NZ207692A

NZ207692A - Soil-release promoting liquid detergent containing terephthalate polymers

Info

Publication number: NZ207692A
Application number: NZ207692A
Authority: NZ
Inventors: M C Crossin
Original assignee: Colgate Palmolive Co
Priority date: 1983-04-04
Filing date: 1984-03-29
Publication date: 1986-04-11
Also published as: DK177884D0; FR2543569B1; NO160217C; AT396368B; MY102609A; CA1228275A; PH22091A; FR2543569A1; NL8401065A; MX159212A; CH659080A5; GB2137652B; DK161716B; FI83233C; NO160217B; DE3411941A1; ZW5284A1; BR8401541A; IT8447981A1; AU560819B2

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £07692 Priority Date(sy: 4 /P. . 6.-.G-.S3 Complete Specification Filed: J?!?; "►?;§!/ Class: .C/.<33??. D" [tt"AWl986 Publication Date: P.O. Journal, No: NO SRMSHfiS NZ. PATS /JfOFPlC tL Patents Foi n No. 5 PATENTS ACT 1953 Number Dated COMPLETE SPECIFICATION SOIL RELEASE PROMOTING LIQUID DETERGENT JfWe COLGATE-PALMOLIVE COMPANY, a corporation organised under the laws of the State of Delaware, United States of America of 300 Park Avenue, New York, New York. 10022, United States of America do hereby declare the invention for which #we pray that a Patent may be granted to K>x/uS and the method by which it is to be performed, to be particularly described in and by the following statement: 1 2 07692 This invention relates to liquid detergent compositions. More particularly, it relates to such compositions which contain a soil release promoting polymer which deposits on polyesters and polyester blend materials during washing thereof and promotes the release from them of subsequently applied lipophilic soils. Preferably the liquid detergent nay include an enzyme to assist in cleaning, with a stabilizer for the enzyme, and may alBo include a fabric softening compound, such as a quaternary ammonium salt. Surprisingly, the invented compositions are physically and functionally stable on storage, even when they contain the enzyme(s) and fabric softener(s). Liquid detergents have been employed for the washing of household laundry items in washing machines and have often been applied to soiled areas of the laundry, such as shirt collars, before washing. The employment of copolymers of polyethylene terephthalate and polyoxyethylene terephthalate in detergent compositions as soil release promoting agents has been described in various patents, some of which related to liquid preparations. However, the liquid detergents described are not of the type of the present invention because those of the patents contain triethanolamine and/or ionizable, water soluble salts (other than anionic detergents) which tend to cause separation of the liquid detergent and destabilize the soil release promoting polymer on storage so that it becomes less effective for promoting soil release afterward. 2 07692 In liquid detergents enzymes tend to lose activity on storage unless stabilized, as by salts, e.g., sodium formate, glycols, e.g., propylene glycol, or other such materials. However the mentioned salts tend to destabilize 5 quaternary ammonium halide fabric softeners and the copolymer ■oil release promoting agents which are desirable components of the present liquid detergents, and such destabilization of the soil release agent is especially bad in the presence of lower alkanolamines or salts thereof, such as triethanol-10 amine (TEA), the presence of which will be avoided. Therefore it was surprising that the present liquid detergents could be made in clear and stable non-separating form, with the various functional components thereof being effective after storage at elevated temperatures. 15 In accordance with the present invention a soil release promoting liquid detergent comprises a detersive proportion of nonionic detergent or a mixture of nonionic and anionic detergents, a Boil release promoting proportion of a soil release promoting polymer of polyethylene terephthalate 20 and polyoxyethylene terephthalate and an aqueous medium, in which the pH is in the range of 6 to 9 and in which there is contained no more than 2% of non-(anionic surface active) water soluble ionizable salt. Also within the invention is a method of manufacturing the described compositions. 2 076 92 Preferred such liquid compositions also contain enzymes and enzyme stabilizers, more preferably with fabric softener also being present. Thus a stable enzyme-containing liquid detergent comprises a detersive proportion of a nonionic 5 detergent, a detergent supplementing and fluorescent brightener substantivity increasing proportion of a higher fatty alcohol polyethoxylate sulfate detergent, a soil release promoting proportion of a soil release promoting polymer of polyethylene terephthalate and polyoxyethylene terephthalate, a proportion 10 of enzyme sufficient to enzymatically hydrolyze proteinaceous and/or amylaceous soils on fabrics during washing thereof with an aqueous washing solution of the liquid detergent, a stabilizing proportion of a stabilizer for the enzyme(s), and an aqueous medium, in which the pH is in the range of about 6 15 to 9 and in which there is present no more than 2% of water soluble ionizable material other than the higher fatty alcohol polyethoxylate sulfate detergent. Similarly a stable fabric softening, soil release promoting, enzyme-containing liquid detergent comprises a detersive proportion of a 20 nonionic detergent, a soil release promoting proportion of a soil release promoting polymer of polyethylene terephthalate and polyoxyethylene terephthalate, a softening proportion of a quaternary ammonium salt fabric softener, a proportion of enzyme sufficient to enzymatically hydrolyze proteinaceous 25 and/or amylaceous soils, on fabrics during washing thereof - 4 - 2 07692 with an aqueous washing solution of the liquid detergent, a stabilizing proportion of a stabilizer for the enzyme(s), . and an aqueous medium, in which the pH is in the range of about 6 to 9 and in which there is present no more than 2% 5 of water soluble ionizable material, such as salts and/or triethanolamine. Although various synthetic organic nonionic detergents of satisfactory physical characteristics may be utilized, including condensation products of ethylene oxide and propylene 10 oxide with each other and with hydroxy1-containing bases, such as nonyl phenol and Oxo-type alcohols, for best results it is highly preferred that the nonionic detergent be a condensation product of ethylene oxide and higher fatty alcohol. In such products the higher fatty alcohol is of 10 15 to 20 carbon atoms, preferably 12 to 15 or 16 carbon atoms, and the nonionic detergent contains from 2 or 3 to 20 or 30 ethylene oxide groups per mole, preferably from 6 to 11 or 12. Most preferably, the nonionic detergent will be one in which the higher fatty alcohol is of about 12 to 15 or 12 to 20 14 carbon atoms and which contains from 6 or 7 to 11 moles of ethylene oxide, e.g., 7. Among such detergents is Alfonic^ 1214-60C, sold by the Conoco Division of E.I. DuPont de XO76?2 Nemours, Inc., and Neodols® 23-6.5 and 25-7, available from Shell Chemical Company. Among their especially attractive properties, in addition to good detergency with respect to oily.and greasy soil deposits on goods to be washed, and 5 excellent compatibility with the present polymeric soil release promoting agents, are compatibilities with soluble anionic detergents of the linear higher alkylbenzene sulfonate and higher fatty alcohol polyethoxylate sulfate types, enzymes, enzyme stabilizers, fabric softeners and other 10 components of the present compositions, and long term viscosity stability in aqueous and aqueous alcoholic solutions The anionic detergent which may be employed in the liquid detergents within the broader aspects of the invention is preferably a higher linear alkylbenzene sulfonate or a 15 higher fatty alcohol polyethoxylate sulfate. Normally, water soluble salts of such materials are preferred, such as the alkali metal salts, and of these, sodium salts are usually preferred over the potassium salts. When the anionic detergent is a sodium higher alkylbenzene sulfonate the 20 higher alkyl will normally be of 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms and more preferably 12 or 13 carbon atoms, e.g., 12. When such anionic detergent is a higher fatty alcohol polyethoxylate sulfate, as is the case with the enzyme-containing liquids, in which the detergent 25 increases detergency and promotes an increase in substantivity of fluorescent brightener present, the higher fatty alcohol will be of 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms and more preferably 12 to 13 or 12 to 15 carbon atoms, 6 2 07692 and the polyethoxylate will include 1, 2 or 3 to 20 ethoxy groups, preferably 3 to 10 thereof, and more preferably 3 to 6 or 7, e.g., 3, 6.5 or 7. While not preferred, mixtures of such anionic detergents may be employed in the non-enzyme 5 compositions usually in ratios of 1:10 to 10:1, such as 1:2 to 2:1. Anionic detergents and surfactants will normally be omitted from the fabric softening liquid detergents. The soil release promoting polymer, which is an' essential component of the compositions of this invention, 10 is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate which is soluble (preferred) or disper-sible in water and is depositable from wash water containing the detergent(s) onto synthetic organic polymeric fibrous materials, especially polyesters and polyester blends, ao 15 as to impart soil release properties to them, while maintaining them comfortable to a wearer of clothing made from such materials and not preventing or significantly inhibiting vapor transmission through such clothing. Such polyesters have also been found to possess anti-redeposition properties 20 &nd often assist in removing stains from substrates. They tend to maintain soil, especially oily or greasy soil, dispersed in wash water during washing and rinsing, so that it is not redeposited on the laundry. Useful such products are copolymers of ethylene glycol or other suitable source 25 of ethylene oxide moiety, polyoxyethylene glycol and tere-phthalic acid or suitable source of the terephthalic moiety. The copolymers may also be considered to be condensation products of polyethylene terephthalate, which may sometimes be referred to as an ethylene terephthalate polymer, and 30 polyoxyethylene terephthalate. While the terephthalic - 7 - 20769 moiety is preferred as the sole dibasic acid moiety in the polymer it is within the invention to utilize relatively •mall proportions of isophthalic acid and/or orthophthalic acid (and sometimes other dibasic acids, too) to siodify the 5 properties of the polymer. However, the proportions of such acids or sources of such supplemental moieties charged to any reaction mix, and the' corresponding proportions in the final polymer will normally be less than 10ft each of the total phthalic moieties present, and preferably will be less 10 than 5% thereof. The molecular weight of the polymer will be in the range of about 15,000 to 50,000, preferably being about 19,000 to 43,000, more preferably being about 19,000 to 25,000, e.g., about 22,000. Such molecular weights are 15 weight average molecular weights, as distinguished from number average molecular weights, which, in the case of the present polymers, are often lower. In the polymers utilized the polyoxyethylene will be of a molecular weight in the range of about 1,000 to 10,000, preferably about 2,500 to 20 5,000, more preferably 3,000 to 4,000, e.g., about 3,400. In such polymers the molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate units (considering O o o o N /-.V H « {0CH2CH20-C- (^j) -Ci and -f (OCH2CH2)n-0-C-^(=^-Cf as such units) will be within the range of 2:1 to 6il, - 8 - 2 076 9 2 highly preferably 5:2 to 5:1, even more preferably 3:1 to 4:1, e.g., about 3:1. The proportion of ethylene oxide to phthalic moiety in the polymer will be at least 10:1 and often will be 20:1 or more, preferably being within the range of 20:1 to 30:1 and more preferably being about 22:1. Thus, it is seen that the polymer may be considered as being essentially a modified ethylene oxide polymer, with the phthalic moiety being only a minor component thereof, whether calculated on a molar or weight basis. It is considered surprising that with such a small proportion of ethylene terephthalate or polyethylene terephthalate in the polymer the polymer is sufficiently similar to the polymer of the polyester fiber substrate (or other polymers to which it may be adherent, such as polyaroides) as to be retained thereon during the washing, rinsing and drying operations. Yet, as shown by comparative experiments and various washing tests in which soil release is measured, the described polymer, in the present detergent compositions, iB effective to deposit on washed synthetics, especially polyesters, so as to make them better able to be washed free of oily soil by a liquid nonionic detergent composition or other detergent product. Zt is considered that the polymer's increased hydrophilicity, attributable to the large proportion of hydrophilic ethylene oxide moieties therein, may be responsible for the excellent soil release properties (for releasing lipophilic soils) which 2 07692 it imparts to the material upon which it is deposited, and such may also help it to coact with the liquid nonionic detergent product components. Various literature articles, texts and patents 5 disclose methods for the manufacture of the