NL8801961A - NON-IONIC DETERGENT WITH IMPROVED DIRT-RESISTANT POWER. - Google Patents

Description

i * VO 1232

Non-ionic detergent with improved dirt repellency

This invention relates to non-ionic synthetic organic laundry detergents with improved soil resistivity. More particularly, the invention relates to detergent compositions, both in finely divided solid and liquid forms, which contain a polyethylene-5-terephthalate-polyoxyethylene terephthalate (PET-PGET) copolymer as a neat soil repellency promoter along with a tight etoxyate ( MIE) nonionic detergent which acts as a detergent, but also significantly improves the effect of the PET-POET copolymer to promote soil repellency.

The improved activity of the disclosed soil repellant compositions is most pronounced when the laundry to be washed (which is treated simultaneously with a soil repellant promoter) consists of a fabric or fabrics comprising synthetic organic polymeric fibrous materials in especially polyesters, and when washing at a low temperature, e.g. 10-30 ° or 15-25 ° C.

Before the present invention, it was known to prepare finely divided synthetic organic detergents with bumpers using non-ionic detergents and phosphate and / or non-phosphate builders. The non-phosphate builders used include both water-soluble and water-insoluble builders. The soluble builders include alkali metal silicates, carbonates, bicarbonates and borates, while the water insoluble builders include zeolites.

All of which are well known in the art. Such compositions are described in a number of U.S. patents ref. Applicant, where products of this type in which non-ionic detergent liquid liquid is absorbed in the spray-dried builder salt base granules are marketed by Applicant under the trademark FRESH START.

PET-POET polymers have been proposed as components of finely divided detergents, in which they promote the release of contaminants from laundry which are applied later. Patents describing such polymers and their function include British Patent 1,088 * 984 and U.S. Patent 3,962 * 152. U.S. Pat. No. 3,962,132 discloses poly-8001961 "2 * 1-2" -acrylates in zeolite builder detergents and U.S. Patent 4,283 * 299 discloses polyacrylate in nonionic phosphate builder detergents because of its anti-graying function.

It has also been indicated in the prior art that polymers that promote soil wetting, such as those used in the present invention (PET-POET), can be incorporated into liquid detergents. It is also known that nonionic detergents are useful detergent components in liquid detergents. In some liquid detergents, both PET-POET 10 copolymer and wide-range ethoxylate nonionic detergents (BRE) have been used.

U.S. Patent 4,441,881 discloses NRE nonionic detergents containing a builder and a small amount of modified cellulose ether, such as hydroxypropylmethyl-15 cellulose or methyl cellulose, as "soil blockers". In this patent, the disclosed nonionic detergent is a higher fatty alcohol narrowly polyethoxylate (NRE) nonionic detergent, which is indicated to smoke or vapor less from the top of a spray tower when a crust mixture, which contains such a non-ionic detergent, it is spray dried. In said patent it is also stated that in the compositions described there, the NRE gave such composition superior cleaning power over similar compositions in which conventional or broad-range etoxylates (BREs) were used as nonionic detergents. It should be noted that in the foregoing sentence and also later, in order to prevent repetition of "nonionic detergent", NRE and BRE relate to such detergents, and not only to types of the etoxy units thereof.

US patents 4,569 * 772 and 4 * 571, 303 both disclose detergents related to some of those of the present invention, except that none of these patents disclose NREs or disclose or imply that use of NREs instead of the BREs in such detergents would lead to a synergistic improvement in the properties of the PET-POET copolymer in such detergents to promote soil removal performance.

Although various components of the present compositions have been incorporated in the prior art. 8801961 "3" - 3 - it is believed

that detergents consisting of a combination of NRE and PET-POET

copolymer are new and that due to the unexpectedly beneficial effects obtained thereby (reinforcement of dirt removal), it is disturbed.

5 has been demonstrated with other formulations based on BRE's obvious nature of the invention.

Although the prior art disclosed above relates to various combinations of the required components of the compositions of the invention, it is not taught to those skilled in the art from NRE * s rather than BREs in detergent compositions containing builders containing PET-POET contain polymers as soil removers, with or without polyacrylate stabilizer (in the finely divided formulation with builders) and from such knowledge it cannot be inferred that the present compositions would have an improved soil removal effect due to the presence of NRE non-ionic detergents instead of BRE non-ionic detergents.

According to the present invention, a detergent composition having improved soil removal performance with improved soil depletion promoting properties in cold water washing of polyester-containing fabrics contaminated with oily soil, which improved soil removal is due to the presence therein of a narrow ethoxylate (NRE) nonionic detergent and a removal promoter of polyethylene terephthalate-polyoxyethylene-25 terephthalate (PET-POET) copolymer instead of a broad-range ethoxylate (BRE) nonionic detergent and PET-POET copolymer, detergent purposes sufficient amount of such an NRE type nonionic detergent, consisting of a polyoxyethylated lipophilic substance, ethoxylated at an average of 5-10 ethylene oxide groups per mole, with at least 70% of the ethylene oxide in polyethoxy groups having 4-12 ethylene oxide is present, as well as sufficient for dirt-removing purposes amount of a PET-POET copolymer as a diluent-promoting agent. Also included within the invention is a laundry washing method utilizing the improved soil removal properties by repeatedly washing the laundry with the composition of the invention.

The active detergent component of the present compositions. 8801061 "4" - 4 and methods consists essentially of a nonionic detergent. Anionic synthetic organic detergents have a tendency to inactivate PET-POET copolymers or may interfere with their soil removal capacity, probably by interfering with the deposition of such copolymers from the wash water on the laundry. However, it is sometimes possible to use anionic detergents in relatively small amounts in substantially non-ionic detergent compositions without this having a detrimental effect on the promotion of soil removal by the PET-POET copolymer.

Preferred nonionic detergents are those which are NRE reaction or condensation products of ethylene oxide and a suitable lipophilic or lipophilic material. Preferred reactants with ethylene oxide are higher alcohols, usually fatty alcohols having 12-18 carbon atoms per molecule, which are the desired provide nonionic detergents for the composition of this invention, but oxo-type alcohols and intermediate phenols, such as nonylphenols, are also useful.

Other members of this well-known class of nonionic detergents, such as higher fatty acid esters of ethylene oxide, are also useful in some formulations and for certain purposes. Preferably, a higher fatty alcohol is used as the lipophilic agent, while the ethylene oxide condensation product is a close ethoxylate nonionic detergent (NRE). By strictly ethoxylate is meant a polyethoxylated lipophile, ethoxylated with ethylene oxide, such that at least 70% of the ethylene oxide in the non-ionic detergent is present in polyetoxy groups with n to (n + 8) moles ethylene oxide per mole, wherein n may be 1-10, although n is preferably 3-5 and especially about 4.

Thus, the narrowly ethoxylate (NRE) nonionic detergent preferably contains at least 70% ethylene oxide thereof in polyethoxy groups containing 4-12 ethylene oxides. Most preferably, such groups contain 5-10 etoxy groups and make up at least 80 or 85% of the etoxy group content of the NERs. Instead of ethylene oxide, in some cases mixtures of ethylene oxide and propylene oxide can be used in such NRE1s, provided that the final product has the desired and unexpected beneficial properties, together with the PET-POET copolymer, which will be described in more detail below "8801961 - 5 - tf '* - 5 - described, such that the removal of the dirt is improved, compared to compositions containing the same PET-POET copolymer but using the normal nonionic detergents of the art instead, i.e. the broad-range ethoxylate 5 (BRE) nonionic detergents. Although it is preferred for the polyetoxylates of the NREs that they fall within certain ranges of etoxy group content in the polyetoxy units thereof, the preparation methods usually result in mixtures of polymers, so that average etoxy group contents must be indicated. Thus, the NRE 10 nonionic detergents will contain on average 4-12 or 5-10 ethylene oxide groups per mole e.g. an average of about 6 or 7 EtOs per mole. The preferred lipophilic substance is from a high fatty alcohol and therefore the ethylene oxide content of the NRE nonionic detergents will be at least 70% higher fatty alcohol ethoxylates with an average of 5-10 ethylene oxide groups per mole, most preferably at least 80 or 85% of the ethylene oxide will be present in such higher fatty alcohol ethoxylates. This can be compared to about 50% or less of such polyetoxy groups in the BREs.

