give antistatic to a polyester fabric. Example 7 shows a 20% aqueous solution of a similar polyester used to create antistatic properties to a polyester fabric. US Patent 4,427,557 to Stockburger, dated January 24, 1984, 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, a dicarboxylic acid (eg dimethyl teraphthalate) and a sulfonated aromatic dicarboxylic acid (eg dimethyl 5-sulfoisophthalate). PEG may in part be substituted by the mono-alkyl ethers of PEG such as methyl, ethyl and butyl ethers. A solution dispersion of the copolyester is applied to the textile material and then heated at elevated temperatures (90 ° C to 150 ° C) to give long lasting dirt-release properties. See also the McIntyre et al. Patent, where Example 2 discloses an irregular copolyester used to give antistatic properties, which is formed by reacting dimethyl teraphthalate = 8 = 35 64,478

sodium dimethyl sulfoisophthalate, ethylene glycol and a PEG having an average molecular weight of 1,540. δ

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In addition, there are various disclosures in the art of the polyesters, more particularly, of their low molecular weight oligo-mers, capable of acting as 2S in laundry products. The foregoing disclosures relate to materials of the modified polyester type, which are not necessarily oligomeric and contain segments without a particular protective finish. They are derived from ethylene glycol / dimethyl terpthalate irregularly intercalated with polyester segments derived from polyethylene glycol. See, for example, U.S. Patent 3,962,152, Nicol et al., June 8, 1976, US Patent 4,166,885 to Derstadt et al., Issued September 7, 1978, Canadian Patent 1,100,262 to Becker et al., May 5, 1981, US Patent 4,238,531 to Rudy et al., issued December 9, 1990, and British Patent Application 2,172,608 to Crossin, issued September 24, 1986.

More recent developments in the field of laundry detergent application ALS include certain protective finishing ester oligomers such as those generally disclosed in Gosselink's United States patents; see, for example, U.S. Patent 4,702,857, October 27, 1987, U.S. Patent 4,721,580, January 26, 1988 and U.S. Patent 4,877,896 to Maldonado, Trinh and Gosselink of October 31, 1989 .

SUMMARY OF THE INVENTION The present invention encompasses soil release agents comprising the oligomeric esterification product of a mixed reaction comprising: = 9 = 35 164,478

5

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Mod. 71-20,000 e *. - 90/08 20

(A) optionally, but preferably a source of C 1 -C 4 (preferably methoxy-terminated) alkoxy terminated, polyethoxy units R - (00-20 - 2) χ - 0 -, or optionally mixtures of said polyethoxy units incorporate small amounts of the propoxy units; (b) one part of terp- thalate units or, optionally, in particular mixtures of terp- thalate and small amounts of the isophthaloyl units; (e) a part of poly (oxyethylene) oxy- (OCH2 CH2) y-O-; (d) a part of oxy-isopropyleneoxy units p -OCHCH2 O-; and (e) a part of oxyethyleneoxy-OCH2 CH2 O- units; said soil release agents being further characterized as having a mole ratio of oxyethyloxy units: oxy isopropyleneoxy units of at least about 0.5: 1?

Suitability-releasing agents, for example, the product of an esterification reaction of a mixed reaction, comprising: a) CH 3 (OCH 2 CH 2) 16 OH; b) dimethyl terephthalate 35 c) polyethylene glycol 1,500 (E,) 10 64 478

10 15

Mod. 71-20,000 ex. D) 1,2-propylene glycol; and e) ethylene glycol; wherein the molar ratio of the oxy-ethyleneoxy: oxy-isopropyleneoxy units is at least about 0.5: 1, preferably at least about 1.25: 1.

Such soil release agents differ from the ALSs disclosed by Gosselink and Diehl, U.S. Patent 4,711,730, supra, as they contain oxy-ethyleneoxy units. The ALS of this invention unexpectedly exhibits better execution than those of the '730 patent. Not intended to be limited by theoretical or structural considerations, it is believed that the preferred ALS for invention are characterized by the general formula: r'o- (ch2ch2o) x

co-ch-ch2o m 25 = \ l Λ A-C0 (CH2CH2O) and 30 n

(CH 2 CH 2) x-R 1, wherein R 2 is lower alkyl (e.g. C 1 -C 4), especially methyl; and R 2 is a mixture of H and CH 2 (both the ethylene and isopropylene moieties are present in the molecular structure) to provide a molar ratio at 35 ° C.

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Mod. 71 -20,000 ex. - 90 (08 64,478

of oxy-ethyleneoxy: oxyisopropyleneoxy of at least about 0.5: 1, preferably at least about 1.25: 1.5 n are In whole numbers formula represented, x, y, and me within the following values: Preferred General More Preferable 10 X 6-100 6-43 12-30 and 6-100 12-77 12-50 m 0.75-30 1.5-25 2.25-20 n 0.25-20 0.5-15 0.75-12 15 m + n + 1 * 1-5 1.2-4.5 1, 5-4 n + 1

This term indicates the average number of adjacent teraphthalate units prior to discontinuation by the PEG unit.

25

It will be understood that the molar ratio of oxysethyleneoxy units: oxypropyleneoxy units; may vary to suit the needs of the formulator. For example, for use with fabric softeners, this ratio is preferably at least about 0.75: 1, more preferably at least about -3.25: 1. For use in liquid detergents, some difficulties may occur in these ratios, so the formulator may choose to select a low ratio, for example, 0.5: 1. The invention also encompasses laundry compositions such as detergents, softeners, rinse additives and the like, comprising at least about 0.1%, preferably about 0.2% to about 10% by weight, of the foregoing ALS. 12 35 1 5

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Preferred fabric softening compositions typically comprise from about 0.3% to about 3% by weight of the ALS and from about 3% to about 25% by weight of a fabric softening component. A liquid, dilutable and concentrated fabric softening composition comprises: a) from about 10% to about 32% by weight of a cationic fabric softener; b) from about 4% to about 20% by weight of an imidazolinium fabric softener; and c) from about 1% to about 5% by weight of the ALS. Typical laundry detergent compositions disclosed herein comprise conventional detersive surfactants, optional activators, optional carriers, and from about 0.1% to about 10% by weight of the ALS. 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 polyhydroxy fatty acid surfactant, especially C-2 fatty acid N-methylglucamide The invention also encompasses a method of providing a tissue-releasing finish by contacting said tissues in an aqueous medium containing at least about of 2 ppm of the preceding ALS. In a preferred mode, the method comprises contacting the fabrics with an aqueous bath comprising at least 3 ppm (preferably about 4 ppm to about 25 ppm) of the foregoing ALS and at least about 10 ppm (preferably about 30 ppm at about 100 ppm) of a cationic fabric softener, for a period of at least 13 hours.