present polymers, included among which are Journal of Polymer Science, Vol. 3 pages 609-630 (1948) and Vol. 8, pages 1-22 (1951). Although suitable methods for making the instant polymers are described in such references it is considered that 10 none of them discloses the particular polymers which are utilized in the present invention (but such are available commercially) and none discloses the present detergent compositions. Such polymers may be considered as having been randomly constructed from polyethylene terephthalate 15 and polyoxyethylene terephthalate moieties, such as may be obtained by reacting polyethylene terephthalate (e.g., spinning grade) and polyoxyethylene terephthalate or reacting the ethylene glycol, polyoxyethylene glycol and acid (or methyl ester) precursors thereof. Yet, it is also within 20 the invention to utilize more ordered copolymers, such as those made by reacting components of predetermined or known chain lengths or molecular weights, so as to produce what - 10 - 2 076 9 2 might be referred to as block copolymers or non-random copolymers. Graft polymers may also be practicable. The described materials are available from various sources, the products of one of which will be described in 5 more detail here. Useful copolymers for the manufacture of the detergent compositions of this invention are marketed by Alkaril Chemicals, Inc., and commercial products of such company that have been successfully employed to produce satisfactory soil release promoting detergent compositions 10 ar© those sold by them under the trademarks Alkaril QCJ and Alkaril QCF, formerly Quaker QCJ and Quaker QCF. Products available from them in limited quantities, designated by them as 2056-34B and 2056-41, have also been found to be acceptable. The QCJ product, normally supplied as an aqueous 15 dispersion, of about 14 or 15% concentration in water, and preferably used to make the present liquid detergents, is also available as an essentially dry solid (QCF). In both such types of products the molar ratio of ethylene oxide to phthalic moiety is about 22:1. In a 16% dispersion in water, as QCJ, 20 the viscosity at 100°C., is about 96 centistokes. The 2056-41 polymer is like a hard, light brown wax and in it the hydrophile:hydrophobe ratio is about 16 to 1, with the viscosity being about 265 centistokes. The 2056-34B polymer appears to be a hard brown wax, with a hydrophile:hydrophobe 25 ratio of about 10.9:1 and its viscosity, under the same - 11 - ? 076-9 2 conditions as previously mentioned, is about 255 centistokes. The higher the molecular weight of the polymer the lower the hydrophile:hydrophobe molar ratio may be therein and still result in satisfactory soil release promotion by the invented detergent compositions. The QCJ and QCF polymers have melting points (by differential thermal analysis) of about 50 to 60°C., a carboxyl analysis of 5 to 20 or 30 equivalents/10® grams and a pH of 6 to 8 in distilled water at 5% concentration. The molecular weights (weight average) are in the range of 20,000 to 25,000 and the ethylene terephthalatepolyoxyethylene terephthalate units molar ratio is about 74:26. All of the mentioned trademarked products are water soluble in warm or hot water (at 40 to 70°C.) or at least are readily dispersible, and may be characterized as of high molecular weight, over 15,000, generally in the range of 19,000 to 43,000, often preferably 20,000 to 25,000, e.g., about 22,000. The enzymes employed in some of the invented compositions include both proteolytic and amylolytic enzymes, such as the alkaline proteases (subtilisin) and alpha-amylase. Among preferred enzyme preparations that are useful are Alcalase 2.5L (2.5 Anson units per gram) and Termamyl 120L, both manufactured by Novo Industri, A/S. However, other suitable proteolytic and amylolytic enzyme preparations may be used, too. The mentioned compositions are in liquid form and contain 51 of active enzyme in combination with 65% of propylene glycol and 30% of water. In this 12 2 076 9 specification proportions referred to are of the active enzyme(s) in the preparations. The stabiliser or a mixture of stabilizers for the enzjine is most preferably sodium formate or includes such 5 salt, but other water soluble formates, such as potassium formate, can also be employed and acetates may also be useful, as may be other equivalent salts or mixtures of such salts and alkali metal formate. The quaternary ammonium salt fabric softener that 10 is employed in some of the invented liquid detergent compositions may be any suitable such material which is stable in the present compositions. In some instances, known imidazo-linium halides of satisfactory stability may be used instead of the usual quaternary ammonium halides. However, the quater-15 nary ammonium halides are preferred. Such compounds will preferably be chlorides, although bromides and iodides may be useful. Of the four substituents on the quaternary nitrogen at least one,and preferably two, will be a long chain sub-stituent such as higher linear or fatty alkyl, and more 20 preferably, two such substituents will be higher fatty alkyl. The chain length will usually be from 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, with chain lengths of 12 to 14 carbon atoms or mixtures thereof, such as coco alkyl (derived from coconut oil or equivalent 25 feed stock), being most preferred. The other substituents on 13 7. 076 92 the nitrogen will be lower alkyl, usually of 1 to 3 carbon atoms, and of such the most preferred is methyl. Thus, although other quaternary ammonium halides can also be useful, at least when they constitute only sane of the 5 quaternary softener, that which is most preferred and of highest stability in the present liquid detergents is di-coco dimethyl ammonium chloride. Such product is available as a liquid comprising 75% active ingredient, 14% of iso-propanol and 11% of water. 10 The aqueous medium employed includes water and prefer ably also includes a lower alkanol. The water is desirably deionized water but city water of a hardness content up to about 300 p.p.m., as calcium carbonate (the hardness is usually of mixed magnesium and calcium ions) may be employed, 15 although it is preferable for the hardness content to be less than 100 p.p.m. to help to avoid any destabilization of the liquid detergent or separations of parts thereof. Some water may be from the starting materials, such as aqueous soil release promoters, enzyme preparations, softeners, 20 alkanols, and dyes. The lower alkanol may be any of ethanol, isopropanol or n-propanol, but ethanol is much preferred. When ethanol is employed it will normally be as a denatured alcohol, such as 3A, which includes a small proportion of water plus denaturant. Small amounts of 25 compatible dissolved salts may also be present in the aqueous medium but normally such will be avoided to the extent feasible. - 14 - ?07692 Another liquid that may desirably be employed in some of the present liquid detergents, such aB those containing enzymes and fabric softeners,is a lower glycol, such as one of 3 to 6 carbon atoms in the alkyl group thereof. While hexylene glycol may be utilized in some formulations, in some others it can promote instability, so propylene glycol is preferred. Various suitable adjuvants may be present in the invented liquid detergents, such as fluorescent dyes, colorants (dyes and water dispersible pigments, such as ultramarine blue), bactericides, fungicides and perfumes. Concentrations of such components will usually be kept low, often less than 1% and preferably less than 0.7%. Thus, the perfume concentration will usually be less than 1%, preferably 0.2 to 0.6%, e.g., 0.4%. Fluorescent brightenerB or optical bleach compounds may be present in the liquid detergent to an extent of 0.02 to 2%, preferably 0.1 to 1% and more preferably 0.2 to 0.5%. The percentages given are of the commercially supplied materials. Such brighteners are known as cotton brighteners, bleach soluble brighteners, polyamide brighteners and polyester brighteners and generally mixtures thereof are employed so as to make the detergent useful for brightening a wide variety of materials being washed, including cotton and synthetics. Exemplary of such good brighteners *re those identified as: TA; DM; DMEA; DDEA; DMDDEA; BS; NTS; BBZ; AC; DP; BBO; BOS; and NTSA, in a well known article entitled 2 076 92 Optical BrlghtenerB and Their Evaluation by Per 8. Stensby, published in Soap and Chemical Specialties in April, May, July, August and September, 1967. Further discussions of the fluorescent brighteners may be found in an article entitled 5 Optical Bleaches in the Soaps and Detergents by P.G. Villaume, appearing in The Journal of the American Oil Chemists' Society (October 1958), Vol. 35, No. 10, pp. 558-566. Useful fluorescent brighteners are sold under the trade names: Calcofluor White ALF (American Cyanamid); ALF-N (American Cyanamid); SOF 10 A-2001 (ClBA); CWD (Hilton-Davis); Phorwite RKH (Verona); CSL, powder, acid (American Cyanamid); FB 766 (Verona); Blancophor PD(GAF); UNPA (Geigy); Tinopal RBS (Geigy); and RBS 200 (Geigy). The various brighteners are normally present as their water soluble salts but may also be employed in the corresponding 15 acid forms. Most such materials are useful for brightening cotton and are of the Btilbene sulfonic acid (or salt) or aminostilbene types, herein referred to as stilbene brighteners, and a preferred such brightener is Tinopal 5BM Extra Cone., from CXBA-Geigy. For the fabric softening detergent 20 the preferred content of brightener will be from 0.05 to 0.25%, preferably 0.05 to 0.15%, e.g., 0.1%. Colorants, such as Polar Brilliant Blue, will be from 0.001 to 0.03%, preferably 0.002 to 0.2% of the liquid detergent, e.g., 0.0025% or 0.01%, if present. The various adjuvant materials 25 will be chosen for a compatibility with the other formula components and for non-separating and non-settling characteris-tics. Because water soluble ionizable salts, whether inorganic or organic, are generally incompatible with soil release promoting agents, their presence will usually be avoided. - 16 - 207692 Among such salts that are desirably avoided are sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, ammonium chloride and ammonium sulfate, but these are only examples of such salts. While sodium formate 5 should also be omitted from many liquid detergents, surprisingly, a limited proportion thereof has been found to be compatible with the other components of the present formulation, in combination. The presences of ionizable species, such as triethanolamine (TEA), diethanolamine, ethanolamine, diiso-10 propanolamine, n-propanolamine and of the lower mono-, di-, tri- and mixed lower alkanolamines of 2 to 4 carbon atoms per alkanol moiety will be avoided because, like the mentioned salts, they destabilize the soil release promoting polymer and/or the liquid detergent. Of these, TEA appears to be the 15 most destabilizing, causing severe separations of the polymer. In this specification such ionizable species, which may form saltB, should be counted as parts of the permissible proportions of any such salts that may be present. Generally it will be desirable to avoid the presences of other adjuvants 20 than colorants, perfumes, fluorescent brighteners, antioxidants and any neutralizing agents that may be employed to adjust the pH of the liquid detergent to the stable range. It is preferred that any neutralizing agent which may be employed, usually to increase the pH of the liquid detergent 25 mixture, should be alkali metal hydroxide, such as sodium hydroxide, in aqueous solution at a concentration of from 5 - 17 - 2 07692 to 40%, e.g., 15 to 25%. Especially to be avoided are triethanolamine salts and free triethanolamine. The liquid detergent made will be of a desirable viscosity, often in the range of 50 to 500 centipoises, 5 preferably 100 to 200 centipoises, and the viBCOsity may be adjusted by modifying the proportion of lower alkanol, within the range given. The liquid detergent will be readily pourable but will possess a desired "body". The pH thereof will be in the range of 6 to 9, preferably 6.1 to 7.9 and 10 often more preferably 6.5 to 7.5. In the invented soil release promoting liquid detergents of this invention, which are of improved stability on storage so that the soil release promoting polymer and enzyme(s) do not deteriorate and do not separate from the 15 rest of the composition, the proportions of the various components will be as are given below. All the various components recited, although stated in the singular, include mixtures too. The proportions of components that follow are for the broad invention, the enzyme-containing product and the enzyme-20 and softener-containing product, respectively. The nonionic detergent (which includes mixtures thereof) or a mixture of nonionic and anionic detergents (both being of the synthetic organic type) will be within the range of 25 to 50% of the product, preferably being 20 to 40% for the - 18 - 2 07692 nonionic detergent and 3 to 15% for the anionic detergent. More preferably, the proportions of such detergents will be 25 to 35% and 5 to 10%, respectively, e.g., about 32% and about 7%, respectively. The soil release promoting polymer will be about 0.5 to 10%, preferably 1 to 6% and more preferably 1 to 3%, e.g., about 2%. The lower alkanol content will be from 3 to 15%, preferably 5 to 12% and more preferably 6 to 