The high fatty alcohol of the higher fatty alcohol ethoxylates will also preferably contain 12-14 carbons, although the fatty alcohol may sometimes contain 10-16 or 12-16 carbons. It is within the scope of the invention to use synthetic lipophilic substances, such as those derived from higher fatty alcohols with odd numbers of carbon atoms in the indicated ranges, or those derived from higher fatty alcohols with even numbers of carbon atoms, such as in natural products, wherein mixtures thereof can also be used.

The NREs currently available are preferably prepared by catalyzed condensation reactions that promote the formation of a narrow range of polyetoxylates rather than the more commonly broad range of polyetoxylates in the alkoxylated lipophilic detergent. Catalytically formed products are characterized by a normal distribution curve when the ethylene oxide (X-axis) content is plotted against the weight percentage (Y-axis), but the peak of the "bell-shaped" curve is not much higher for the NRE than for the BRE ionic detergents. Similar products with similar distribution curves are available from BRE's or .8801861. 6.

To "top" other NREs and "remove the bottom fraction", such as. by removing higher and lower polyetoxylates by solvent extract! ash, distillations and other suitable physical methods.

The BRE nonionic detergents will contain lower percentages of highly desirable polyetoxylates, such as those with 4-12 or 5-10 EtOs, often less than 50%, compared to more than 70% for the NREs. They will also comprise at least about 1% of all unit degrees of etoxylation of 1-16 or 1-20, even if it is desired that the average ethylene oxide content e.g. at 7 moles is 10 per mole. An NRE with an average of 7 moles of EtO per mole usually does not have a higher polymer of ethylene oxide than 15, with the amounts of polyoxyethylene in the 4-12 and 5-10 EtO ranges being significantly increased. Due to such an increase and the narrower distribution range of the polyetoxy units, the properties of the NRE are clearly improved when it is incorporated in a detergent composition containing PET-POET copolymer. The reason for this effect is not fully understood at present, but it may be related to a lesser interference of the nonionic detergent on the deposition of the PET-POET copolymer on the detergent substrate prior to the final removal of the dirt from subsequent washing. Within the "peak" area of an NRE curve, such as from 5-10 etoxy groups per polyoxyethylene unit, the percentages of the 5-10 EtO units for the NREs, compared to BREs, can range from 15% or more to 60 % or more, with the peak differences for the 7 and 25 EtO polyetoxylates.

Among preferred NRE nonionic detergents useful in the present invention is Tergitol

non-ionic detergent 24-L-60N, which has the formula RO (CHgCHgO) -H

wherein R is a mixture of straight alcohols and n 30 is on average about 7.0. Such a product has a cloud point of 60 ° C for a 1% aqueous solution and is a narrow ethoxylate. The properties are described in a product information brochure published by the manufacturer, Union Carbide Corporation, the

bearing that date of April 1987. Other Tergitol non-ionic wax-35 active substances that are also at least partly with the 24-L-60N

useful, including 26-L-60N, 24-L-45N and 24-L-75N, the 60, 45 and 75 indicating the cloud points in degrees C.

.8801961 7 # - 7 -

It is also possible to substitute similar products manufactured by Shell Chemical Company identified as Shell 23-7P and Shell 23-Z, although the results will not be as satisfactory.

Etoxylate distributions of the various NREs are listed in brochures on Tergitol surfactants entitled Etoxylate Distribution of Tergitol 24-L Nonionic Detergents by Gas Chromatography, published by the Ethylene Oxide Derivatives Division of Union Carbide Corporation. The following table, Table A, summarizes the ethoxylate distribution (by gas chromatography) of two of the above preferred NREs and of comparable BREs.

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The PET-POET copolymers of this invention usually have molecular weights ranging from 19000 to 43000, most preferably about 19000 to 25000, especially about 22000, according to molecular weight assays performed on samples thereof which are commonly used. Such molecular weights are weight average molecular weights, distinguished from number average molecular weights, which are usually lower for the subject polymers. In the polymers used, the polyoxyethylene will usually have a molecular weight in the range of about 1000 to 10000, preferably about 2500 to 5000, most preferably 3000 to 4000, especially 3400.

In such polymers, the mole ratio of the polyethylene terephthalate to polyoxyethylene terephthalate units (considering the groups of formulas 1 and 2 of the formula sheet as such 15 units) will range from 2: 1 to 6: 1, preferably 5: 2 to 5: 1, most preferably 3: 1 to 4: 1, and in particular are about 3: 1.

The amount of ethylene oxide relative to the phthalic acid unit in the polymer is normally at least 10: 1 and will often be 20: 1 or 20 more, and is preferably from 20: 1 to 30: 1, particularly preferably about 22: 1. It is thus seen that the polymer can essentially be considered a modophic ethylene oxide polymer, the phthalic acid unit being only a minor component thereof, be it on a molar or weight basis. It was considered surprising that with such a small amount of ethyl. 8801 961 - to - ί - 10 - leen terephthalate or polyethylene terephthalate in the copolymer, such a copolymer being sufficiently equivalent to the polymer of the polyester fiber substrate (or other polymers to which it can adhere, such as polyamides) to be washed thereon during the wash, rinse - and be held dry for 5 steps.

While the PET-POET copolymer described is the polymer normally used by the applicant of the present invention, and is highly preferred because of its desired functions, other PET-POET polymers, such as some of those described in U.S. Patent 3,962,152 and British Patent 1,088,984 are used and they may sometimes be effective soil removal promoters in the composition of the invention. Usually, however, the soil removal promoting properties of such materials are less good than those of the preferred polymers.

The PET-POET copolymers useful in the practice of the present invention are available from Alkaril Chemicals,

Ine. in powder or aqueous dispersion form as Alkaril QCF (powder) and Alkaril QCJ (aqueous liquid). For the preparation of liquid detergent compositions, the use of the QCJ product is of course preferred. Other copolymers which also contain polyacrylate stabilizer (usually in a 4: 1 copolymer: polyacrylate weight ratio) are supplied by that company under the names Alkaril Base C and Alkaril Vel veto! 251-C.

Various builders and combinations thereof which effectively supplement and improve the performance of the non-ionic synthetic organic detergents, especially in finely divided detergents, include both water-soluble and water-insoluble builders. Of the water-soluble builders, both inorganic and organic builders are useful, but the inorganic are preferred, usually as all potassium salts. Among the water-soluble inorganic builders are preferred: various phosphates, usually polyphosphates, such as the tripolyphosphates and pyrophosphates, more particularly the sodium tripolyphosphates and sodium pyrophosphates, e.g. pentasodium tripolyphosphate, tetrasodium pyrophosphate; sodium 35 carbonate, sodium bicarbonate; sodium silicate; sodium borate or borax; and mixtures thereof. Instead of a mixture. 8801 961 '11' 4 - 11 - of sodium carbonate and sodium bicarbonate it is sometimes possible to use sodium sesquicarbonate. The alkali metal or sodium silicate, when used, normally has an iOiSiOS or ^ OrSii ^ ratio within the range of 1: 1.6 to 1: 3, preferably 1: 2.0 to 1: 2.8, e.g. 1: 2.4 (or 1: 2.35).