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(preferably from about 1 minute to about 10 minutes) prior to separation of the tissues from the aqueous bath. (It should be understood that even lower levels of ALS may be effective with multi-cyclic treatments). It should be understood that such methods can readily be carried out during the rinse cycle in a conventional automatic washing machine. All percentages, ratios and proportions mentioned herein are by weight, unless otherwise specified. DETAILED DESCRIPTION OF THE INVENTION The Ala of the present invention are prepared by esterification of the hydroxy- and carboxyl-substituted-reactants, disclosed below. The following examples further illustrate the preparation of the ALS according to this invention, but are not limiting. EXAMPLE I Synthesis of a PM 750 Poly (Ethylene Glycol) Methyl Ether Polyether, Dimethyl Terephthalate, Poly (Ethylene Glycol) PM 1500, Ethylene Glycol and Propylene Glycol - A 250 ml 3-necked round bottom flask (THERM-0-WATCH, 1Â °) is added poly (ethylene glycol) methyl ether of MW, 750Â ° C (300Â ° C), and a thermostatic condenser equipped with a magnetic stirrer bar with a modified Claisen head, condenser Aldrich, 50.0 g, 0.067 mol), dimethyl terfthalate (35.6 g, 0.183 mol), polyethylene glycol PM 1500 (Aldrich, 50.0 g, 0.033 mol), ethylene glycol (Baker, 7 (Fisher, 8.9 g, 0.117 mol), tin oxide mono-butyl hydrate (Μ & T Chemicals, 0.30 g, 0.2% by weight reaction total), and hydroxide = 14 = 3515

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butylated luene (Calbiochem, 0.15 g, 0.1% by weight of the total reaction). This mixture is heated to 180-2C and held at that temperature overnight under the action of argon, methanol and distilled water in the reaction vessel. 1 C-NMR (DMSO-d 6) has a residual resonance for methyl esters at 52 ppm. The temperature is raised to 200 ° C for 5 hours, and then additional ethylene glycol (7.2 g, 0.116 mol) and pro-pylene glycol (8.9 g, 0.117 mol) are added. The temperature is lowered to 190 ° C where it is maintained from one day to the next. <1> 1 H-NMR (DMSO-d6) shows this level of the reaction to be completed by the disappearance of the resonance of the methyl esters. The material is transferred to a one neck, round bottomed bottle liter and heated gradually for about 20 minutes at 230 ° C in a Kugelrohr apparatus (Aldrich) at about 1.5 mm Hg and held for 1 hour. The vial is then allowed to cool rapidly to ambient temperature under vacuum. (~ 30 min). The reaction of 124.1 g of a tan solid. (DMSO-d6) has a very tight resonance of about 3.5 ppm for the poly (oxyethylene) segments, a resonance of about 8.0 ppm for the terptalates, resonances of about 1.4 ppm for the methyl group of the doubly esterified propylene glycol, and from about 4.7 ppm to the doubly esterified ethylene glycol. comparison of the resonances at 1.4 and 4.7 ppm indicates that the molar ratio of the ethylene glycol-derivative units to the propylene glycol-derivative units is approximately 2.2: 1. This is referred to as the E / P ratio . C-NMR (DMSO-d6) is also consistent with the desired structure of the polymer, having resonance at 70.2 (polyoxyethylene segments), 16.5 ppm (double esterified CH 2 CH 2), 63.6 ppm (doubly esterified ethylene glycol), and 58.4 ppm (CH₂OCHCC OO)). The lack of resonance of about 60 ppm for any monoester of 15 35 1 64 478

5-ethylene glycol (-COOCOCH-CHOHOH) or about 20 ppm for the methyl group of one of the isomeric monoesters of propylene glycol (- (COCH2CH2CH2OH) indicates that the degree of polymerization is high.

An oligomer with a low E / P ratio can be obtained using the same synthetic conditions, except for the initial ratio of ethylene glycol: propylene glycol which is reduced. Typically, an initial glycol ratio of about 0.25: 1 gives a final E / P ratio of about 0.5: 1. EXAMPLE 2

Mod. 71-20,000 ex. - 90/08

Ethylene Glycol Polymer, Dimethyl Terephthalate, Poly (Ethylene Glycol) Methyl Ether of 750 PM, Poly (Ethylene Glycol) of MW 1,500 and 1,2-Propylene Glycol (with E / P = 1.5) -For one 5 liter 3-necked flask, redon bottom, equipped with a magnetic, heating cover, internal thermometer, distillation head, condenser for switching off, inert gas passage, and a THERM-0-WATCH (I2R) for control of temperature, the following products are placed:

Grams Soft Source Ethylene Glycol 130.2 2.1 MCB Dimethyl Tetraphthalate 640.2 3.3 Aldrich Poly (Ethylene Glycol) 300. or, 4 Union Carbide Methyl Ether M.M. 750 Poly (Ethylene Glycol) 1,500 1.0 Union Carbide of P.M. 1,500 1,2-Propylene Glycol 322 4.2 Fisher 16 ¢ 119¾ 64,478

yy (Cont.)

Grams Soft Source Tin Oxide 5.5 Μ & T Chem mono-butyl hydrate (FASCAT 4,100)

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Toluene hydroxide 3.2 Butylated Carbiochem (HTB)

Mod. 71 -20,000 ex. The system is agitated as the temperature is gradually raised to 185 ° C and thus maintained for 28 hours as methanol discharges the reaction. Thereafter, see frit glass passage tube is inserted near the bottom of the flask and inert gas is passed in high velocity, the temperature gradually rising to 240Â ° C. This process is continued for approximately 13 hours. The resulting polymer is allowed to cool to give about 2400 g of a soft solid which is almost completely soluble in water at room temperature, when tested by overnight stirring at a level of 10% solids. The H-NHR (d 6 -DMSO) has a natural resonance of about 3.45 ppm for the polyoxyethylene segments, a complex resonance of about 8.05 ppm for the teraphthalates, resonance of about 1.4 ppm for the doubly esterified propylene glycol methyl group, and from about 4.7 ppm for doubly esterified ethylene glycol. Comparison of the resonances of 1.4- and 4.7 ppm indicates that the molar ratio of the ethylene glycol derivative units to the propylene glycol derivative units is approximately 1.5: 1. This is referred to as the E / P ratio. 0 ° C-NMR (d 6 -DMSO) is also consistent with the structure of the desired polymer, having resonances at 70.2 ppm (polyoxyethylene segments), 16 ppm (CH of 17 = 35 64,478

A virtually no resonance at about 60 ppm of any of the ethylene glycol monoesters (-C (O) OCH2 CH2 OH) or to about 10 ppm of 20 ppm for one of the isomeric monoesters of propylene glycol (C- (O) OCH (CHq) - (CHgOH) indicates that the degree of polymerization is high.