10%, e.g., about 8%, and the water content, when lower alkanol is present, will be about 30 to 60%, preferably 45 to 55%, and if no lower alkanol is present such ranges will be increased to allow for replacement of the lower alkanol with water. The contents of ionizable water soluble salts, whether organic or inorganic, should be kept low, usually being no more than 1% of the liquid detergent, preferably less than 0.5% and more preferably less than 0.3%, and the content of triethanolamine will similarly be limited, to avoid separation of the soil release promoting polymer, with the desirable limits being 0.5%, preferably 0.2% and most preferably 0%. In some instances the Bait content will be held to limits lower than the allowed alkanolamine content because some salts can be even more detrimental to product stability than the alkanolamines. Of course, the content of anionic detergent present, which may be considered to be an ionizable salt, will not be included in the limiting proportions of such salt present because it does not appear to have the same type of destabilizing 19 2 07692 influence on the present compositions. While suitable adjuvants may be present in the liquid detergent, such as the colorant, perfume and fluorescent brightener, previously mentioned, normally the contents of such adjuvants will be 5 minimized, usually being less than 2%, preferably less than 1% and more preferably less than 0.8%, but the dye and brightener are not destabilizing. For the enzyme-containing product (without softener) the synthetic organic nonionic detergent content will 10 normally be within the range of 25 to 40% of the product, preferably being 28 to 36% and more preferably 30 to 34%, e.g., 32%. The fatty alcohol alkoxylate sulfate content will usually be 1 to 8%, preferably 2 to 7% and more preferably 2 to 6%, e.g., 3% or 5%. The fluorescent bright-15 ener content is in the range of 0.02 to 2% and preferably 0.1 to 1%, e.g., 0.2% or 0.4%. The percentage of active ingredient of the brightener may often be 0.01 to 1%, such as 0.01 to 0.1%. The soil release promoting polymer content will be about 0.5 to 5%, preferably 0.8 to 3% and more 20 preferably 0.8 to 2.5%, e.g., about 1% or 2% (on an active ingredient basis). The total enzyme content will usually be in the range from 0.0005 to 0.15%, preferably 0.025 to 0.1%, of which the protease content is 0.005 to 0.1% and the amylase content, if amylase is present, is 0.005 to 0.05%. 25 Preferred contents of the enzymes are 0.01 to 0.11 and 0.01 20 2 07692 to 0.03%, respectively. More preferably, 0.02 to 0.05% is the percentage of protease. Specific formula percentages are about 0.03 and 0.02%, respectively. The stabilizer for the enzymes, usually an alkali metal salt of a lower 5 aliphatic acid of 1 to 3 carbon atoms, such as sodium formate, will usually be from 0.2 to 2%, preferably 0.5 to 1.5%, and aore preferably 0.7 to 1.3%, e.g., 1%. The lower alkanol content will be from 3 to 12%, preferably 4 to 9% and more preferably 5 to 8%, e.g., 5.5 or 7.5%. The water content 10 will be about 40 to 65%, preferably 46 to 62%, more preferably 50 to 60%, e.g., about 54 or 55%. The contents of ionizable water soluble salts, whether organic or inorganic, should be kept low, less than 2%, usually being no more than 1% of the liquid detergent, prefer-15 ably less than 0.5% and more preferably less than. 0.3%, and the content of triethanolamine will similarly be limited to avoid separation of the soil release promoting polymer, with the desirable limits being 0.5%, preferably 0.2%, and most preferably 0%. In some instances the salt content will be 20 held to limits lower than the allowed alkanolamine content because some salts can be even more detrimental to product stability than the alkanolamine. However, in the present compositions the contents of water soluble alkali .metal lower carboxylate, such as sodium formate, may be up to 2% 25 because such components stabilize the enzymes, and at such concentrations, especially at about 1% or less, are compatible with the detergent product and the soil release promoting polymer, so that polymer separation does not occur. - 21 - 2 07692 For the enzymatic and softening liquid detergents the synthetic organic nonionic detergent (which includes Biixtures thereof) content will be within the range of 10 to 35% of the product, preferably being 15 to 30% and more prefer-5 ably 20 to 25%, e.g., 22%. The soil release promoting polymer content will be about 0.5 to 5%, preferably 0.7 to 2% and more preferably 0.8 to 1.5%, e.g., about 1%, (on an active ingredient basis). The content of quaternary compound will be 1 to 10%, preferably 3 to 8% and more preferably 3 10 to 6%, e.g., 4.5%. The enzyme content may be from 0.005 to 0.15%, preferably 0.025 to 0.05%, of which the protease content is 0.005 to 0.1% and the amylase content, if amylase is present, is 0.005 to 0.05%. Preferred contents of the enzymes are 0.01 to 0.05% and 0.01 to 0.025%, respectively. More pre-15 ferably, the content of protease will be from 0.015 to 0.04%. Specific formula percentages are about 0.023 and 0.015%, ; respectively. The stabilizer for the enzymes, a lower aliphatic acid salt, such as sodium formate, will usually be from 0.2 to 2%, preferably 0.5 to 1.5%, and more preferably 20 0.7 to 1.3%, e.g., 1%. The lower alkanol content will be from 1 to 10%, preferably 1.5 to 3% and more preferably 2 to 2.5%, e.g., 2 or 2.2%. The lower glycol content is 2 to 10%, preferably 3 to 8%, more preferably 4 to 7t, e.g., 6%. The water content will be about 40 to 80%, preferably 50 25 to 70%, more preferably 60 to 65%, e.g., about 63%. - 22 - 2 076 9 2 The contents of ionizable water soluble salts, whether organic or inorganic, should be kept low, usually being no more than 1% of the liquid detergent, preferably less than 0.5% and more preferably less than 0.3%, and the content of triethanolamine will similarly be limited to avoid separation of the soil release promoting polymer, with the desirable limits being 0.5%, preferably 0.2%, and most preferably 0%. In some instances the salt content will be held to limits lower than the allowed alkanolamine content because some salts can be even more detrimental to product stability than the alkanolamine. However, in the present compositions the contents of water soluble alkali metal lower carboxylate, such as sodium formate, may be up to 2% because such components stabilize the enzymes, and at such concentrations, especially at about 1% or less, are compatible with the detergent product. The invented liquid detergents may be made by mixing the various components thereof with the aqueous medium, preferably containing at least some of the lower alkanol, until they dissolve (or satisfactorily disperse) therein, or different components may be selectively dissolved in portions of the water and/or lower alkanol and/or lower glycol, and/or liquid soil release promoting polymer preparation, and/or liquid enzyme preparation, and then the various liquid fractions may be mixed together. It will often be preferable to adjust the pH of the liquid to within the range of 6.1 to 7.9, often more preferably 6.5 to 7.5, by 23 2 076 9 2 Addition of a suitable neutralizing agent (not triethanolamine) which will not have a destabilizing influence on the ■oil release promoting polymer, the enzyme(s), the softener, or the liquid product containing them, so that such will not deteriorate and will not separate from the liquid detergent on storage, especially at elevated temperature. The preferred neutralizing agent is an aqueous solution of sodium hydroxide, which will normally be between 10 and 40% sodium hydroxide, preferably 15 to 25%, although more dilute concentrations may sometimes be desirable. Subsequently, the viscosity of the product may be adjusted by means of alkanol and/or water addition. The invented liquid detergent composition may be used to wash (and treat) laundry containing synthetic fibers, <D such as those of polyester, e.g., Dacron^, in the normal manner used in washing with other liquid detergents. However, less of the present product may be employed because of the soil release promoting action thereof, and in many cases the cleaning and softening effects obtained will be superior. Different concentrations of the liquid detergent may be used, normally being from about 0.02 or 0.04 to 0.3 or 0.6%, preferably 0.05 or 0.1 to 0.15 or 0.3%, with the concentration generally being about 1/2 cup per wash in a top loading machine for the product containing softener, and about 1/4 cup per wash for the other two types of products. Generally, it will be advised to use about 1/4 or 1/2 cup (about 60 or 120 ml.) of the liquid detergent per standard wash load (about 07692 1? gallons, for a top loading washing machine), which is a concentration of about 0.1 or 0.2% of the liquid detergent in the wash water. About the same concentration may be used when washing is in a front loading machine, although the water 5 employed is less (so less detergent composition is employed). Normally about 7 or 8 pounds (3 to 3.5 kg.), of laundry will be charged to the washing machine. The wash water temperature will preferably be at least 120°F. (49°C.) but good washing and treatments by the soil release promoting polymer, the enzymes 10 and the softener in the liquid detergent, are obtainable at temperatures in the range of about 40 to 80°C., preferably 45 to 70°C. The dry weight of materials being washed and treated will usually be from about 5 to 15 or 20% of the weight of the aqueous washing medium, preferably about 5 to 15 10% thereof. The wash will be conducted with agitation over a period of about five minuteB to one-half hour or one hour, often from 10 to 20 minutes. Then the washing materials will be rinsed, usually with several rinses, and will be dried, as in an automatic laundry dryer. Preferably, the 20 first washing of the material to be treated will be when that material is not unduly dirty, so that the soil release promoting polymer will be deposited on as clean a surface as possible. However, this is not necessary, and improvements in the cleaning of subsequently soiled materials and swatches 25 will be observed when no special effort is made to have the first washing be that of a cleaner substrate. Up to a - 25 - >2 076 limit, •onetimes about 3 or 5 treatments, plural washings with the liquid detergent of this invention increase the soil releasing properties of the treated material. When polyester and polyester/cotton blend fabrics 5 are washed in the manner described with the compositions of this invention, and are then soiled or spotted with dirty motor oil and washed with a detergent of this invention or another commercial detergent (often of the built type), significant removal of the lipophilic soil is noted, compared 10 to similar treatments in which the liquid detergent employed initially did not contain any soil release promoting polymer. In other comparisons, when substantial proportions of water soluble ionizable salt, such as 5% of sodium sulfate, or more than 1% of triethanolamine or a salt thereof, are present in 15 the liquid detergent it is found that after storage at elevated temperature (43°C.) for two weeks, simulating a lengthier storage at room temperature, phases separate from the liquid detergent body and the soil release promoting properties of the polymer contained therein are diminished, 20 as are the enzymatic and softening activities, when such materials are in the formula. When the enzyme stabilizer is omitted enzymatic action is decreased substantially on storage. Thus, the compositions of this invention are important because they are stable, resulting in more 25 effective products for the purposes intended, soil release improvement, cleaning effects and softening of the 26 - £07692 fabrics laundered, and also resulting in a more attractive liquid detergent composition, which does not separate on storage. The following examples illustrate the invention but do not limit it. Unless otherwise indicated, in the following examples and claims, all parts are by weight and all temperatures are in C. Component EXAMPLE 1 Percent Neodol 23-6.5 (condensation product of approximately 32.0 6.5 moles of ethylene oxide and a higher fatty alcohol averaging 12 to 13 carbon atoms per mole) Sodium linear dodecylbenzene sulfonate (LOBS) 7.0 Sodium sulfate (accompanies the LOBS) 0.2 Soil release promoting polymer (a copolymer of 14.3 polyethylene terephthalate and polyoxyethylene terephthalate of a molecular weight of about 22,000 wherein the polyoxyethylene is of a molecular weight of about 3,400, the molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate units is about 3:1 and the proportion of ethylene oxide to phthalic moiety in the polymer is about 22:1, sold by Alkaril Chemicals, Inc. as Alkaril QCJ, as a 14% solution in water) Denatured ethanol (3A) 8.0 Fluorescent brightener (Tinopal 5BM, Extra Cone.) 0.24 Dye (Polar Brilliant Blue) 0.01 Perfume 0.4 Deionized water q.s. 100.00 N.Z. PATENT Off® - 27 - 0 3FEB 1986 rrr% JaeS * Sm "Ml V > ; 92 The formula liquid detergent is made by nixing together % a portion of the water with the nonionic and anionic detergents, followed by addition of the soil release promoting polymer, the •thanol, fluorescent brightener, dye and any remaining water. 