Of the water-soluble inorganic builder salts, phosphates, if not objectionable, can be used, sometimes with a small amount of sodium silicate. In the preferred nonphosphate compositions, carbonates can be used in conjunction with bicarbonates and sometimes with borates and / or small amounts of sodium silicates.

Silicates are rarely used alone. Instead of using individual polyphosphates, it is sometimes better to use mixtures of sodium tripolyphosphate and sodium pyrophosphate in ratios ranging from 1:10 to 10: 1, preferably 1: 5 to 5: 1. Obviously, changes in the phosphate chemical structure may occur during slurry making and spray drying so that the final phosphate content may be slightly different from the phosphate components added to the crutch, as those components have been indicated herein. . Although sometimes water-soluble organic builders can also be used, such as tri-sodium nitrilotriacetate (NTA), water-soluble inorganic builders are generally preferred, as already indicated above. The various water-soluble builder salts can be used in hydrated forms, which is sometimes preferred, while the water-soluble builders, hydrated or anhydrous, are normally sodium salts, or mixtures of alkali metal salts, with sodium salts usually being preferred. In some cases, such as when producing neutral or slightly acidic detergent compositions, the acidic forms of the builders are preferred, but normally the salts are either neutral or basic in nature, and usually have a 1% aqueous solution of the detergent composition a pH in the range from 9 to 11.5, e.g. 9 to 10.5.

Advantageously, insoluble builders, usually of the zeolite A type, usually hydrated, such as with 15 to 25% hydrate-35 water, can be used in the compositions of the present invention.

Hydrated zeolite X and Y are also useful, as well as in the fe8801961, 2 - 12 - naturally occurring zeolites and zeolite-like materials and other insoluble ion exchanger compounds that can act as builders for detergents. Of the various zeolite A products, the zeolite 4A is often preferred. Such materials are well known in the art and processes for their preparation need not be described here. Usually such compounds have the formula (Na 2 O) x. (Al 2 O 3) y./SiO 2) zw H 2 O wherein x is 1, y is 0.8-1.2, preferably about 1, z 1.5-3.5, 10 is preferably 2 to 3 or about 2 and w is 0-9, preferably 2.5-6.

The zeolite builder should be a univalent cation-exchanging zeolite, i.e. it should be an aluminosilicate of a univalent cation, such as sodium, potassium, 1 ithium (when feasible) or another al potassium metal, or ammonium. Preferably, the univalent cation of the zeolite type mentioned is an al-potassium cation. especially sodium or potassium, most preferably sodium, as indicated in the previous formula. The zeolites, either crystalline or amorphous, are capable of reacting rapidly with hard water calcium ions such that, alone or in conjunction with other water softening compounds in the detergent composition, they soften the wash water before adverse reactions of water hardness ions with other components of the synthetic organic detergent composition take place. The properties of the zeolites can be indicated as a high exchange capacity for calcium ions, which is normally about 200 to 400 or more mg. equivalents of calcium carbonate hardness per gram of the aluminum minosilicate, preferably 250 to 350 mgeq./g. is, on an anhydrous zeolite basis. Preferably, they also rapidly reduce the hardness in wash water, usually within the first 30 seconds to 5 minutes after they are added to the wash water, whereby they can reduce the hardness to less than a milligram of CaCO3 per liter within such a time period. The hydrated zeolites have a normal moisture or hydrate water content in the range of 5-30%, preferably about 15-50%, and most preferably 17-22%, e.g. about c 8801 961 - 13 - 20¾. The zeolites as fed to a crutch mixture from which the base grains are made should be in a finely divided state, the final particle diameters being up to 20 microns, e.g. 0.005 to 20 µm, preferably 0.01 to 8 µm average particle size, e.g.

3 to 7 microns if crystalline and 0.01 to 0.1 microns, e.g. 0.01 to 0.05 micrometers, if amorphous. Although the final particle sizes are much lower, usually the zeolite particles have sizes within the range of a No. 100 to 400 screen, preferably a No. 140 to 325 screen, (US series) as fed to the crutcher for the preparation of the basic granules. In the base grains, the zeolite is usually accompanied by a suitable builder salt or salts, e.g. sodium tripolyphosphate and sodium silicate (in relatively minor amounts) or sodium carbonate and sodium bicarbonate. Sodium silicate can sometimes form agerates with zeolites so that the amount thereof in the zeolite builder base granules is limited, or the sodium silicate can be omitted altogether, especially from the carbonate-containing mixtures, but sometimes up to 10¾ in the final detergent compositions present, such as others when no suitable binder or anti-corrosion agent is present.

The polyacrylate used to stabilize the ΡΕΤ-Ρ0ΕΤ copolymer in the finely divided compositions is a low molecular weight polyacrylate, such as al potassium polyacrylate, e.g. sodium polyacrylate, the molecular weight of which is usually in the range from about 1000 to 5000, preferably in the range from 1000 to 3000, and most preferably between 1000 and 2000, e.g. is about 2000. The average molecular weight is normally in the range of from 1200 to 2500, such as from 1300 to 1700. Although other water-soluble polyacrylates may sometimes be substituted for some of the disclosed sodium polyacrylate, including some other alkali metals. polyacrylates, e.g. potassium polyacrylate, it is preferred that such substitution, when permitted, be limited to a minor amount of the material; preferably the polyacrylate used is an unsubstituted sodium polyacrylate. Such materials are available from Alco Chemical Corporation under the name of Alcosperse.

c 8801 961 '4 - t - 14 -

The sodium polyacrylates are available as clear amber liquids or powders, completely water-soluble, the solutions having a solids content of about 25 to 40%, e.g. 30%, and the pH of such a solution or of a 30% water solution of a powder is in the range of 7.5 to 9.5. Preferred products of these are currently sold as Alcosperse 104, 107, 107D, 109 and 149, of which Alcosperse 107D is a particularly preferred 100% solids powder, although Alcosperse 107, a 300% water solution, may also be used instead, with little difference in results (provided it is dried first). Both are sodium polyacrylates with the liquid (107) having a pH in the 8.5 to 9.5 range and the pH of the powder (107D) in the 7.0 to 8.0 range at 30% concentration in water. The powder is preferably anhydrous but it may contain a minor amount of water, normally less than 10%, which is largely removed during each melting operation carried out, such as when the PET-POET copolymer and the polyacrylate are melted together and then cooled until they solidify .

To make the stabilized soil widening enhancing polymer components of the compositions of the invention, the PET-POET polymer is melted by applying it to a temperature above its melting point, preferably to a temperature within the normal procedure. range from 70 to 150 ° C to liquefy, after which powdered solid sodium polyacrylate is added thereto. When a uniform melt is obtained, it can be cooled, after which the solidified mass can be reduced by suitable means. Preferably, cryogenic grinding or flocculating operations are used such that the product is in the form of finely divided powder or flakes, which are readily miscible with other finely divided powder components of a formulated detergent without unacceptable demixing phenomena. A cryogenic size reduction, which is often undertaken at a temperature below 0 ° C and sometimes below -50 ° C, is performed by grinding or other size reduction operation in the presence of liquid nitrogen or other cryogenic material. Optionally, a suitable grinder may be used .8801961 5 '- 15 - such as a hammer mill, a cage mill or a Raymond Imp mill, and instead of liquid nitrogen or another liquid cryogenic coolant, one can use solid carbon dioxide (dry ice) with mix the resins to be ground, or other cooling options can be utilized to prevent overheating of the material and keep it in a cold, easily breakable form; the listed grinders, others with equivalent functions can be used, including the Raymond Ring Roll Mill, which contains an internal separator and is capable of producing very finely divided resinous materials.