EXAMPLE III

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Polymer of Ethylene Glycol, Dimethyl Teraphthalate, Poly (Ethylene Glycol) Methyl Ether of PM 750, Poly (Ethylene Glycol) of PM 1500 and 1,2-Propylene Glycol - into a 5-liter, 3-necked flask with round bottom equipped with magnetic mixer, indoor thermometer heating cover, distillation head, condenser for distillation, passage for inert gas, and a THERM-0-2-WATCH (IR) for temperature control, the following products are placed:

Grams Moles Source Ethylene glycol 408 6.58 Fisher Dimethyl terephthalate 1024 5.28 Aldrich Poly (Ethylene glycol) Methyl ether PM 750 480 0.64 Aldrich Poly (Ethylene glycol) PM 1500 2400 1.60 Aldrich 1,2-Propylene glycol 510 6.71 Mallinkrodt Tin mono-butyl oxide. hydrated (FASCAT 4100) 3 M & T Chem Butylated toluene hydroxide (HTB) 3 Calbiochem 18 35 64,478

1 5

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Mod. 71-23,000 ex. The system is agitated as the temperature is gradually raised from 175 ° C to 195 ° C over a period of 36 hours, as 290 g of the distillation product (methanol, for the most part) are added. collected. The temperature is then raised to 210 ° C for 18 hours as more product of the distillation is collected. Thereafter, a passing frit tube is inserted near the bottom of the flask, and inert gas is passed at high speed with the temperature maintained at 200 ° C. This is continued for 4 days as a small amount of the distillation product is collected. The resulting polymer is allowed to cool to give about 3. 800 g of a solid which is about 65% soluble in water at room temperature when tested by stirring overnight at a solids level of 10%. solids content solutions the solvent fraction appears to be considerably high). 1 H-NMR (d 6 -DMSO) exhibits a very strong resonance of about 3.45 ppm for the polyoxyethylene segments, a complex resonance of about 8.05 ppm for the teraphthalenes, resonances at about 1, 4 ppm for the methyl group for doubly esterified propylene glycol, and at about 4.7 ppm for the doubly esterified ethylene glycol. Comparison of the resonances at 1.4 and 4.7 ppm indicates that the molar ratio of ethylene glycol-derived units to the derived propylene glycol units is approximately 1 to 2.6: 1. This is referred to as the E / P ration. ¹H-NMR (D 6 -DMSO) is also consistent with the desired polymer structure, having resonances at 70.2 ppm (polyoxyethylene segments), 16 ppm (doubly esterified CH 2, propylene glycol), 63.6 ppm ethylene glycol double-esterified), and a very fine peak of 58 ppm (CH 2 OCH 2 SO 3). The virtual absence of resonances at about 60 ppm for any ethylene glycol monoester (~C (OCHCHCH2 OH) of 20 ppm for one of the isomeric monoesters of propylene glycol indicates that the grade of 19 = 355

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polymerization is high.

Tissue Treatment Composites

According to this invention, the ALS may be employed in a variety of circumstances where it is desired to give the finished fabrics released from dirt, especially in a laundry operation. For example, these ALS can be added directly to a laundry or rinsing bath of an automatic washing machine. Alternatively, the ALS may be sprayed onto the fabrics during the ironing operation. Otherwise, the ALS may be deposited in the fabrics during a drying operation in an automatic laundry dryer.

From a mocfc &gt; Preferably, they are not deposited on fabrics by an aqueous bath containing fabric softener, such as cationic fabric softeners, well known in the art. In fact, various ALS may be selected from those presented herein which are quite compatible with the cationic ones and do not disadvantageously increase the viscosities, even of the liquid, triple-concentrate, &quot; fabric softener products, which have recently entered the market. In general, low molecular weight ALS will result in lower viscosity increases. Accordingly, the preferred compositions disclosed herein provide both a fabric softening component and an ALS component and are designed to provide a fabric softening (and anti-static) benefit concurrently with a soil release conditioner. The following is intended to assist the formulator in the manufacture of soil release compositions combined with fabric softeners, but is not intended to be limiting

Liquid Fabric Softeners - As 20 1 64,478 1

5

liquid fabric softener compositions of the present invention comprise an effective amount of the above-defined ALS. What is an &quot; effective amount &quot; will depend on the particular ALS used, the particular type of fabric softener formulation and the desired benefits. Generally, ALS's are effective when included in an amount of about 0.01 to about 10% by weight of the composition. In terms of benefits the soil release agents, the preferred fabric softener compositions, may comprise from about 0.1% to about 5% by weight of the ALS, but typically comprise from about 0.3% to about 3% by weight of the ALS. % by weight of these compounds. 15

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The fabric softening compositions of the present invention further comprise from about 2 to about 50% (preferably from about 3 to about 25%) by weight of the fabric softening components. For regular strength (1x) fabric softener compositions the fabric softening component typically comprises from about 3 to about 10% by weight of the composition. For fabric softener compositions, concentrated (eg 3X) the fabric softener component, typically comprises from about 15 to about 25% by weight of the composition. The fabric softening component typically comprises a mono or bi (higher alkyl) quaternary ammonium salt or mixtures of such salts. See U.S. Patent 3,928,213 to Temple et al., December 23, 1975, especially Column 2, line 57 to column 45, line 34, and US Patent 4,399,045 to Bruns, 16 August 1983 , especially from column 4, line 23 to column 7, line 2 (incorporated herein by reference), which has suitable quaternary ammonium salts. By &quot; higher alkyl &quot; as used in the context of the quaternary ammonium salts is intended to mean alkyl groups having from 8 to 30 carbon atoms, preferably from 12 to 22 carbon atoms. EXAMPLE 21

Examples of such conventional quaternary ammonium salts include:

Monobasic quaternary ammonium salts of the formula: â € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒR,

15

Mod. 71-20,000 ex. R 2 is a hydroxyalkyl or saturated alkyl group selected from the groups R 2 (preferred) or R 2 and R 2 is hydrogen; is an anion such as chlorine, bromide or methyl sulphate.

Examples of suitable mono-quaternary ammonium salts are mono-tallowtrimethylammonium chloride (CMSTA), di-tallow-methyl ammonium chloride (CDSMA), di-tallow dimethyl ammonium methyl sulfate, di (hydrogenated tallow) dimethyl ammonium chloride, dibehenyldimethylammonium chloride, dihexadecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, dieicosyldimethylammonium chloride, didocosyldimethylammonium chloride; dihexadecyldiethylammonium chloride, di-tallowdipropylammonium bromide, di (coconut alkyl) dimethylammonium chloride; and mixtures thereof; 2. Quaternary ammonium diammonium salts of the formula: wherein R 1 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy,

5

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Mod. 71-20,000 ex. Wherein R3 is an aliphatic hydrocarbon group R1 and R2 are both divalent alkylene groups having 1 to 3 carbon atoms; R8 is a saturated alkyl or hydroxyalkyl group; is Rg or the moiety (CaH2a0) bH, wherein a, is 2 or 3 and b, is 1 to about 5; and A is an anion.