5 Then, an acid or base (NaOH is preferred) nay be used, if desired, to adjust the pH to within the desired range. In the above example the pH is 7.8 (undiluted). However, when the pH is lower than desired an aqueous solution of sodium hydroxide (20%) is used to raise it to the desired level, e.g., 7.5, and 10 the proportion employed is small, e.g., about 0.2% or less NaOH. Next, the formula proportion of perfume is added. The product made is tested by being stored at 43.3°C. for two weeks, after which it is observed to be in a single phase, essentially like that first produced. 15 Shortly after making the liquid detergent it is used to wash a test load of clean fabrics, including some of polyester material and others of 65% polyester and 35% cotton material. The washing concentration is 0.1% by weight of the liquid detergent, on the basis of the weight 20 of the wash water, and the swatches washed are about 5% by weight of the wash water. After washing in a standard testing washing machine, using standard conditions previously described, is completed, the swatches are rinsed and dried. Subsequently each test swatch is stained with about 25 three drops of dirty motor oil of a standard type used for - 28 - 2 07692 such testing and is washed in the Bane type of machine, using a commercial detergent. As controls, swatches that were not previously treated with the present liquid detergent are employed. The washing-treating and subsequent washing temperatures are the same in all cases, being 49SC., which is considered to be an optimum temperature for treat-Bent. In some-experiments, the subsequent washing is with the invented liquid detergent composition. In all experiments the treated swatches are significantly whiter to the eye and by reflectometer testing than the control swatches, showing that the soil release promoting component of the liquid detergent composition effectively aided in the removal of such applied soil from the swatches during the subsequent washings. Also, it is noted that the redeposition onto unsoiled portions of the fabrics of the dirty motor oil removed (from the spotting application) is diminished when soil release polymer is applied to the fabric before test soiling thereof. Thus, the liquid detergent containing soil release promoting polymer, in addition to aiding removal of the soil, also helps to maintain it suspended, inhibiting deposition of such removed soil on other parts of the test material. When 2% or 3% of triethanolamine is present in the liquid detergent of the formula previously given, in replacement of part of the water thereof, after two weeks of storage at 43.3°C. the detergent is found to have separated. Separation also occurs - 29 - 2 07692 under such conditions when the triethanolamine is absent and 5% of sodium sulfate is present in the formula. Also, when the triethanolamine is present, the soil removal promoting action oT the liquid detergent is significantly decreased, 5 compared to the experimental formula of this invention after two weeks of elevated temperature aging at 43.3*C., followed by testing in the manner previously described. Furthermore, storage at room temperature also resultB in such diminution of soil release promoting activity of the formula containing 10 triethanolamine, compared to the experimental formula. When the amount of soil release promoting polymer is decreased to 1% or increased to 3% the same results reported above are obtained, with the modifications that the 3% release polymer formulation is more effective than the 21 15 formula in promoting soil release according to the tests described, and the 1% formula is slightly less effective, although at both 1% and 3% concentrations good and excellent results, respectively, are obtained. When similar tests are made using other lipophilic 20 soils, such as corn oil (red), butter, shoe polish, lipstick, French dressing and barbeque sauce, similar results are obtained, with the greatest improvements of the experimental over the control being with respect to the corn oil, lipstick and dirty motor oil. Release is 100% for the corn oil, 25 butter, French dressing and barbeque sauce stains and is - 30 - 2 07692 almost 100% for lipstick. Similar resultB are obtained when the test fabrics are single knit Dacron , double knit Dacron and Pacron/cotton blends, and are also obtained with treatment temperatures above 32°C. Such results are also obtained when a commercial or home laundry machine of the top loading or side loading type is employed instead of the laboratory testing washing machine. EXAMPLE 2 In the primary formula of Example 1 the sodium linear dodecylbenzene sulfonate is replaced with the corresponding tridecylbenzene sulfonate in one instance and with Neodol 25-3-S, which is the sodium salt of a sulfated condensation product of approximately 3 moles of ethylene oxide and a higher fatty alcohol averaging between 12 and 15 15 carbon atoms per mole, in another instance, and the nonionic detergent is replaced by Neodol 25-7 in both cases. When the compositions resulting are tested for elevated temperature stability and for storage stability, as described in Example 1, similar good results are obtained. Similarly, when more than 0.5% 20 of triethanolamine is present in the compositions in place of an equal proportion of water and/or when 2% of sodium sulfate or other water soluble ionizable salt is present separation of components of the liquid detergent takes place. When the liquid detergents of this example are employed in 25 washing polyester fabrics of the types mentioned in Example 31 - 207692 1, after which the fabrics are soiled and subsequently washed, improved lipophilic soil removals result, compared to controls which contain no soil release promoting polymer of the type used in the formulas of this example. Also, when store than 0.5% of triethanolamine and/or 2% of water soluble ionizable salt, such as sodium sulfate, is present in each of the formulas, after elevated temperature or room temperature aging for periods of two weeks and three months, respectively, if the separated composition is shaken to disperse the various components thereof and is then used in the manner previously described the soil release effect thereof is still diminished significantly, compared to the experimental formulas containing neither triethanolamine nor such salt. EXAMPLE 3 The first formula of the invention given in Example 1 is modified by replacing the anionic detergent thereof with Neodol 25-7, so that the product contains 39% of nonionic detergent, and replacing the ethanol with deionized water. The product is non-separating on storage and is of soil removing characteristics similar to those of the invented products of Examples 1 and 2. Also, the experimental product is stable during accelerated aging at elevated temperature storage and during longer periods of room temperature storage, whereas a comparative product containing 1% of triethanolamine and/or 2% of sodium sulfate separates. Similarly, such comparative products do not help to release deposited lipophilic soil to the extent that is obtainable with the experimental products of this example. 2 07692 EXAMPLE 4 When the contents of the various experimental formulas of this invention, given in Examples 1-3 are varied -10% and -25%, while keeping the proportions of the various 5 materials within the ranges recited in the specification and when, in such formulations instead of employing the QCJ soil release polymer (aqueous solution), 2% of QCF (Alkaril Chemicals CAS 9016-88-0) and 12.3% of water are substituted, with the QCF first being dissolved in the water, good soil 10 release promotings result, like those described in Examples 1-3, and the products made are stable and non-separating on storage. Such is also the case when the fluorescent dye, colorant and perfume are omitted from the formulas of this example. Similarly, when triethanolamine or ionizable salt 15 is present in such formulas beyond the limits given the product becomes less stable and less effective in promoting soil release during washing. In other variations in this example the nonionic detergent is a mixture of equal parts of Neodol 25-7 and 20 Neodol 91-6 and the anionic detergent is Neodol 45-2.25-S. Results like those previously reported in Examples 1-3 are obtainable in both test washing machines and actual laundering, employing either top loading or side loading commercial or household washing machines. Such is also the situation 25 when pH adjustments are with potassium hydroxide and when 33 - 2 07692 such adjustments, made with sodium hydroxide or potassium hydroxide, are to pH's of 7.0, 6.6 and 7.4. Normally such pH adjustments will utilize less than 1% of sodium hydroxide solution, preferably less than 0.5% thereof and more preferably 5 less than 0.2% thereof. In some instances the sodium hydroxide stay be added as a formula constituent in said proportion as iB known to give the desired pH control (based on past experience with the formula) but it will still be preferred for it to be added before the perfume, although such is not necessary. 10 Similarly, while a 20% sodium hydroxide solution concentration may often be preferable, other concentrations thereof may be employed, too. EXAMPLE 5 Component Percent 15 Neodol 25-71 Neodol 45-2.25S2 Alkaril QCJ soil release promoting polymer (15%) Denatured ethanol (3A) 32.0 13.4 3.0 5.5 Sodium formate 20 Alcalase 2.5L^ 1.0 0.6 4 Terroamyl 12 0L Tinopal 5BM"* 0.4 0.27 Dye (Polar Brilliant Blue) Perfume 0.0025 0.4 25 Deionized water q.s 100.00 - 34 - •2 07 1. Condensation product of approximately 7 moles of ethylene oxide and a higher fatty alcohol averaging 12 to 15 carbon atoms per mole 2. Sodium salt of the sulfuric acid ester of the 5 nonionic condensation product of higher fatty alcohol averaging 14 to 15 carbon atoms, with 2.25 moles of ethylene oxide 3. Proteolytic enzyme, sold by Novo Industri, A/S (5% enzyme active ingredient, 65% propylene glycol 10 and 30% water) 4. Amylolytic enzyme sold by Novo Industri, A/S (5% enzyme A.I., 65% propylene glycol and 30% water) 5. A stilbene-type fluorescent brightener, sold by CIHA-Geigy 15 The formula liquid detergent is made in a manner like that of Example 1, by mixing together a portion of the water with the anionic and nonionic detergents, followed by additions of the soil release promoting polymer, the ethanol, fluorescent brightener (sometimes dissolved in ethanol or ethanol-water solutions) 20 enzymes, sodium formate (dissolved in some water), dye, and any 35 2 016 9 ^ remaining water. Then, an acid or base (NaOH is preferred) may be used, if desired, to adjust the pH to within the desired range, e.g., 7. When the pH is lower than desired an aqueous solution of Bodium hydroxide (20%) is used to 5 raise it to the desired level. The proportion employed is small, e.g., about 0.2% or less NaOH. Next, the formula proportion of perfume is added. The product made is tested by being stored at 43.3°C. for a week, after which it is observed to be a clear light blue liquid in a stable single 10 phase, essentially like that when it was made. The protease activity is better than that of a control liquid detergent containing 7% sodium dodecyl benzene sulfonate, 2.8% of triethanolamine (TEA) and no alcohol ether sulfate, and is much better than in other compositions like the control but con-15 taining no sodium formate in one case and no TEA in the other. When both the formate and TEA are omitted from the control formula (in all cases the differences are made up with water) both protease and amylase activities are drastically reduced. The control and the first two variations are unstable on 20 storage, with the polymer settling out. Shortly after making the liquid detergent it is used to wash a test load of clean fabrics, including some of polyester materials and others of 65% polyester and 35% cotton material. The washing conditions are the .same as those 25 in Example 1 and the results are very similar, except for the additional enzymatic cleaning action obtained. Such - 36 - 2 07692 desirable activities are obtained despite the presence in the liquid of the sodium formate and any other salt(s). When 2.8% of triethanolamine or TEA salt is present in the liquid detergent of the formula previously 5 given, in replacement of part of the water thereof, after storage for a week at 43.3°C. the detergent is found to have separated. Separation also occurs tinder such conditions when the triethanolamine is absent and 5% of sodium sulfate is present in the formula. Storage at room temperature also 10 results in such separation and corresponding diminution of soil release promoting activity of formulas containing the indicated proportions of triethanolamine and/or sodium sulfate, compared to the experimental formula. Tests on the liquid detergent for enzymatic cleaning 15 power are satisfactory, indicating that the proteolytic and amylolytic enzymes are functionally effective in the stable liquid detergent. This is so despite the fact that enzymes are often unstable in liquid detergent systems, especially at elevated temperatures. 