Instead of using cryogenic or low temperature grinding devices to reduce the solidified melt of PET-POET and polyacrylate, the melt can be sprayed and cooled to the desired grain sizes, usually through a No. 10 15 sieve (US sieve series ) and are preferably passed through a No. 30 screen.

The products produced by using the described method of the present invention can be considered as a PET-POET copolymer bearing polyacrylate. Because the amount of polyacrylate is relatively small (although its effect is significant), the PET-POET copolymer provides a medium for the distribution of the polyacrylate through a detergent composition with which it is mixed. In addition to the stabilizing effect of the polyacrylate on the PET-POET copolymer, the polymer thus promotes the dilution of the polyacrylate so that it is more uniformly distributed throughout the detergent composition and thereby imparts more uniformly desirable properties of the polyacrylate to such composition, such as promoting clay contamination of laundry during washing and preventing graying of the laundry during washing. The "carrying" of the polyacrylate through the stabilized polymer also eliminates the need to spray the detergent granules or base granules with a polyacrylate solution to evenly distribute them throughout the detergent composition.

The stabilized PET-POET copolymers, with which the preferred polyacrylate stabilizer is in close contact, are used in the present invention for their soil wicking promotion in 8801961. "_ • * - 16 - the detergent compositions described. It has been found that laundry, especially laundry in which the fabrics consist of polyesters or polyester fiber blends (often with cotton), is more likely to have various contaminants in the wash water during washing with synthetic organic detergent composition with builder, especially those based on nonionic detergents, release, if the soiling of the laundry occurs after it has been washed with such a detergent composition containing the PET-POET copolymer. Some of the copolymer is retained on the laundry during the wash operation so that it is present thereon when the laundry is subsequently soiled, its presence promoting the removal of the later applied dirt and / or stains during a subsequent washing step. It would be expected that the polyacrylate, in the same particles as the PET-POET copolymer, would promote dispersion of the polymer and prevent its deposition on the laundry, but this is not the case. Instead, the polyacrylate increases the soil removal promoting activity of the PET-POET polymer in detergent compositions. One mechanism that provides this enhancement is that the polyacrylate counteracts the decomposition or degradation of the polymer when it comes into contact with alkaline materials, such as in such builder detergent compositions in which the builder salt is alkaline (as many of them are), in especially at elevated temperatures.

In addition to the NRE, builder and PET-POET copolymer, or in addition to the three components and polyacrylate stabilizer mentioned, the finely divided detergent composition of the invention usually also contains water (or moisture) and one or more auxiliaries. A wide variety of adjuvants are useful in the finely divided products, such as those normally present in the detergent compositions of various types, but in the present compositions, preferred adjuvants include enzymes, such as mixed proteolytic and amylolytic enzymes, fluorescent whiteners, such as Stil bone. whiteners, dyes, such as colorants and pigments, mixing aids, such as citric acid materials and magnesium sulfate and perfume. In some cases, fabric softeners, such as bentonite or quaternary ammonium halides or amines, are used and sometimes can. 6801961 * r.

- 17 - - 17 - flow improvers, which often contain special clay products. Bleaches such as sodium perborate and bleach activators can be included in the present composition, often in greater amounts than any of the other auxiliaries used, being most likely to be useful in hot water wash detergent compositions. Fillers such as may also be present.

In the finely divided detergent compositions of the invention, normally 10-35¾ of the NRE nonionic detergent 10 is present, preferably 15-25%, most preferably about 20%. The builder content is usually within the range of from 30 to 75%, preferably from 55 to 70%, and most preferably from 58 to 61%, e.g. 58 and 61%. When the detergent composition contains phosphates, the phosphate content is normally in the range of 30 to 75%, with 0 to 15% water soluble silicate, preferably 50 to 65% sodium tripolyphosphate, and 2 to 10% sodium silicate, and most preferably about 58 % sodium tripolyphosphate and about 5% sodium silicate. For detergent compositions without phosphates, the builders content is usually 30 to 75%, consisting of 15 to 40% ion exchange zeolite, 10 to 30% sodium carbonate and 5 to 20% sodium bicarbonate, preferably 55 to 70% in total, with 20 to 40% zeolite, 15 to 25% carbonate and 5 to 15% bicarbonate, and most preferably about 61% total builder, with 30% zeolite (anhydrous base), 20% carbonate and 11% bicarbonate. The percentages of PET-POET copolymer 25 for both types of detergent compositions are usually in the range of 0.5 to 10%, preferably 2 to 6%, most preferably about 4%, while the percent ranges for the polyacrylate stabilizer usually range from 0.1 to 5%, preferably 0.5 to 5%, and the most preferred percentage is about 1%. The ratio of sodium polyacrylate to PET-POET copolymer is normally within the range of 1: 6 to 1: 2, and is preferably 1: 5 to 1: 3, most preferably about 1: 4.

The amount of auxiliary agents, with the exception of bleaches and fillers, which may make up 5 to 40% of the detergent composition in total, with the required components proportionally reduced as compensation, is usually not more than 10% of the total composition , and is preferably less than 5% c 8801961 18 '- 18 - thereof, and most preferably is in the range of 1 to 4%, eg 2 and 4%, for finely divided detergent composition with phosphate builder and without phosphate, respectively. Individual excipients (other than bleaches, bleach activators and fillers) normally make up less than 2% of the composition, and often less than 1.5%.

To prepare the finely divided detergent compositions, base grains of inorganic builder are made by using an aqueous crust mixture of such a builder or builder mixture, usually at a solids content in the range of 40 to 75%, at a temperature in the 40-75 range. and spray-drying it in a spray tower at a temperature in the range of 250 to 450 ° C, obtaining substantially spherical granules with a particle size in the range of the numbers 10 to 100 US sieve series. If larger and smaller particles are also produced by spray drying, they can be sieved or air-sorted to the desired range or other such range that is considered acceptable for the intended purposes. Then, in the spray-dried granules after cooling, the non-ionic detergent liquid liquid is absorbed therein by spraying the desired non-ionic liquid detergents in the present case, the NRE non-ionic detergent, on the moving surfaces of the granules. and. An advantage of the present invention is that the NREs are liquid at room temperature (25 ° C) or are at least more easily liquefied by heating than BREs and thus penetrate better into the interior of the spray dried base granules, thereby improving processing and allowing more free flowing products. The PET-POET copolymer can be dispersed and / or dissolved in the non-ionic detergent and absorbed in the spray-dried base grains with the non-ionic detergent, but in particular when polyacrylate stabilizer is used to improve the soil removal promoting properties of the PET -POET copolymer, the copolymer melts together with the polyacrylate, after which the melt can be allowed to solidify, either by spray cooling to particles with dimensions equal to those of the base granules, or the size can be appropriately reduced in a cryogenic manner .

See U.S. Patent No. 4, 569,772 which is incorporated herein by reference c 880 1 96 1 - 1 - - 19 - for a more detailed description of the preparation of the stabilized copolymer. The spray dried base beads containing the nonionic detergent and the stabilized polymer can then be mixed together and various other auxiliaries not previously included in such components can be added afterwards by mixing and / or spraying. Usually such auxiliaries include enzymes and perfumes, with flow improvers of choice being added. Sometimes anti-static agents will also be added afterwards, either as finely divided solids or in a liquid state. Such post additions are normally made in a suitable mixing equipment, such as an inclined drum mixer, but usually any suitable type of mixing equipment can be used.