Examples of suitable quaternary ammonium di-amide salts are methyl bis (tallowamidoethyl) (2-hydroxyethyl) ammonium methyl sulfate, methyl bis (hydrogenated tallow amidoethyl) sulfate (2-hydroxyethyl) ) -ammonium methyl, and ethoxylated methyl sulfate-bis (2-tallow-amidoethyl) ethoxylated ammonium;

These materials are available from Sherex Chemical Company under the trade names VARIS0FT 222, VARIS0FT 220 and VARIS0FT 110; 3. the quaternary imidazolinium salts, such as the sulfate (sold under the tradename VARIS0F 475), 1-methyl-1-tallowamidoethyl-2-tallowimidazolinium methyl (sold under the tradename VARIS0FT 445), sulfate of 1-methyl-(tallowamidoethyl hydrogenated) -2-tallowimidazolaminomethyl (sold under the trademark VARIS0FT 6112); and methylsulphate of 1-methyl-2-tallow-3- [tallowamido-ethylsulaminoethyl] imide zolinium (sold under the tradename VARIS0FT 3012).

For concentrated fabric softening compositions, a fabric softening component comprises: (A) from about 2 to about 25% by weight of mono-quaternary ammonium salts (B) from 0 to about 14% by weight of quaternary ammonium di-amide salts; (C) from about 2 to about 13% by weight of the quaternary imidazolinium salts; The total amount of the salts A, B and C being from about 15 to about 22.5% by weight. See U.S. Patent 4,399,045 to Burns, August 16, 1983 which is hereby incorporated by reference. = 23 = 64,478

The fabric softening component may also comprise certain cyclic amines (higher alkyl, typically as a mixture with a quaternary ammonium salt (salts).) These cyclic amines have the formula: &gt; - R <9

Mod. 71-20,000 e *. Wherein c is 2 or 3, preferably 2; Rg and Rg are independently C1-6 alkyl or alkenyl group; Preferably, alkyl or mixtures of such alkyl radicals, such as those obtained from coconut oil, tallow &quot; soft &quot; (not hardened) and hardened tallow; Q, is CH or N, preferably N; Z is

In which T is O or NR? R?, R?, H or C? -C? Alkyl, preferably H; and R10 is a divalent C6 -C10 alkylene (C1 -C4) alkylene, wherein d is a number from 1 to 8, or

Specific examples of such amines are as follows: 1-tallowamido-ethyl-2-tallowimidazoline; g-alkyl-amido-ethyl) -2- (Î ± -alkyl-4,5-dihydroimidazole; 1-stearyl-amido-propyl-2-stearyl-

10 J 15

Mod. 71-20,000 ex. - 90/08 20

25 64,478 imidazoline; and 1-tallowamido-butyl-2-tallow-piperidine.

These amines and methods for their preparation are fully described in British Application 8,508,130 of March 28, 1985, Koening and Buzzacarini which is hereby incorporated by reference (see also U.S. Patent 4,711,730, column 28). C. Optional Ingredients 1. Acids and Bases - When the amide crystals are present in the fabric softening component, the pH of the fabric softening composition is important for the proper dispersion of the amines. Moreover, a rather acidic pH is preferred for the hydrolytic stability of the soil-releasing compounds of the present invention. Accordingly, acids and / or bases may be added to the composition to adjust their pH. The amount of acid or base should be such that the pH of the dispersion after stirring ranges from about 2.5 to about 6.5.

Examples of suitable acids include inorganic mineral acids, carboxylic acids, in particular the low molecular weight carboxylic acids (C 1 -C 4) and alkanesulfonic acids.

Suitable inorganic acids include HCl, H2 SO4, HNO3 and H2 O3. Suitable organic acids include formic, acetic, methanesulfonic and ethanesulfonic acids. Preferred acids are hydrochloric, phosphoric, formic and methanesulfonic acids.

Suitable bases include NaOH and

Na2 SO4. 2. Organic Solvent - The Compositions 25 1 64,478 1

The fabric softening compositions of the present invention may be formulated without the use of any organic solvent. However, the presence of organic solvents (e.g., water-miscible, low molecular weight aliphatic alcohols) does not impair the storage stability, viscosity or softening of the compositions. Examples of such solvents include ethanol and isopropanol. 10 &gt; 15

Typically, the quaternary ammonium salt (s) (or cyclic amines) will be obtained from a major chemical supplier in solid form or as a solution in an organic solvent, e.g. isopropanol. There is no need to remove such solvent during the preparation of the compositions. In fact, additional solvent may be added if deemed necessary.

Mod. 71-20,000 ex. 3. Nonionic Optional - Nonionic fabric softening compositions as disclosed for use in softening compositions. Such nonionics and levels of use have been disclosed in U.S. Patent 4,454,049, MacGilp et al., Issued June 12, 1984, which is hereby incorporated by reference.

25 35

Specific examples of nonionics suitable for the fabric softening compositions include esters of glycerol (eg glycol monostearate), fatty alcohols (eg stearyl alcohol) and alcoholated fatty alcohols. If used, the nonionic is typically used at a level in the range of about 0.5 to about 10% by weight of the composition.

While considered to generally have fabric softening properties, nonionics are not considered part of the fabric softening component for the purpose of calculating the amount of fabric softening component in the composition. 4. Optional Silicone Component - The composition of &lt; RTI ID = 0.0 &gt; 15

Mod. 71-20,000 ex. - 90/08 20 J 25 64,478

The fabric softener composition optionally contains an aqueous emulsion of a predominantly linear polyalkyl or alkyl aryl siloxane in which the alkyl groups may have from 1 to 5 carbon atoms and may be wholly or partially fluorinated. Suitable silicones are polydimethyl siloxanes having a viscosity at 25 ° C ranging from about 100 to about 100,000 centistokes, preferably ranging from about 1,000 to about 12,000 centistokes. The characteristics of the ionic charge of the silicone, as used in the combination, may be important in determining the extent of deposition and the uniformity of the distribution of the silicone and consequently the properties of the tissue, as treated. Silicones with a cationic character show a marked tendency for deposition. Silicones are considered to be of great value because they provide de facto benefits in the tissues, have a predominantly linear character and are preferably polydialyl siloxanes in which the alkyl group is most often methyl. Such silicone polymers are often commercially manufactured by emulsion polymerization using a strong acid or a strong alkaline catalyst in the presence of a nonionic or mixed, nonionic-anionic emulsifier system. The optional silicone component also comprises a silicone of a cationic character which is defined as having one of: (a) a predominantly linear poly-C1 -C4 -alkyl or -alkyl, aryl polysiloxane prepared by emulsion polymerization using a cationic surfactant as emulsified; (b) an alpha-omega-di-quaternized di-C --C --C --alkyl, siloxane-aryl polymer; or (c) an amino functional polymer di (poly-35-mer alkyl or siloxane aryl-alkyl in which the group = 27 = 15

10 J 15

Mod. 71-23,000 ex. - 90/08 20 J 25 30 64,478

amino group may be substituted and may be quaternized and in which the degree of substitution (G.S.) ranges from 0.001 to 0.2, preferably from 0.01 to 0.073; provided that the viscosity at 25 ° C of the silioone is from about 100 to about 100,000 centistokes.