20 EXAMPLE 6 In a modification of the formula of Example 5, when the proportion of Neodol 45-2.25S is increased to 5%, the proportion of ethanol is increased to 7.5%, 0.01% of Polar Brilliant Blue dye is used instead of 0.0025%, and the brightener 25 i> replaced by 0.24% of Tinopal 5BM and 0.1% of Phorwite BHC, a stable liquid detergent having soil release promoting properties, enzymatic effectiveness and detergency like that of the - 37 - 2 07692 composition of Example 5, or better, results. The liquid detergent is clear blue and in the absence of dye may be of a light color, so that it can be desirably colored by use of other dyes, too. Instead of the brightener system mentioned, 5 equivalent proportions of Tinopal RBS-200, Tinopal 4226 (CIBA-Geigy) or Phorwite RKH (Nobay Chemical Company) and mixtures thereof may be substituted. In all such cases the substantivity of the fluorescent brightener is improved due to the presence of the higher fatty alcohol ethoxylate 10 sulfate and, unlike other anionic detergents, such as sodium linear dodecyl benzene sulfonate, the fatty alcohol ethoxylate sulfate does not destabilize the polymeric soil release promoting agent in the presence of enzyme and enzyme stabilizer. EXAMPLE 7 15 The formula of Example 5 is changed so that 5% of Neodol 25-3S is present instead of the 3% of Neodol 45-2.25S. The product made is stable and clear after storage at elevated temperature, and the Alcalase and Texmamyl stabilities equal those for the primary control mentioned in 20 Example 5. However, when 2.8% of TEA is also present in the formula the product is unstable, with the QCJ soil release polymer flocculating out after storage at 43*C. for one week. - 38 - 2 076 91 EXAMPLE B The contents of the various experimental formulas of this invention given in Examples 5-7 are varied ^10% and ^25%, while keeping the proportions of the various 5 materials within the ranges recited in the specification. In such formulations instead of employing the QCJ soil release polymer (aqueous solution), 2% of QCF (Alkaril Chemicals CAS 9016-88-0) and 11.4% of water are substituted, with the QCF first being dissolved in the water. AIbo other 10 enzymes, stabilizers, alcohols and colorants, as described in the specification, may be employed within the proportion ranges given. The detergents resulting are clear, stable and non-separating and possess good soil release promoting, cleaning and brightening properties, like those described in 15 Examples 5-7. Such is also the case when the fluorescent dye, colorant and perfume are omitted from the formulas of this example. Similarly, when triethanolamine or ionizable salt is present in such formulas beyond the limits given, and when other anionic detergents, such as sodium higher alkyl 23 benzene sulfonates, are substituted for the alcohol ethoxylate sulfate the product becomes less Btable and less effective in promoting soil release during washing, and when the sodium formate is omitted the effects of the enzyme are lost after only a few days storage at the elevated test temperature. - 39 - 2 076 9 2 IrTother variations in this example the nonionic detergent is Neodol 23-6.5 or a mixture of equal parts of Neodol 23-6.5 and Neodol 25-7, with the same total proportion being employed and a stable effective product resultB. Also, the alcohol ethoxylate sulfate may be an equal mixture of Neodols 25-3S and 45-2.25S, and good results are obtained. With such variations results like those previously reported in Examples 5-7 are obtainable in both teBt washing machines and household and commercial washing machines,'which are XO either top loading or side loading. Such is also the situation when pH adjustments are made with potassium hydroxide and when such adjustments, made with sodium hydroxide or potassium hydroxide, are to pH's of 6.6, 7.4, 7.9, and 8.6. Normally such pH adjustments will utilize less than 1% of sodium 15 hydroxide solution, preferably less than 0.5% thereof and more preferably less than 0.2% thereof. In some instances the sodium hydroxide may be added as a formula constituent, in said proportion as is known to give the desired pH control (based on past experience with the formula) but it will 20 still be preferred for it to be added before the perfume, although such is not necessary. Similarly, while a 20% sodium hydroxide solution concentration may often be preferable, other concentrations thereof may be employed too. From Examples 5-B and the preceding descrip-25 tion it is seen that the present invention is of a stable - 40 - 2 076 9? and attractive liquid detergent which contains various components that night have been expected to interfere with the stability of the final product. Yet, surprisingly, a stable product is obtainable in accordance with the invention. 5 Such product has desirable soil release promoting, soil decomposing, fluorescent brightening (when the brightener is present) and detergent properties. Several of the components of the invented compositions exert dual effects therein. For example, the alcohol ethoxylate sulfate aids detergency 10 end helps to make the substrates (laundry fibers) more substantive so that the fluorescent brighteners are more effective. The sodium formate, which is a stabilizer for enzymes, does not destabilize the soil release agent, as would have been expected. The various components of these 15 liquid detergents coact to produce a surprisingly attractive, stable and effective detergent composition. Thus, it is seen that the present compositions represent an unpredictable advance in the art of making.stable products which are preferably attractively clear (transparent or translucent), 20 although in some instances opalescent and semi-clear or intentionally creamy products may be made. - 41 - 2 0769? EXAMPLE 9 Component Percent Neodol 25-7 22.0 Alkaril QCJ soil release promoting polymer (15%) 6.7 5 Adogen 462® 6.0 Propylene glycol 5.0 Denatured ethanol (3A) 2.2 Sodium formate 1.0 Alcalase 2.5L 0.45 10 Termamyl 120L 0.3 Dye (Polar Brilliant Blue) 0.0025 Perfume 0.4 Deionized water g.s. 100.00 15 6. Di-coco dimethyl ammonium chloride, sold by Sherex Industries (contains 75% active ingredient, 14% isopropanol and 11% water) The formula liquid detergent is made in a manner essentially like that used for Examples 5-8 but including 20 the fabric softener and omitting anionic detergent. The product made is tested by being stored at 43.3°C. for a week, after which it is observed to be a clear light blue liquid in a stable single phase, essentially like that when it was made. The protease activity is 70% of that when the liquid 25 detergent was made and the amylase activity is 85% of its initial value. - 42 - 2 076 < Shortly after Baking the liquid detergent it iB used to wash a test load of clean fabrics, including some of polyester materials and others of 65% polyester and 35% cotton material. The washing concentration and the other conditions for that washing are the same as in Example 5 and the results are essentially the same, too, except for improved fabric softening being obtained in this example. Similarly, when 2% or 3% of triethanolamine or TEA salt is present in the liquid detergent of the formula previously 10 given, in replacement of part of the water thereof, after two weeks of storage at 43.3°C. the detergent is found to have separated. Separation also occurs under such conditions when the triethanolamine is absent and 5% of Bodium sulfate is present in the formula. Also, when the triethanolamine 15 is present, the soil release promoting action of the liquid detergent is significantly decreased. Storage at room temperature also resultB in such diminution of soil release promoting activity of formulas containing the indicated proportions of triethanolamine and/or sodium sulfate, compared to the 20 experimental formula. When the amount of soil release promoting polymer is decreased to 0.8% or increased to 2% the same types of results as given above are obtained. Tests on the liquid detergent for fabric softening and enzymatic cleaning power are satisfactory, indicating 25 that the quaternary ammonium halide and the proteolytic and 43 - 2 076 92 amylolytic enzymes are functionally effective in the stable liquid detergent. This is so despite the fact that enzymes and quaternary ammonium halides are often unstable in liquid detergent systems, especially at elevated temperatures. However, replacement of propylene glycol with higher glycols, such as tl>ose of 8 to 12 carbon atoms, will result in separation of the product into two phases. In the particular formula given a complete replacement of propylene glycol with hexylene glycol will also cause phase separation although hexylene glycol and amylene glycol are considered to be useful glycol components of the present type of liquid detergent if employed in lesser proportions and if employed in conjunction with lower glycols, such as propylene glycol. Similarly, if the di-coco dimethyl ammonium chloride is replaced by di-hydrogenated tallow dimethyl ammonium chloride, the liquid detergent also separates into two phases, especially in the presence of the hexylene glycol (in replacement of propylene glycol). However, again, in some circumstances the di-hydrogenated tallow dimethyl ammonium chloride can be employed in a stable product, by decreasing the proportion thereof present and mixing it with di-coco dimethyl ammonium chloride or other di-higher alkyl di-lower alkyl quaternary ammonium halides wherein the higher alkyls are of 12 to 14 carbon atoms and the lower alkyls are of 1 or 2 parbon atoms. As an alternative, a more hydrophilic quaternary ammonium halide, such as ditallow dimethyl ammonium chloride, which possesses a greater degree of unsaturation and thus is more tolerant of electrolytes, may be successfully used. 2 07692 EXAMPLE 10 When, in the primary formula of Example 9, the nonionic detergent is replaced by Neodol 23-6.5, 0.01% of Polar Brilliant Blue dye iB used instead of 0.0025%, and a •tilbene fluorescent brightener is present, e.g., Tinopal RBS-200, Tinopal 5BM or Tinopal 4226 (all sold by CIBA-Geigy), or Phorwite RKH or Phorwite BBP (sold by Mobay Chemical Co.) to the extent of 0.1%, a stable and effective product which functions like that of Example 9 results but it has a greater whitening power due to the presence of the brightener, which is stable in the product. The product of this example is also of attractive clear appearance and is stable on storage. EXAMPLE 11 The contents of the experimental formulas of Examples 9 and 10 are varied -10% and -25%, while keeping the proportions of the various materials within the ranges recited in the specification. In such formulations instead of employing the QCJ soil release polymer (aqueous solution), 1% of QCF (Alkaril Chemicals CAS 9016-88-0) and 5.7% of water are substituted, with the QCF first being dissolved in the water. Also other enzymes, stabilizers, fabric softeners, glycols, alcohols and colorants, as described in the specification, may be employed within the proportion ranges given. The detergents resulting are clear, stable and non-separating and possess good soil release promoting, softening, cleaning and brightening properties, like those described in Examples 9 and 10. 2 07692 Such is also the case when the fluorescent dye, colorant and perfume are omitted from the formulas of this example. Similarly, when triethanolamine or ionizable salt is present In Such formulas beyond the limits given, the product becomes 5 less stable and less effective in promoting soil release during washing, and when the sodium formate and glycol are omitted the effects of the enzyme are lost after only a few days storage at the elevated testing temperature. In other variations in this example the nonionic 10 detergent is a mixture of equal parts of Neodol 23-6.5 and Neodol 25-7, with the same total proportion being employed. Results like those previously reported in Examples 9 and 10 are obtainable in both test washing machines and household and commercial washing machines, which are either top loading 15 or side loading. Such is also the situation when pH adjustments are made with potassium hydroxide and when such adjustments, made with sodium hydroxide or potassium hydroxide, are to pH's of 6.6, 7.4, 7.9, and 8.6. From Examples 9-11 and the preceding examples, as 20 well as the description, it is seen that the present invention is of a stable and attractive liquid detergent despite the fact that it contains various components that might have been expected to interfere with the stability of the final product. Yet, surprisingly, a stable product is.obtained, 25 which has desirable soil release promoting, fabric </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 2 076 9 2. softening, soil decomposing and detergent properties. Several of the components of the invented compositions exert dual effects therein. For example, the propylene glycol may help to solubilize lipophilic materials in the formulation while at the same time helping to stabilize the enzymes. The sodium formate, which is a stabilizer for enzymes, does not destabilize the soil release agent, as would have been expected. Although some quaternary ammonium halides and some glycols can destabilize liquid detergent formulas like those of this invention, the present materials do not do so. This is surprising because hydrophobic quaternary ammonium halides, which are normally flocculated from solution by electrolytes, are stable in the invented liquid detergents. Thus, it is seen that the present compositions represent an unpredictable advance in the art of making stable liquid detergents. The invention has been described with respect to various illustrations and preferred embodiments thereof but is not to be limited to these because one of skill in the art, with the present specification before him, will be able to utilize substitutes and equivalents without departing from the invention. 207652 WHAT WE CLAIM IS:

1. A soil release promoting liquid detergent comprising a detersive proportion of nonionic detergent or a mixture of nonionic and anionic detergents, a soil release promoting proportion of a soil release promoting polymer of polyethylene terephthalate and polyoxyethylene terephthalate and an aqueous medium, in which the pH is in the range of 6 to 9 and in which there is contained no more than 2% of water soluble ionizable salt which is not an anionic surface active water soluble salt.

2. A liquid detergent according to claim 1 wherein the proportion of nonionic detergent or a mixture of nonionic and anionic detergents is within the range of 25 to 50%, the proportion of soil release promoting polymer is within the range of 0.5 to 10% and the soil release promoting polymer is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate of a molecular weight in the range Of substantially -15,000 to 50,000, wherein the polyoxyethylene , of the polyoxyethylene terephthalate is of a molecular weight in the range Of substantially 1,000 to 10,000, with the nnlar ratio of ethylene terephthalate to polyoxyethylene terephthalate units being within the range of 2:1 to 6:1. JiZ#ATENT GFPSSS 2 07692

3. A liquid detergent according to claim 2 which comprises from 20 to 40% of nonionic detergent, which is a condensation product of a higher fatty alcohol of 10 to 20 carbon atoms and 3 to 20 moles of ethylene oxide per mole 5 of higher fatty alchol, from 3 to 15% of anionic detergent selected from the group consisting of sodium linear higher alkylbenzene sulfonate wherein the higher alkyl is of 10 to 18 carbon atoms, and sodium higher fatty alcohol polyethoxylate sulfate wherein the higher fatty alcohol is of 10 to 20 carbon 10 atoms and the polyethoxy is of 3 to 20 ethoxy groups, and from 3 to 15% of a lower alkanol of 1 to 3 carbon atoms. HI ' ►20765-2_