The finely divided compositions of the invention are used in substantially the same manner as described in U.S. Patent 4,571,303, which is hereby incorporated by reference, with the suitability for commercial use being tested against a wide variety of impurities. found in normal washing, including dirty motor oil, because an important advantage of the strong-acting nonionic detergent compositions or similar binder compositions is that they effectively remove oily stains from the laundry, in particular special laundry that contains polyester fiber materials. In examining the effect in such applications, wipes of the material to be investigated, such as single knitted polyester, double knitted polyester, woven polyester and polyester / cotton blends, are pre-washed with an automatic top loading washing machine with a capacity of 67 liters, water of hardness 150 ppm, as calcium carbonate (mixed calcium and magnesium hardness) at regular intervals with a 10 minute wash cycle, after which the laundry is rinsed, spun and then dried in an automatic laundry dryer (with a 30 min cycle drying). The light reflections from the canvases are then read and averaged. Then cloths are stained, such as with dirty motor oil (usually three drops per cloth) and then left overnight.

The next day, the reflections of the stained areas of such fabrics are read and the wipes are washed and dried in the manner previously described, followed by readings of the reflections of the previously stained areas. If the reflection of the non-stained wipe is Rd ^ and that of the stained wipe for washing is Rd25 and the final reflection is Rd3, the percentage of dirt removal is 5 (Rdg-Rd2) / (Rd ^ -Rd2) x 100. Obviously averages are taken for a plurality of wipes so that the average percentage of soil removal for a particular stain on a particular material, for a plurality of stains on such a material, for a particular stain on a plurality of materials, or for a plurality of stains on a 10 multiple of materials can be found.

the

Thus, soil removal promoting activity of the detergent composition can be compared to that of another composition by comparing the percentages of soil removal under identical washing conditions. Normally, cold water washing is the most difficult test for a detergent composition and, therefore, comparisons under such conditions are considered a strong indication of the activity of experimental detergent compositions, with such experimental cold water stain removal compositions and best wash often being those produced by the Consumers' 20s are most appreciated. Furthermore, cold water washing is energy saving, less expensive and within the reach of more countries in both the industrialized and third world countries, so that the removal of dirt and stains under such washing conditions is particularly desirable.

According to the above test, the NRE nonionic detergent compositions of the present invention synergistically enhance the soil removal promoting effects of the ΡΕΤ-Ρ0ΕΤ copolymer significantly compared to similar compositions in which the NRE components are replaced by the BRE nonionic 30 detergents. In comparative tests where the ΡΕΤ-Ρ0ΕΤ copolymer is present in the same types of detergent compositions, no superiority of the NRE nonionic detergent-containing composition over the BRE compositions is shown. It is thus clear that the strong improvement in soil removal advancing effect of the present compositions (and methods) is due to a collaboration of the PET-POET copolymer soil removal promoter and c-8801 96 1 -21 -21- the NRE non-ionic detergent, • which collaboration or synergy is not evident from the prior art.

In liquid detergent compositions of this invention, the fluorescent brighteners are substantial with respect to the washed laundry and serve to convert the invisible radiation into visible light, making the laundry surfaces on which these compounds are deposited appear whiter. Such fluorescent brighteners are a known group of materials in the detergent art 10 and therefore need not be described in detail. Suffice to note that they are normally of the stilbene type and more particularly they are of the Stilbenesulfonic acid or sulfonic acid salt type. Brighteners used in the compositions of the present invention are e.g. manufactured by Mobay Chemical 15 Corp., sold under the trademarks Phorwite HRS and Phorwite BHC, containing 4,4l-bis-4-anilino-6- (methylamine) -s-triazin-2-yl-amine-2,2 ', respectively -stilbene disulfonic acid and 4,4'-bis- (4-phenyl-2N-1,2,3-triazol-2-yl-1,2 "" Stilbene disulphanic acid, are potassium salt. Although the aforementioned fluorescent brighteners are The present composition works very effectively, one may also use other types of substantive whiteners instead, without losing the unexpected beneficial improvement in the soil removal characteristic of the compositions of the invention.

Also, in preferred embodiments of the liquid detergent compositions of the invention, an anionic detergent may be included to enhance the substantivity of the fluorescent whitener while also adding their defensive properties to the composition (anionic detergents are particularly effective in removing particulate impurities from tissues). The anionic detergent agent is preferably of the sulfate or sulfonate type, normally in the form of a water-soluble salt, such as an al potassium metal e.g. the sodium salt. Such detergents are described in detail in various textbooks, including Surface Active Agents (Their Chemistry and Technology) 35 by Schwartz and Perry, and the various annual releases of John W. McCutcheon's Detergents and Emulsifiers.

. 880 1 96 1. 22.

- 22 -

Although higher fatty alcohol sulfates and various other sulfates and sulfonates are useful, it is preferred that the detergent be a higher alkyl benzene sulfonate, such as one having an alkyl group of 12-18 carbon atoms. Most preferably, the alkyl 5 is straight and contains 12-16 carbon atoms, e.g. dodecyl and the cation is sodium.

An enzyme component of the present compositions may be any suitable enzyme which is effective against a particular type of contamination found on the laundry to be laundered. The major enzymes are the proteolytic and amylolytic enzymes, with mixtures thereof being preferred. Such mixtures normally contain one part of proteolytic enzyme to 0.5 to 2 parts of amylolytic enzyme, with approximately equal amounts usually being preferred. A suitable commercial product is sold under the trade name Alcamyl, which is manufactured by Novo Industrii, but other products of the Maxatase type are also acceptable. Enzymes can be formulated with carriers or they can be dissolved or dispersed in liquid media to facilitate more accurate weighing and formulation. In the preparation of the compositions of the present invention, preference is given to using liquid preparations of the said dual enzymes which dissolve more readily than powders.

A stabilizer or a stabilizing combination is normally present with the enzymes; this prevents the enzymatic activity after storage of the liquid detergent composition containing the enzyme or the enzyme mixture from deteriorating; suitable stabilizers include lower carboxylic acid salts usually having 1-3 carbon atom, preferably alkali metal salts, e.g. sodium salts. Of the lower carboxylic acid salts, the formates are preferred, most preferably such a stabilizer is sodium formate. Most preferably, the said enzyme stabilizer is accompanied by water-soluble calcium and / or magnesium salts, preferably salts of highly organic acids, such as calcium chloride, magnesium chloride and / or magnesium sulfate. Such salts form a stabilization system with the lower carboxylic acid salts and improve the stabilization of the enzymes present.

Because not always the desired components of the liquid. Detergent compositions of this invention are readily soluble in their aqueous medium, it is often desirable to use an auxiliary solvent to aid in the dissolution of such components (such as the fluorescent brighteners) ensure that stratification of the liquid detergent composition or sagging of its components is prevented. The co-solvent can also exert an anti-freeze function, thus keeping the composition uniformly liquid even at temperatures below freezing point. Preferred auxiliary solvents are lower molecular polar organic compounds, which are preferably lower alkanols, such as ethanol or isopropanol, with ethanol (usually denatured) being preferred. Such an auxiliary solvent can be mixed with another solvent, such as a diol or a polyol, to form a more complex auxiliary system. Suitable diols and polyols are glycerol and glycols.

The water used can be tap water, distilled water or deionized water or treated water, such as a boiler supply water taken from the boiler supply system from the production site. It is normally desirable that such water has a relatively low hardness, and normally it has a hardness less than 100 ppm, such as CaCO3, preferably less than 50 ppm. and most preferably, the hardness will be about 0.