The fabric softening compositions described herein may contain more than about 10%, preferably from about 0.1% to about 5% of the silicone component. 5. Other Optional Ingredients - In order to further improve the stability of the fabric softening compositions and to further rectify their viscosities, these compositions may contain relatively small amounts of electrolytes (eg 0.1% -3%), such as such as NaCl, KBr, LiCl, MgCl2 or CaCl2. The fabric softening compositions may also optionally contain other ingredients known to be suitable for use in textile softeners. Such adjuvants include perfumes, germicidal preservatives, colorants, driers, fungicides, stabilizers, bleaches, and opacifiers. If used, these adjuvants are usually added to their conventional levels (ca 0.1% - 5%). However, in the case of the composition of the ingredients used for a treatment effect of fabrics for example perfumes, these materials may 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. The following illustrates liquid compositions of the foregoing type. 35 = 28 = 64 478

10

J 15

Example IV

A fabric softener base composition is prepared from the following ingredients:

Ingredient D-tallow dimethyl ammonium chloride 1-methyl-1-tallow-amido ethyl-2-tallowimidazoidinium methyl sulfate (VARISOFT 475)

Weight% 4.33 1.0

Mod. 71-20,000 ex. - 90108 20

Ethanol Isopropanol Perfume * Residual Dyes Water 0,70,1 0,420,1 more than 0,1 Remainder

Preservatives, NaCl, NaOH, anti-oxidant solution. To this base composition is added 1% by weight of the ALS of Examples I and II, respectively, to provide ALSIVA and IVB / fabric softener compositions. 30

Examples V-VIII The average strength and the concentrated fabric softening base compositions are prepared from the following ingredients: = 29 35 64.478

Ingredient Weight% VI VIII VIII Disehodimethyl ammonium chloride 3.65 7.7 2.33 7.0 1-tallowamido-ethyl-2-tallowimidazoline chloride 3.65 14.3 4.33 3.0 Sebotrimethyl chloride -ammonium polydimethylsiloxane 0.5 0.5 - -

25 30

Bactericidal to the base medium strength compositions, VII and VII are added 0.5% by weight of the ALS of Examples I and III respectively. To the concentrated base compositions, VI and VIII are added 1.5% by weight of the ALS of Examples I and II, respectively.

Example IX

A concentrated fabric softener base composition is prepared from the following ingredients:

Mod. 71-20,000 e *. - 90J08 (viscosity 5,000 centistokes 0.2 0.6 1.33 4.0 Perfumes 0.25 0.45 0.25 0.45 * Residuals 0.13 0.13 0.13 0.13 HCl - up to pH 4 - - Water --- Balance --- - - - * = 30 = 35% by weight 13 3 80 ppm 0,265 0,75 0,92 1,36 Balance

Ingredient

Dehydrogenated sebodimethylammonium chloride

Sulfite 1-methyl-1-tallowamidoethyl-2-tallowimidazolinimethyl-methyl

To this concentrated base composition, 1.5% by weight of the ALS of Examples I, II and III, respectively, are added, respectively, to provide concentrated softening compositions plus ALS IXA, IXB and IXC.

Example X

A preferred softening composition is of the following sequence

Ingredient% by weight of the final formula

PREMIX DTDMAC 1% MTTMAC 0.67 VARISOFT 475 * 2.00 5 64.478

Example X (Cont.)

Ingredient PREMIX% by weight of the final formula

15

Mod. 71-23,000 ex. - 70/08

Water based Base Deionized water Silicone DC-15.20 (antifoam) ** Lytron Lytron 621 (ink) ** # ALS After remaining addition0.02 0.35 0.75 2.25 KATH0N (preservative 0.04 **** Poly (dimethyl siloxane) 0.20 Perfume 0.30

25 30 35 *

Imidazolinium fabric softener **

Enough to have a final product with pH of 3-3.5.

Prepared according to Example I; 1.5 E / P ratio

A 55% polydimethylsiloxane water emulsion (350 cps) The premix is combined with aqueous base, then continued with the Post Addition Mixture.

Example XI

Using the ingredients shown = 32 = 64,478

10 &gt; 15

Mod. 71-20,000 ex. In Example X, a 3X concentrated fabric softener is prepared as follows:

Ingredient

% By weight of General Formula DT0MAC VARIS0FT 475 Aqueous Base Deionized Water Silicon DC_-1520 * HCl Lytron 621 (ink) ALS (E / P 1.5 per Example II) 14,676.00

Remainder0.02 0.35 0.75 1, 50

After addition KATH0N Poly (dimethylsiloxane) Perfume 0.04 0.54 1.05 sufficient for the final product to have a pH of 3-3.5

Laundry Detergent - The ALS of the present invention are also useful in certain laundry detergent compositions to provide soil-release properties. These compositions may be used as laundry detergents, laundry additives and pre-laundry treatments.

The laundry detergent compositions of the present invention contain a releasing component = 33 = 64,478

1 of dirt containing an effective amount of HLS previously defined. What is meant by an &quot; effective amount &quot; will depend on the particular ALS used, of the particular type of detergent formulation (liquid, granular, etc.) and the desired benefits. Generally, ALS's are effective when included in an amount of about 0.01 to about 10% by weight of the composition. In the case of soil release benefits, the preferred laundry detergent compositions may comprise from about 0.1 to about 5% by weight of the ALS, but typically comprise from about 0.3 to about 3% by weight of these compounds. 15

Mod. 71-20,000 ex. - 90/08 20 J 25 30

For granular detergent formulations, the ALS component typically comprises the ALS compounds plus any matter which is protective. When making the granular detergent formulations, the ALS can be exposed to highly alkaline materials, such as NaOH and KOH. ALS, in particular those with small key structures, can be degraded by alkaline environments, especially those with a pH below about 8.5. Accordingly, the ALS are preferably coated with a material which protects them from the alkaline environment of a granular detergent formulation, but which allows the dispersion of the ALS in the laundry operation. The coated materials include nonionic surfactants, polyethylene glycol (PEG), fatty acids, esters of fatty acids of diols and polyols, anionic surfactants, film-forming polymers and mixtures thereof. Examples of suitable nonionic surfactant coating materials comprise some of those described below and are also useful as detersive surfactants in the compositions. Examples of suitable PEG coating materials are those having an average MW of about 2,000 to 15,000, preferably from about 3,000 to about 10,000 more preferably from = 34 = 35,164,478

15

Mod. 71-20,000 ex. - 90/08

from about 4,000 to about 8,000. Examples of materials! of coating of higher fatty acids having 12 to 18 carbon atoms. Examples of suitable fatty acid ester coating materials include fatty acid esters of sorbitan (eg, sorbitan monolaurate). Other examples of suitable coating 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 hereby incorporated by reference. The ALS may be coated according to methods set forth in this patent by Murphy et al.