4. A liquid detergent according to claim 3 in which the nonionic detergent is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and 6 to 11 moles of ethylene oxide per mole of higher fatty alcohol, the anionic detergent is sodium linear higher alkylbenzene sulfonate wherein the higher alkyl is of 12 to 13 carbon atoms, the soil release promoting polymer is of a molecular weight in the range of 19,000 to 25,000, the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight in the range of 3,000 to 4,000, the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the polymer is within the range of 3:1 to 4:1 and the molar ratio of ethylene oxide to phthalic moiety therein is from 20:1 to 30:1, the lower alkanol is ethanol, the content of water soluble ionizable salt other than anionic surface active water soluble salt is less than 0.5%, the liquid detergent contains less than 0.2% of triethanolamine and the proportions of nonionic detergent, anionic detergent, soil release promoting polymer, alcohol and water are within the ranges of 25 to 35%, 5 to 10%, 1 to 6%, 5 to 12% and 30 to 60%, respectively. 2 076 9 2

5. A liquid detergent according to claim 4 consisting essentially of about 32% of nonionic detergent which is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and about 7 moles of ethylene oxide 5 per mole of higher fatty alcohol, about 7% of sodium dodecyl-benzene sulfonate, about 2% of soil release promoting polymer of a weight average molecular weight of about 22,000, in which the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight of about 3,400, the molar ratio of 10 ethylene terephthalate to polyoxyethylene terephthalate units of the polymer is about 3:1 and the molar ratio of ethylene oxide to phthalic moiety therein is about 22:1, about 0.2% of fluorescent brightener, about 8% of ethanol, and about 51% of water, wherein the pH is about 7.8, which 15 liquid detergent contains no triethanolamine and in which the content of any water soluble ionizable salt other than anionic surface active water soluble salt that may be present is less than 0.3%.

6. A process for making a soil release promoting liquid detergent which comprises mixing together a detersive proportion of a nonionic detergent or a mixture of nonionic and anionic detergents and a soil release promoting propor-5 tion of a Boil release promoting polymer of polyethylene terephthalate and polyoxyethylene terephthalate in an aqueous medium and admixing with such mixture an aqueous neutralizing agent to adjust the pH of the detergent to within the range of 6.1 to 7.9, which detergent, after such neutralization, 10 contains no more than 1% of water soluble ionizable salt other than anionic surface active water soluble salt. -si-

7. A process according to claim 6 wherein the liquid detergent comprises 25 to 35% of a nonionic detergent which is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and 6 to 11 moles of ethylene oxide per mole of higher fatty alcohol, 5 to 10% of anionic detergent which is a sodium linear higher alkylbenzene sulfonate wherein the higher alkyl is of 12 to 13 carbon atoms, 1 to 6% of a soil release promoting polymer which iB of a molecular weight in the range of 19,000 to 25,000 and in which the 10 polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight in the range of 3,000 to 4,000, the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the polymer is within the range of 3:1 to 4:1 and the molar ratio of ethylene oxide to phthalic moiety 15 thereof is from 20:1 to 30:1, 5 to 12% of ethanol, 0.1 to 0.5% of fluorescent brightener and 30 to 60% of water, with the content of water soluble ionizable salt other than anionic surface active water soluble salt being less than 0.5% and the content of triethanolamine being less than 0.2%, and in which 20 the neutralization is effected with an aqueous solution of sodium hydroxide. 207692

8. A 6table soil release promoting liquid detergent according -to'claim 1 comprising a detersive proportion of a nonionic detergent, a detergent supplementing and fluorescent brightener substantivity increasing proportion of a higher fatty alcohol polyethoxylate sulfate detergent, a soil release promoting proportion of a soil release promoting polymer of polyethylene terephthalate and polyoxyethylene terephthalate, a proportion of enzyme sufficient to enzymatically hydrolyze proteinaceous and/or amylaceous soils on fabrics during washing thereof with an aqueous washing solution of the liquid detergent, a stabilizing proportion of a stabilizer for the enzyme (s), and an aqueous medium, in which the pH is in the range of substantially 6 to 9 and in which there'is present no more than 2% of water soluble ionizable material other them the higher fatty alcohol polyethoxylate sulfate detergent.