Various adjuvants can be included in the liquid compositions of the invention, often the same as for finely divided products, the most common being perfume and colorant.

The perfume will normally be lipophilic but easily solubilized by the surfactant and solvent components of the composition. The dye can be a water-dispersible finely divided pigment, but usually a water-soluble dye or a mixture of suitable such dyes is used, whereby mixtures of dyes and pigments are also possible. Other components of the composition of the invention that may be considered as auxiliaries are alkaline and acidic materials useful for adjusting the pH of the liquid detergent composition in a desired range. Normally it will not be necessary to use both acidic and alkaline materials for the pH adjustment. 880 1 961 - 24 - - 24 - but sometimes this may be desirable. A preferred acidic material is citric acid, which is preferably used as an aqueous solution, e.g.

50% aqueous citric acid is used, while a preferred alkaline neutralizing agent is aqueous sodium hydroxide, usually of a 38% aqueous concentration. Another aid commonly used in the present composition is an anti-corrosion aid for metallic equipment in which the composition is stored, processed or transported. The most effective of such anti-corrosive agents for the present compositions are the alkali metal nitrates, e.g. sodium nitrate.

The amounts of the various components of the present liquid detergent compositions are kept within certain ranges to obtain a product with the desired properties, which has an improved washing power over oily contaminants such as dirty motor oil, at a multiple of fabrics, especially with respect to polyesters and cotton / polyester blends, and which also has an acceptable appearance and acceptable physical properties. The main component of the liquid detergent composition of the invention is water, and the amount thereof will normally be sufficient to solubilize (optionally in conjunction with an auxiliary solvent present) the NRE, the PET-POET copolymer and any other components of the composition. The water content is in the range of 50 to 85% and is preferably 60 to 80%, most preferably 65 to 75%, especially 70% or about 70%. The amount of NRE will be sufficient for washing purposes, which is usually in the range of 10 to 30%, preferably 12 to 20%, and most preferably 14 to 18%, especially 16 or about 16%. The amount of the PET-POET copolymer will be an amount sufficient to promote soil removal, usually in the range of 0.2 to 3%, preferably 0.5 to 2%, most preferably 0, Is from 7 to 1.5% and is in particular 1% or about 1%.

When a fluorescent whitener or whitener mixture is present, the amount thereof will range from 0.05 to 2%, preferably 0.05 to 0.3%, and in particular is 0.2% or 88%. 1 96 1. 25.

- 25 - about 0.2%. The amount of the anionic detergent is sufficient to increase the whitener substantivity, and is in the range of 1 to 10%, preferably 2 to 5%, and in particular 3.5% or about 3, 5%. The amount of enzymes will be an amount sufficient for enzymatic purposes, and is within the range of 0.1 to 5%, preferably 0.3 to 3%, and most preferably 0.8% or about 0. 8%. Such amounts are based on the commercially supplied enzymes, including any carriers. The enzyme stabilizer or stabilizing system will be present in an amount effective for stabilizing purposes, in the range of 0.5 to 6%, preferably 2 to 4%, most preferably the amount being about 3%, e.g. Is 3.2%.

The co-solvent is effective amount for co-solvent purposes, i.e. in the range of 3 to 15%, preferably 4 to 10%, in particular 5% or about 5%.

The total amount of auxiliaries present is in the range of 0.1 to 5%, and is preferably 0.2 to 2%, such as 1% or about 1%.

As for the individual adjuvants, the content of the anti-20 corrosion compound is in the range of 0.2 to 2%, preferably 0.3 to 1%, and most preferably is 0.5% or about 0.5% .

The amount of perfume is in the range of 0.1 to 1.52, preferably 0.2 to 1%, and in particular is 0.35% or about 0.35%.

The content of the neutralizing or pH adjusting agents is in the range of 0.05 to 0.5%, preferably 0.1 to 0.3%, most preferably 0.15% or about 0.15 %. The content of dye or other colorant is in the range of 0.00001% to 1%, preferably 0.00002 to 0.01%, and in particular is 0.00004% or about 0.00004%.

The liquid detergent compositions with improved soil removal performance normally have a cloud-like appearance and sometimes they can be translucent. They can be made transparent, pearly or cloud-like, if desired, using appropriate additives. The pH of the product will normally be in the range of 7.3 to 35 8.1, ideally about 7.7 while the viscosity will normally be in the range of 65 to 115 centipoise at 25 ° C, and at * 880 1 96 1. 26.

- 26 - preferably about 90 cp. is.

The preparation of the liquid composition according to the invention is relatively simple, with virtually no critical treatment steps required. Usually, the formula-5 amount of water or about 80¾ or more of such amount is pumped into a mixing vessel or tank and the various components of the detergent composition are successively mixed in the aqueous medium, followed by addition of the rest of the water .

Sometimes the co-solvent can be added first and at other times a portion thereof or the total amount can be retained with the rest of the water for later addition, at or near the end of the mixing process. In many instances, certain components, such as the fluorescent whitener, will first be dissolved in the co-solvent or in some of the water containing some or all of the co-solvent. While such techniques may facilitate faster preparation of the liquid detergent, in desired form and appearance, the intended product is usually also available without performing such process variations, except for pre-dissolving the fluorescent whitener . After mixing in all other components is complete, the residual amount of water, if applicable, can be added, also with stirring, and the pH adjusted. After pH adjustment and viscosity control to ensure that they are within specifications, the product can be bottled immediately.

The use of the liquid compositions according to the invention is simple and satisfactory from the user's point of view, since the consumer need only measure the desired amount of liquid detergent and add it to the wash water in an automatic washing machine. Such machines have a content of 60 to 70 liters of water, with about 67 liters of water being customary, and half a cup of liquid detergent, corresponding to about 120g thereof, is used per washing step, although such amount can be varied depending on the load on the washing machine and the degree of soiling of the laundry to be washed. The laundry (usually about 3kg., ± 50%) c 8 8 0 1 9 6 1 - 27 - - 27 - is added to the wash water and the machine is turned on. The wash water normally has a hardness of no more than 300 ppm, as CaCO3 while the water temperature is normally in the range of 10 to 90 ° C. It will rarely occur in practice that the temperature of the wash water reaches the boiling point, but the wax and soil removal promoting processes of this invention are useful also at such higher temperatures. The best effects of promoting dirt removal are compared at lower temperatures. The water hardness is preferably not higher than 200 ppm, the range being from 100 to 200 ppm. is considered normal. However, it is also possible to use a wash water of lower hardness. Within the aforementioned broad temperature range, a preferred range is 10 to 50 ° C, and for the most significant improvements in soil removal promotion as well as the resulting washing power, compared to that obtained using similar BRE assemblies, such a range is 10 to 25 ° C, e.g. about 20 to 21 ° C.

Normally, the wash cycle (during which the ΡΕΤ-Ρ0ΕΤ copolymer is applied simultaneously to the laundry) will be 5 to 30 minutes 20, with a rinse cycle of 1 to 5 minutes, when an automatic washing machine is used and sometimes a multiple, usually 2 to 3 rinse cycles are used. The drying times are between 10 and 60 minutes, usually the drying times are in the 20 to 40 minute range, the drying usually being carried out at "normal" drying temperatures of automatic laundry dryers instead of at the "higher" settings. Both the washing and drying conditions will of course be determined by the nature of the laundry, the contamination and / or the stains thereon and the characteristics of the washing and drying devices used. Top-of-the-line automatic washing machines are usually used, but side-loading machines are also acceptable and the stated advantages are also obtained when the laundry is hand washed and line dried.