For formulations of liquid detergents :; the ALS component may be fully comprised of ALS or may further include a water soluble organic solvent or a hydrotropy to assist in dissolving the ALS. Suitable organic solvents are generally aromatic and may include ethyl benzoate, phenoxy ethanol, methyl-O-toluate, 2-methoxybenzyl alcohol and pyrrolidone. Suitable hydrotropes include the methyl and polyester-coated small structure PEGs. These polyesters of small structures are more soluble in water and therefore can function as hydrotropes for ALS with their long structures and less soluble in water. The amount or even the need for organic or hydrotropic solvents to prepare liquid detergent formulations containing the ALSs of the present invention will depend upon the ALS used, especially their water soluble fraction, of the ingredients present in the laundry detergent system, and if an isotropic, homogeneous liquid is desired. For the isotropic liquid detergent formulations, it is necessary that the ALS be dissolved as much as possible, which sometimes requires the use of organic or hydrotropic solvents. It is also believed that by dissolving the ALS in the detergent formulations = 35

Mod. 71-20,000 ex. The liquid can make them more effective as soil release agents, facilitating their dissolution in the washing solution and thereby their absorption in the target tissues .

The laundry compositions of the present invention preferably comprise from about 5 to about 75% by weight of a non-interfering, preferably nonionic, detersive surfactant. The nonionic detersive surfactants preferably comprise from about 10 to about 40% by weight of the composition, and more preferably from about 15 to about 30% by weight.

Nonionic surfactants suitable for use in laundry compositions of the present invention are generally disclosed in Laughlin et al., U.S. Patent 3,929,678, December 30, 1975 to column 13, line 14, until to column 16 line 6 (incorporated herein by reference). The classes of the included nonionic surfactants are: 1. The polyethylene oxide is condensed into alkyl phenols. Examples of compounds of this type include nonylphenol condensed with about 9.5 moles of ethylene oxide per mole of nonylphenol. dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol. These 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 Rohm &amp; Haas Company. 2. The condensation products of aliphatic alcohols having from about 1 to about 25 moles of ethylene oxide. The alkaline chain of the aliphatic alcohol may either be linear 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 = 36 = 351 64,478

10 J 15

Mod. 71-20,000 ex. - 90/08 20

N

about 10 moles of ethylene oxide per mole of alcohol and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains having a composition ranging from 10 to 14 atoms of carbon). Examples of commercially available nonionic surfactants of this type include TEHGIT0L 15-S-9, marketed by Union Carbide Corporation, NE0D0L 45-9, NE0D0L 23-6.5, NE0D0L 45-7 and NE0D0L 45-4, marketed by the Shell Chemical Company, and KYR0 E0B, marketed by THE PROCTER &amp; GAMBLE COMPANY. 3. The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. Examples of compounds of this type include some of the commercially available PLUR0NIC surfactants marketed by Wyandotte Chemical Corporation. 4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide with ethylenediamine. Examples of this type of nonionic surfactant include some of the commercially available TETRONIC compounds marketed by Wyandotte Chemical Corporation. Non-ionic, semi-polar detergent surfactants including water-soluble amine oxides containing an alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl and hydroxyalkyl groups from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing an alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl and hydroxyalkyl groups containing about 1 to 3 carbon atoms; and water soluble sulfoxides containing an alkyl moiety of from about 10 to about = 37 = 1 64,478

15

Mod. 71-20,000 ex. - 90/08 20

25

18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of about 1 to 3 carbon atoms. Preferred amine oxide detergent surfactants are C1-C8 alkyl dimethyl amine oxide and C8 -C12 alkoxy ethyl dihydroxy ethylamine oxide. The alkyl polysaccharides shown in European Patent Application 70,074 to Ramon A. Lie , of January 19, 1983, containing a hydrophobic group having from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, eg a polyglycoside, a hydrophilic group of about 1.5 to about 10, preferably from about 1.5 to about 3, more preferably from about 1.6 to about 2.6 saccharide units. 7- Amide fatty acid detergent surfactants (see U.S. Patent 4,711,730, column 17, line 35, for a description of such surfactants). 8. Polyhydroxy fatty acid surfactants; see U.S. Patent 2,965,576 of December 20, 1960; and also GB Patent 809,060. Preferred nonionic detergent surfactants for use in laundry compositions of the present invention are the ethoxylated alcohols and alkylphenols, especially the condensation products of alcohols having from about 3 to about 7 moles of ethylene oxide per mole of alcohol, eg: C 13 -C alcohol, condensed with about 6.5 moles of ethylene oxide per mole of alcohol. The glucamine-amide, N-alkyl type surfactants as described in U.S. Patent 2,965,576 and British Patent 809,060 to E. R. Wilson constitute another class of nonionic surfactants preferred for this use. = 38 = 35 1 64,478 5

The laundry compositions of the present invention may also comprise from 0 to about 15% by weight (preferably from 0 to about 10% by weight) of synthetic anionic detergent surfactants. These synthetic anionic detergent surfactants include the water-soluble salts, typically the alkali metal ammonium and alkyl ammonium 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 oxide of a sulfuric acid ester group (included within the term &quot; alkyl &quot;) is the alkyl moiety of the acyl groups.

Mod. 71-20,000 ex. - 90/08 20 J 25 30

Examples of this group of synthetic anionic surfactants are sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols carbon atoms) and sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in a straight or branched chain configuration, e.g. such as those described in U.S. Patent 2,220,099 and 2,477,383. Included in this class of surfactants are the straight chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C 1 -C 8 LAS. Synthetic anionic surfactants also include: polyethoxylated sulfates; the sodium alkyl glyceryl ether sulfonates; the water soluble alpha-sulfonated fatty acid esters of esters containing about 6 to 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the ester group; the salts of the water-soluble 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and about 9 to about 23 carbon atoms in the alkane moiety; the alkyl sulfates = 39 = 35 64,478

containing about 10 to 20 carbon atoms in the alkyl group and about 1 to 30 moles of ethylene oxide; salts of water-soluble olefin sulfates containing from about 12 to 24 carbon atoms; and beta-alkyloxyalkanosulonates containing from about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane moiety.

The laundry compositions of the present invention may also include cationic and amphoteric, zwitterionic detergent surfactants as well as alkali metal soaps.

Ampholytic surfactants can be generically described as aliphatic derivatives of secondary and tertiary amines, or derivatives of secondary and tertiary heterocyclic amines, wherein the aliphatic radical may have a straight or branched chain and wherein one of the substituents aliphatic radicals contains from about 8 to 18 carbon atoms and at least one contains a water-soluble anionic group, for example carboxy, sulfonate, sulfate. See U.S. Patent 3,929,678 to Laughlin et al., December 30, 1975, column 19, lines 18-35 (incorporated herein by reference) for examples of ampholytic surfactants.

Zwitterionic surfactants can generally be described as derivatives of secondary or tertiary amines derived from secondary and tertiary heterocyclic amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent 3,929,678 to Laughlin et al., December 30, 1975 in column 19, line 38 to column 22, line 48 (incorporated herein by reference) for examples of zwitterionic surfactants.