9. A liquid detergent according to claim 8 wherein the proportion of nonionic detergent is within the range of 25 to 40%, the higher fatty alcohol polyethoxylate sulfate is a sodium salt and 1 to 8% thereof is present, the soil release promoting polymer is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate of a molecular weight in the range of substantially 15,000 to.50,000, wherein the polyoxyethylene of the polyoxyethylene terephthlate is of a molecular weight in the range of substantially. 1,000 to 10-,000, with the molar ratio of ethylene terephthalate to polyoxyethylene N.Z. PATENT OS**® RECEIVED -S3 2,076 92 terephthalate units being within the range of 2:1 to 6:1, . and 0.5 to 5% thereof is present, the enzyme includes a proteolytic enzyme, and 0.005 to 0.1% thereof is present, and .from 0.2 to 2% of stabilizer for the enzyme is present.

10. A liquid detergent according to claim 9 which comprises from 28 to 36% of nonionic detergent, which is a condensation product of higher fatty alcohol of 10 to 20 carbon atoms and 3 to 20 stoles of ethylene oxide per nole of 5 higher fatty alcohol, 2 to 7% of sodium higher fatty alcohol polyethoxylate sulfate wherein the higher fatty alcohol iB of 10 to 20 carbon atoms and the polyethoxylate is of 1 to 20 ethoxy groups per mole, 0.02 to 2% of fluorescent bright-ener(s), 0.01 to 0.1% of proteolytic enzyme, 0.005 to 0.05% 10 of amylolytic enzyme, 0.5 to 1.5% of stabilizer for the enzyme and from 3 to 12% of a lower alkanol.

11. A liquid detergent according to claim 10 in which the nonionic detergent is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and 6 to 11 moles of ethylene oxide per mole of higher fatty alcohol, 5 the higher fatty alcohol polyethoxylate is one wherein the alcohol is of 10 to 15 carbon atoms and contains 1 to 5 ethoxy groups per mole, the fluorescent brightener is a stilbene brightener, the soil release promoting polymer is of a molecular weight in the range of 19,000 to 25,000, the 10 polyoxyethylene of the polyoxyethylene terephthalate is of a -st- 076 92 molecular weight in the range of 3,000 to 4,000, the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the polymer is within the range of 3:1 to 4:1 and the molar ratio of ethylene oxide to phthalic noiety therein 15 is from 20:1 to 30:1, the enzyme stabilizer is sodium formate, the lower alkanol is ethanol, and the proportions of nonionic detergent, higher fatty alcohol polyethoxylate sulfate, fluorescent brightener, soil release promoting polymer, proteolytic enzyme, amylolytic enzyme, sodium formate, 20 ethanol, and water are within the ranges of 30 to 34%, 2 to 6%, 0.1 to 1%, 0.8 to 3%, 0.02 to 0.05%, 0.01 to 0.03%, 0.7 to 1.3%, 4 to 9%, and 46 to 62%, respectively.

12. A liquid detergent according to claim 11 which is clear and consists essentially of about 32% of a nonionic detergent which is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and about 7 moles of ethylene 5 oxide per mole of higher fatty alcohol, about 5% of sodium higher fatty alcohol polyethoxylate sulfate wherein the higher fatty alcohol is of 12 to 15 carbon atoms and the ethoxylate is of about 3 moles of ethylene oxide per mole of higher fatty alcohol, about 0.3% of stilbene fluorescent 10 brightener, about 2% of soil release promoting polymer of a weight average molecular weight of about 22,000, '.in which the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight of about 3,400, the molar ratio of ethylene terephthalate .to polyoxyethylene terephthalate 15 units of the polymer is about 3:1 and the molar ratio of ethylene oxide to phthalic moiety therein is about 22:1, -J/- 207692 about 0.031 of proteolytic enzyme, about 0.02% of anxiolytic enzyme, about 1% of sodium formate, about 5.51 of ethanol, about 0.4% of perfume and about 54% of deionized water.

13. A stable fabric softening, soil release promoting liquid detergent according to claim 1 comprising a detersive proportion of a nonionic detergent, a soil release promoting proportion of a soil release promoting polymer of polyethylene terephthalate and polyoxyethylene terephthalate, a fabric softening proportion of a quaternary ammonium halide fabric softener, a proportion of enzyme sufficient to enzymatically hydrolyze proteinaceous and/or amylaceous soils on fabrics during washing thereof with an aqueous washing solution of the liquid detergent, a stabilizing proportion of a stabilizer for the enzyme(s), and an aqueous medium, in which the pH is in the range of substantially 6 to 9 and in which there is present no more than 2% of water soluble ionizable material. i NX l-ATg-n- C^>*; 0 3FEB1986 p&Z&fafED -St,' 207692

14. A liquid detergent according to claim 13 wherein the proportion of nonionic detergent is within the range of 10 to 351, the soil release promoting polymer is a polymer of polyethylene terephthalate and polyoxyethylene 5 terephthalate of a molecular weight in the range of substantially 15,000 to 50,000, wherein the polyoxyethylene of the polyoxyethylene tarephthlate is of a molecular weight in the range Of substantially 1,000 to 10,000, with the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate 10 units being within the range of 2tl to 6sl, and 0.5 to 5% thereof is present, the quaternary ammonium halide is a di-higher alkyl dimethyl ammonium halide and 1 to 10% thereof is present, the enzyme includes a proteolytic enzyme, and 0.005 to 0.1% thereof is present, and from 0.2 to 2% of the 15 stabilizer for the enzyme is present.

15. A liquid detergent according to claim 14 which comprises from 15 to 30% of nonionic detergent, which is a \ condensation product of higher fatty alcohol of 10 to 20 carbon atoms and 3 to 20 moles of ethylene oxide per mole of 5 higher fatty alcohol, 3 to 8% of quaternary ammonium halide, which is a chloride and in which the higher alkyls are of 12 to 18 carbon atoms, 0.005 to 0.05% of proteolytic enzyme, 0.005 to 0.05% of amylolytic enzyme, 0.5 to 1.5% of a stabilizer for the enzymes and from 1 to 10% of a lower alkanol. N'.£. PATENT Qpygig 0 3FEBJ986 RECgtVEO "SI- 2 07692

16. A liquid detergent according to claim 15 in which the nonionic detergent ia a condensation product of higher fatty alcohol of 12 to 15 carbon atoms and 6 to 11 moles of ethylene oxide per mole of higher fatty alcohol, 5 the soil releasing polymer is of a molecular weight in the range of 19,000 to 25,000, the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight in the range of 3,000 to 4,000, the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the 10 polymer is within the range of 3:1 to 4:1 and the molar ratio of ethylene oxide to phthalic moiety therein is from 20:1 to 30:1, the quaternary ammonium halide is di-coco dimethyl ammonium chloride, the enzyme stabilizer is sodium formate, the lower alkanol is ethanol, from 2 to 81 of 15 propylene glycol is present and the proportions of nonionic detergent, soil release promoting polymer, fabric softener, proteolytic enzyme, amylolytic enzyme, Bodium formate, ethanol, propylene glycol and water are within the ranges of 20 to 25%, 0.8 to 1.5%, 3 to 6%, 0.015 to 0.03%, 0.01 to 20 0.025%, 0.7 to 1.3%, 1.5 to 3%, 3 to 8%, and 50 to 70%, respectively. - si- 2.07^^

17. A liquid detergent according to claim 16 which is clear and consists essentially of about 22% of a nonionic detergent which is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and about 7 aoles of ethylene 5 oxide per mole of higher fatty alcohol, about 1% of soil release promoting polymer of a weight average molecular weight of about 22,000, in which the polyoxyethylene of the polyoxyethylene terephthalate is of a molecular weight of about 3,400, the molar ratio of ethylene terephthalate to 10 polyoxyethylene terephthalate unit;* of the polymer is about 3:1 and the molar ratio of ethylene oxide to phthalic moiety / therein is about 22:1, about 4.5% of di-coco dimethyl ammonium chloride, about 0.023% of proteolytic enzyme, about 0.015% of amylolytic enzyme, about 1% of sodium formate, 15 about 2% of ethanol, about 6% of propylene glycol, about 0.4% of perfume and about 63% of deionized water. WEST-WALKER, McCASE per: ATTORNEYS FOR THE APPLICANT -s°t - </div>