In the washing treatment process, it is highly preferred to add the described liquid detergent composition to the washing machine, but it is also possible to add the various components thereof to the washing machine alone or in mixture to be used in. 880 1 96 1. 28.

- 28 - essentially achieve the same wash water composition. The resulting wash water then contains a detergent amount of NRE and a soil removal promoting amount of the PET-POET copolymer. Such amounts are in the ranges of 0.01 to 0.1% and 0.0002 to 0.01%, preferably 0.01 to 0.05% and 0.0005 to 0.006%, respectively, and most preferably 0.02 to 0.04% and 0.001 to 0.005%, e.g. about 0.03 to about 0.003%, respectively. The concentration of the fluorescent whitener is usually in the range of from 0.0001 to 0.01%, preferably from 0.0002 to 0.001%, such as 0.0003%. The concentration of the anionic detergent is usually in the range of 0.001 to 0.03%, and is preferably 0.002 to 0.02%, e.g. about 0.007%. Concentrations of other components of the liquid detergent composition (excluding water) in the wash water and their ranges, in percentages of the wash water, can be obtained by multiplying such exemplary concentrations for the liquid detergent composition by 0, 0018, for the ideal concentration thereof in the wash water, or one can calculate lower and higher percentage ranges of such concentrations by multiplying the liquid detergent composition-20 concentrations in percentages by 0.0010 (for the lower limit) and 0.0030 (for the upper limit ). However, it is most preferred to use the liquid detergent composition at a concentration in the wash water of about 0.18%, with such concentration depending on the nature of the laundry ranging from 0.10 to 0.3% or can be within a narrower preferred range of 0.15 to 0.25%.

The following examples provide an illustration without limitation of the invention. Unless otherwise indicated, in these examples and in the claims all parts by weight and all temperatures are in 30 ° C.

, 8801961 - «- - 29 -

EXAMPLE I

Component Percentage

Sodium tripolyphosphate 57.3 * Narrow range ethoxylated higher fatty alcohol 20.0

Water 10.0 5 Sodium silicate (Na20: Si02 = 1: 2.35) 4.5 ** PET-POET copolymer 3.6

Mixed proteolytic and aminolytic enzymes 1.3 (Maxatase MP)

Sodium sulfate 1.1 10 Fluorescent whitener (Tlnopal 5BM Extra concentrated) 1.0

Sodium Polyacrylate (Alcosperse 107D) 0.9

Colorant (dye mixture) 0.1

Perfume 0.2 15 100.0 * Condensation product of linear alcohol and an average of 6 to 7 moles of ethylene oxide per mole of alcohol, with about 88% of the ethylene oxide being present in polyoxyethylene groups with 5 to 10 EtO's (Tergitol 24-L-60N, produced by 20 Union Carbide Corp.).

** PET-POET copolymer having a weight average molecular weight of about 22000, the molecular weight of the polyoxyethylene about 3400 and the molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate units about 3: 1.

25 (Alkaril QCF, manufactured by Alkaril Chemicals, Ine., And supplied by them in finely divided form, in a 4: 1 ratio, with sodium polyacrylate, as pre-melted Alkaril Base C).

A finely divided detergent composition of the above formula is made by mixing a 45% solids crust screen mixture 30 of the tripolyphosphate, silicate, sulfate, fluorescent whitener and dye in tap water at a temperature of about 60 ° C and in hot drying gas sprayable in a spray tower at a temperature of about 40 ° C to form granules of dimensions in the range of Nos. 10-100, US sieve. 8801 96 1 - 30 · 5 - 30 - series, with a moisture content of 13.5¾. After cooling, 74 parts of such base granules are sprayed with 20 parts of the NRE nonionic detergent, in the liquid state at elevated temperature, e.g. about 40 ° C, which detergent is absorbed into the granules. Then 4.5 parts of a 4: 1 QCF / Alcosperse mixture (in finely divided form with approximately the same particle size as the spray dried granules) and 1.3 parts of the enzyme mixture are mixed with the builder nonionic detergent granules, then the product is perfumed with 0.2 part liquid perfume sprayed thereon, during which treatment steps the materials are agitated in an inclined drum mixer.

The dirt-promoting effect of the disclosed detergent composition containing the synergistic combination of NRE nonionic detergent and PET-POET copolymer is measured by the DM0 (dirty engine oil) method as previously described. Test cloths of different materials are first washed in an automatic washing machine with the experimental detergent composition at a concentration of 0.15%, in 21 ° C wash water with a hardness of 150 ppm, as calcium carbonate, followed by automatic drying, staining 20 of the test cloths with three drops of dirty motor oil (DM0) each, then stand overnight and wash again with the experimental detergent composition under the same conditions. The reflections of the test wipes are measured after the first wash, after staining and after the second wash, and the percentages of soil removal are known here according to the formula previously given.

A counter-test system was made in which the same amount of non-ionic detergent was used, but consisting of a BRE (Neodol 25-7) with substantially the same average ethoxylate-30 content and with substantially the same fatty alcohol component, with only the significant difference between the detergents. wide range distribution of the ethylene oxide polymer in the BRE detergent agent and its narrow range distribution in the NRE detergent agent. For such a control product, the same base granules and auxiliaries are used with the same amounts of the different nonionic detergent being absorbed into such granules.

* 8801 961 - 31 - - 31 -

The following table provides a comparison of the percentages of dirt removal (or stain removal) found.

TABLE B

Dirt removal (¾) 5 Tissue type cloth Experimental Control

Dacron double-knitted 88.7 73.1

Dacron single knitted 94.0 91.1

Woven polyester 91.5 80.8 65:35 Dacron: cotton blend 47.3 35.7 10 50:50 Dacron: cotton blend 32.2 26.7

Nylon tricot 79.4 59.4

Acetate jersey 81.9 72 <1

Since a 5¾ difference in soil removal under the conditions of the trial is considered significant, significant differences were obtained for all test 15 wipes except the Dacron single knit, but even in the latter case the experimental sample is better than the control. The average improvement is 10.9%. The visual observation of the test wipes was even more convincing in terms of the unexpected beneficial promotion of soil removal of the synergistic composition of this invention. It should be noted that in the test mentioned, the staining was more severe than that normally found and that the test was conducted under washing conditions (cold water) which are considered unfavorable. Even better dirt removal results are thus obtained when using warm or hot washing water. When multiple washings e.g. 2 to 6, with the compositions preceding staining with DM0, the soil-promoting properties of the composition of the invention are also more pronounced. The soil removal performance obtained for a DM030 is also obtained when a plurality of other oily types of contaminants are used in the described test, and the improvements over controls are also significant.

. 8801 961 - 32 - 32 -

EXAMPLE II

Component Percentage

Sodium zeolite (Zeolite 4A, anhydrous base) 30.1

Sodium carbonate (anhydrous) 20.1 * NRE non-ionic detergent 20.0 5 Sodium bicarbonate 10.8

Water 9.5

White montmorillonite (anhydrous) 1.4

Enzyme mixture (Maxatase MP) 1.3

Fluorescent whitener (Tinopal 5BM extra concentrated) 1.0 10 ** PET-POET copolymer 4.0

Sodium polyacrylate (Alcosperse 107D) 1.5

Perfume ff, 2

Colorant (dye mixture) 0.1 100.0

15 * See example I

** See example I (Alkaril Velvetol 251-C used instead of Alkaril base C).

Two control compositions are made, A and B, where A is the same as the above experimental formula except that Tergitol 24-L-60N is replaced by Neodol 25-7, and with such BRE substitution also in control B from which the QCF + the stabilizing 1% Alcosperse 107D have been removed (the remainder of the Alcosperse 107D is added in the crutch mixture).