Suitable cationic surfactants are disclosed in Murphy U.S. Patent 4,259-217, 31 = 40 = 64,478

10J 15

Mod. 71-20,000 e *. · 90/08 20 J March 25, 1981, hereby incorporated by reference.

Useful alkali metal soaps include sodium, potassium, ammonium and alkylammonium salts of fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms. carbon.

The laundry detergent compositions of the present invention may optionally comprise inorganic or organic detergent builders to assist in controlling the resistance of the mineral. Such activators will typically comprise above about 60% by weight of the compositions. Liquid formulations generally comprise from about 1% to about 25% by weight of the binder activators, more preferably from about 3% to about 20% by weight, while the granular formulations generally comprise from about 5% to about of 50% by weight of the detergent activator, more preferably from about 10% to about 30% by weight.

In the literature, a wide variety of detergent activators are known and it is not intended to reproduce here a complete list of such materials. The formulator may refer, for example, to U.S. Patent 4,711,730 at the beginning of column 19, for a typical list of such materials. However, the convenience of the formulator, and not as a limitation, some representative suitable detergent activators are listed below.

Suitable detergent activators include crystalline alumino silicate exchange materials, generally referred to as &quot; Zeolite A &quot;, &quot; Zeolite P &quot; and &quot; Zeolite X &quot;, especially zeolites having a particle size of about 0.1 to about 10 microns. Zeolites, suited for activating purposes, have a calcium ion exchange rate of at least about 4 units / gallon / minute / gram / gallon. Also used are alum- = 41 64,478

Mod. 71-20,000 ex. - 90/08

25 30

non-silicates especially those having a magnesium ion exchange rate of at least about 1 unit / gallon / minute / gram / gallon. A method for producing aluminosilicate ion exchange materials is set forth in U.S. Patent 3,985,669. A particularly preferred hydrated alumino-silicate has the formula:

(SiO 2) 2] x H 2 O wherein x is from about 20 to about 30, especially 28.

Other detergent activators include water-soluble alkali metal (or ammonium) phosphates, polyphosphates, phosphonates, carbonates, siliciates, acetates, polyhydroxysulfonates, and especially polycarboxylates. Various polycarboxylate activators are disclosed in U.S. Patent 3,308,495. Specific examples of preferred polycarboxylate activators for this use are oxy-succinates (aka &quot; oxo-succinates &quot;), mono- and di-succinate tartrate.

Lavender detergent compositions may also optionally include soil and / or antiredeposition soil removal agents and such materials are usually present in a range of about 0.1% a. about 10% by weight of the compositions. Such materials include various ethoxylated amines and the like, referred to in U.S. Patent 4,711,730. Another group of soil and / or antiredeposition soil removal agents are cationic compounds described in Europen Patent Application 11,965 of June 27, 1984. Such materials are also described in great detail in the above cited U.S. Patent 4,711,730. Other optional ingredients that may be included in laundry detergent compositions = 42 = 35 64,478

Mod. 71-20,000 e *. 908 1 of the present invention at levels established by conventional air for use (ie, from about 0% to about 20% by weight) include solvents, bleaching agents, bleach activators, corrosives, paints, additives, bleaches, germicides, pH regulating agents, enzymes, enzyme stabilizers, perfumes, and the like. The inclusion of such optional ingredients in full detergent formulatory compositions is a criterion issue, according to the formulator's objectives. The granular detergent compositions incorporating the ALSs in the present invention may be formed by dry blending the ALS in compositions formed by other conventional techniques, ie by coating the other individual components in water and then atomising by dry spraying the resulting blend , or by drum or pan granulation of the ingredients, or by fluid bed processes. 20 J 25 30

The liquid formulations may be in the form of single phase compositions (preferred) or may be in multiphase or dispersant form &quot;. The dispersions conventionally employ viscosity modifiers to produce systems having plastic shear characteristics to maintain the dispersions stable and prevent phase separation or solids deposition. While the laundry detergent compositions of the present invention are operative within a wide wash pH range, they are particularly suitable when formulated in liquids to provide a near neutral wash pH, ie: an initial pH of about 6.0 to about 8.5 at concentrations 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 the long-term stability of ALS. The pH of the product in such formulations is preferably from about 6.5 a = 43 = 35 64.478 / 10

The following illustrates specific embodiments of laundry detergent compositions employing the ALS of the present invention, but is not intended to be used in the manufacture of laundry detergent compositions. limiting.

Example XII A liquid detergent composition contains

Mod. 71-20,000 ex. - 90J08 20 25

Ingredient * ALS Sodium sulphate C-alkylethoxy (1) 12 C12 polyethoxylated alcohol C13 N-methyl glucamide Ethanol Tetra sodium acetate ethylenediamine

Residuals and H20

Weight% 1.0 9.510.2 7.5 5.5 0.3 Remaining ALS, Example I, above. 30

Example XIII

A granular detergent composition contains 35

Ingredient * ALS

Weight% 3.5 = 44 64,478

Example XIII (Cont.)

Ingredient Weight% Polyethoxylated C 2₂ ^ 13 alcohol 10.0

MgSOâ, "1.0

Zeolite 4A hydrated (1-10 micron) 26.0 18.3

NaHC03 15.0

Maxatase MP (protease) 1.5

Bleach 1.2 Water and Residues to 100 ALS, Example II, above, wrapped in polyethylene glycol with an average MW of 8,000. The composition of Example XIII was prepared using standard mesclage methods to incorporate the ALS.

As can be seen from the foregoing, the ALS of the present invention may be employed from laundry compositions and household type softeners to manufacturing compositions in the care of formers. Alternatively, ALS may, for example, be directly added to rinsing baths in aqueous washings in association with fabrics. Yet as yet another alternative, ALSs may be removably affixed to the sheet substrate, or the like, designated for use in automatic tumble driers. Such: • sheet substrates may additionally have removably affixed various fabric softeners and or antistatic agents of the types = 45 = 64,478 well known in commercial practice. In practice, wet tissues are woven with the sheet substrates thereby causing the ALS, and the optional fabric softeners / antistatic agents, if present, to be transferred from the sheet substrate to the fabric surfaces. These and other methods of applying tissue ALS are also contemplated herein.

While the foregoing Examples illustrate preferred coated ALS, the following illustrates the optional uncoated ALS also covered by this invention. 15

It is envisaged that uncoated ALS may be used in laundry formulations as mentioned above. s

Mod. 71-20,000 ex. 20 J 25 30

Example XIV Synthesis of an Uncoated Oligomer of Dimethyl Teraphthalate, Poly (Ethylene Glycol) (MW = 1450), Ethylene Glycol and Propylene Glycol (with E / P = 2.2) - To a 250 ml bottle of tris bottlenecks, (thermometer), and temperature controller (THERM-O-WATCH IR), PM1450 poly (ethylene glycol) is added (Union Carbide, 93, 3 g, 0.064 mol), dimethyl teraphthalate (25.0 g, 0.129 mol), ethylene glycol (Baker, 16.0 g, 0.258 mol), 1,2-propylene glycol (Fisher, 19.0 g, 0.258 mol), and monobutyltin oxide (M & T Chemicals, 0.27 g, 0.2% by weight of the total reaction). This mixture is heated to 180 ° C and maintained at this temperature overnight under agonist attraction as well as methanol and distilled water from the reaction vessel. A 1 C-NMR (DMSO-d 6) has this level of reaction to be complete by disappearance of the methyl ester resonance at -52 ppm. The material is transferred to a 500 ml vial = 46 = 3515

10 J 15

Mod. 71-20,000 ex. - 20 J 25 30 64,478

single neck and round bottom and gradually heated for about 20 minutes to 240Â ° C in a Kugelrohr apparatus (Aldrich) to about 1 mm Hg and thus held for 40 minutes. The flask is then allowed to cool rapidly under vacuum until it reaches room temperature (~ 30 minutes). The reaction gives 94.8 g of light tan solid. A C NMR (DMSO-dâ, †) has a resonance of 63.2 ppm (diester) -C (O) CHCH2CH2 C (O) a resonance of 59.4 ppm (monoester) and a large peak of 69.8 representing poly (oxyethylene) units. The height ratio of the diester peak to the height of the monoester peak is about 5.8. The appreciable concentration of terminal groups, consisting of monoesters of ethylene glycol, shows that the product is a low molecular weight polymer (2). Peaks in the region 1.1-1.3 ppm show that propylene glycol monoesters are present at an appreciable level. The peak area rate of the methylene groups of ethylene glycol diesters at 4.7 ppm is measured at the peak area of the methyl group of the propylene glycol diesters at ~ 1.4 ppm. From this the ethylene / propylene glycol (E / P ratio) molar ratio incorporated is calculated as 2.2: 1. The solubility is tested by weighing a small amount of material in a flask, adding sufficient distilled water to make a 5% by weight solution, and shaking the flask vigorously. The material is soluble under these conditions. As can be seen from the foregoing, a wide variety of fabric softener compositions and laundry detergent compositions may be prepared using ALS. In fact, modern liquid fabric softeners are currently being supplied as high (5X-6X) liquid (H 2 O) concentrates which are designed to be diluted with water by the consumer at home. Thus, the concentration of the ingredients of Example XI, mentioned above, can be essentially duplicated = 47 = 35

10 J 15

Mod. 71-20,000 ex. 20

64,478 to provide such high concentrates. Thus, compositions comprising from about 10% to about 30% by weight of the cationic fabric softener (eg DTDMAC), from about 4% to about 20% by weight of the imidazolinium fabric softener and from about 1 to about 5% by weight of the above are also encompassed by this invention.

Regarding laundry detergent compositions, the highly preferred compositions comprise from about 0.3% to about 3% by weight of the ALS and as the detersive surfactant from about 3% to about 20% by weight of an acid (see US Pat. No. 2,965,576, corresponding to GB 809 066 cited above, hereby incorporated by reference), preferably in combination with about 5% to about 25% by weight of a sulfated or sulfonated surfactant anionic surfactants such as the alkyl benzene sulfonates O-O-g, C -C-C alquil alkyl ethoxy sulfonates (average EO 3-10, preferred) together with conventional amounts (15 # -50%) of activators conventional compositions, including preferred activators such as Zeolite A, compositions comprising conventional detergent ingredients at conventional levels. 25

Lisbon, 26. JUN. 1992

For, THE PROCTER &amp; GAMBLE COMPANY

is Industrial and Industrial Property, Arcadia-Conceicao, 3, = 48 = 30

Claims (1)

64,478 A release agent comprising the oligomeric esterification product of a mixed reaction characterized in that it has: &gt; 15 Mod. 71-20,000 ex. - 90j08 20 A) Optionally, a source of alkoxy terminated polyethoxy units), or optionally mixtures of said polyethoxy-terminated units incorporating small amounts of the peroxy units; b) a source of terftaloyl units or, optionally, mixtures of terftaloyl and small amounts of isophthaloyl units; c) a source of poly (oxyethylene) units οχί- (00Η20Η2)--Q-; d) a source of oxy-isopropyl-lenoxy units -O-CHCH20-; and e) a source of oxyethylene-oxy-OCH2 CH2 O- units; said soil release agents further characterized in that the mole ratio of oxy-ethyleneoxy units: oxy-iso-propyleneoxy units is at least p: 5: 1. = 49 = 35 64,478 Mod. 71-20,000 ex. 2. A soil release agent according to claim 1, characterized in that it comprises: a) CH 3 (OCH 2 CH 2) 160H; b) dimethyl terephthalate; c) polyethylene glycol 1500 d) 1,2-propylene glycol; and e) ethylene glycol; wherein the mole ratio of oxy-ethyleneoxy: oxy-isopropyleneoxy units is at least 0.5: 1. The soil release agents according to claim 1, characterized in that it has the following general formula: R 2 -CH 2 -CH (Wherein R 2 is lower alkyl (eg C 1 -C 4), in particular R 2, R 2, R 2, R 3, methyl; x and y are each an integer from 6 to 100; m is an integer from 0.75 to 30; n is an integer from 0.25 to 20; and R 2 is a mixture of H and CH 2, for 50 30 64 488 15 Mod. 71-20,000 ex. - 90/08 J 25 providing a mole ratio of oxyethyleneoxy; oxy-isopro-pentoxy of at least 0.5: 1. Soil release agents characterized in that the molar ratio of the oxyethylene: oxy-isopropyleneoxy units is at least 0.75: 1, preferably 1.25: 1. A method of providing the release of fabric dirt by contacting said fabrics with an aqueous medium containing at least 2 ppm of soil release agent prepared according to claim 1. Laundry compositions in the form of detergents, softeners, rinse additives and the like characterized in that they comprise at least 0.1% of the soil release agent prepared according to claim 1. A fabric softener composition according to claim 6, comprising from 0.3% to 3% by weight of the soil release agent and from 3% to 25% by weight of a fabric softening component. The liquid fabric softening composition according to claim 6, characterized in that it comprises: a) 10% to 32% by weight of a cationic fabric softener; b) 4% to 2% by weight of a imidazolinium fabric softener; and c) 1% to 5% by weight of said soil release agent. Laundry detergent composition according to claim 1, characterized in that it comprises conventional detersive surfactants, optional activators, optional conveyors and 0.1% to 5% by weight of a soil release agent. Composition according to Claim 9, characterized in that it comprises 0.3% to 3% by weight of said soil release agent and 3% to 20% by weight of a polyhydroxy fatty acid surfactant. Lisbon, -2E.JW.1992 15 Mod. 71-20,000 ex. - 90/08 20 By, THE PROCTER &amp; GAMBLE CQMPANY ▼ ASCO MMICC LCTW Ag * na CK'fli is »PfCpfiCdf 'Indusinel Office - Arc · a · Conceiçà®, 3, Lô & 25 30 52 35