Test wipes were washed, stained and washed again with the experimental, Control A and Control B compositions, the results of which are summarized in the following table.

t 8801 961 - 33 - - 33 -

TABLE C

Dirt removal (%)

Wipes tissue type Experimental Control A Control B

Dacron double knitted 66.0 27.9 3.6 65:35 Dacron: cotton blend 40.2 31.8 13.8 5 Nylon jersey 39.3 17.4 26.7

Acetate jersey 48.8 33.5 10.8

The above data demonstrate that the experimental formula of this invention is significantly better than any of the control formulas in promoting the removal of the test wipes described from a stubborn oily contamination, an even dirtier motor oil than that used for the experiments of Example 1. Since a 5% difference is considered to be very significant, it is clear that very remarkable differences have been achieved compared to the best of the controls in which a BRE non-ionic detergent instead of the NRE non-ionic detergent the compositions of the invention are used. Thus, the average improvement in soil removal for the four materials listed is 20.9¾. A visual observation of the test wipes confirms that the soil removal promoting activity of the composition of the invention is far superior to that of the controls.

EXAMPLES III AND IV

The compositions and controls of Examples I and II are made with an NRE nonionic detergent available from Shell Development Company, which is identified as 23-7P, 25 in place of Tergitol 24-L-60N. Wipe tests such as those of Examples I and II show that such detergent compositions are essentially equivalent in soil removal promoting activity to the experimental composition of Examples I and II, confirming that Shell's 23-7P is within the scope of the specification of the NREs of the present compositions also synergistically enhances the soil removal promoting activity of the PET-POET copolymers in the present compositions.

, 8801 961 - 34 - - 34 -

EXAMPLES V AND VI

The compositions and controls of Examples I and II are made with an NRE nonionic detergent available from Shell Development Company, which is identified as 23-7Z, 5 and substitutes for Tergitol 24-L-6QN. Wipe tests such as those of Examples I and II show that they are essentially equivalent in soil removal promoting activity to the experimental compositions of Examples I-IV, confirming that 23-7Z from Shell, which is within the scope of the 10 description of the NRE1s of the present composition also synergistically enhances the soil removal promoting activity of PET-POET copolymers in the present compositions. Similar results are achievable using the shell etoxylate from Shell Development 15 Company designated as Neodol 23-6.5 NRE, which is a narrow etoxylate comparable to Neodol 23-6.5, a product of Shell Chemical Company (which product is a BRE). Also, mixtures of the aforementioned substitute NRE nonionic detergents can be made with similar improvements in soil removal promotion observed.

EXAMPLE VII

Several changes were made to the compositions of Examples I-VI without departing from the scope of the invention. For example, in the wash treatment steps, the concentrations of the detergent composition can be varied in the range of from 0.05 to 0.3% depending on the wash water hardness and temperature, the washing machine type and design, the laundry type and the contamination of the to treat and wash laundry.

Various builders, PET-POET polymers, polyacrylates, fillers, enzymes and other auxiliary materials can be used, as well as various mixtures thereof. Different mixtures of narrowly ethoxylate nonionic detergents are useful while individual amounts of the components of the detergent composition of the invention can be changed by ± 10%, ± 20% and ± 30%, provided they are within the ranges and Descriptions of the present application are 8801961 _ 35 _ ψ - 35. Although normally anionic detergents are not present in the composition of the invention, their presence can be up to a reasonable limit, e.g. 10% of such a composition, are sometimes desired. Of the anionic detergents, the straight upper alkyl benzene sulfonates, the higher fatty alcohol sulfates and the higher fatty alcohol polyetoxy sulfates are preferably as sodium salts and with alkyl groups and alcohols having 10-18 carbon atoms, most preferably 12-14 carbon atoms.

When the modifications of the formulas of Examples I-VI 10 as mentioned herein are made, the resulting compositions and the methods employed appear to be effective in promoting soil removal from various synthetic organic polymeric textile materials (especially polyesters) and from synthetic natural fiber blends. It is important, however, that the nonionic detergent compositions contained in such composition and used in such methods are of the NRE type, as previously described, and in amounts such as those contained herein.

. 880 1 96 1, 36.

"36"

EXAMPLE VIII

Component% * NRE Tergitol Nonionic Surfactant 24-L-60N 16.00 5 ** Alkaril QCJ (15% Aqueous Solution) 6.67 *** Fluorescent Whitener 0.16

Sodium linear dodecylbenzene sulfonate 6.67 (52.5¾ active component, in aqueous solution) 10 Enzyme mixture (Alcamyl) 0.75

Calcium chloride dihydrate 0.17

Sodium formate 3.00

Sodium nitrate 0.50

Blue dye (Cl Acid Blue 182, 15 0.38¾ aqueous solution) 1.00

Ethanol (denatured with methanol) 5.41

Perfume 0.35

Sodium hydroxide (38% aqueous Na2U solution) for pH adjustment q.s.

20 Citric acid (50% 1 s aqueous solution) for pH adjustment q.s.

**** Water (softened) 59.32 100.0 * A narrowly ethoxylate nonionic detergent which is a condensation product of a higher fatty alcohol with 12-14 carbon atoms and an average of 7 moles of ethylene oxide per mole, with more than 90¾ thereof with 4-10 ethoxylate groups per mole.

** Polyethylene terephthalate-polyoxyethylene terephthalate copolymer having a molecular weight of about 22000, polyoxyethylene molecular weight of about 3400, and mole ratio of polyethylene-30 terephthalate to polyoxyethylene terephthalate units of about 3: 1.

*** Stilbene type fluorescent whiteners (0.11¾ Phorwite RKH and 0.05% Phorwite BHC, both manufactured by Mobay Chemical Co., any such whiteners can be replaced but they are c 88 0 1 96 1 - 37.

- - 37 - preferably of a stilbene sulfonate or stilbene sulfonic acid type).

**** The percentage given is for formulations to which neither sodium hydroxide nor citric acid has been added (for pH adjustment).

If one is used, the percentage of water is lowered accordingly. It should be noted that the percentage of water in the final liquid detergent composition is greater than indicated because various components are accompanied by some water.

A liquid detergent of the above composition is made by mixing all components with the water in any suitable order, provided that the fluorescent whitener is previously dissolved in the manufacturing process. Either sodium hydroxide solution or citric acid solution is added at the end of the mixing process to adjust the pH, either up or down, as desired, with the perfume normally added after the pH adjustment is made. Optionally, the listed components, some of which are dissolved in the cosolvent or in the aqueous cosolvent, may be mixed with the appropriate amount of the formula amount of water (such as 1/2 or 4/5), leaving the rest of the water can be added at the end or shortly before the pH adjustment and / or the perfume addition.

The resulting product is a blue liquid which is cloudy or translucent in appearance and with a viscosity of 90 centipoise at 25 ° C, measured with a Brookfield (RV) viscometer, using a # 1 spindle, which rotates with 20 revolutions 25 per minute. The pH of the product is 7.7. The liquid detergent composition is stabilized at room temperature for at least 6 months and often for a year or more without stratification or sagging of the component, the dirt-promoting activity of the PET-POET copolymer-component remaining high after storage. , apparently because of the presence in the product of the NRE. If a BRE replaces the NRE, a significant reduction in the soil removal promoting activity is noted after storage.

The liquid detergent composition according to the invention is tested for soil removal promoting effect compared to a control composition which is therefore identical to the off. 88 0 1 96 1 38 - * * - 38 - without replacement of the Tergitol non-ionic detergent 24-L-60N with Neodol 25-7. The following is a description of the test procedure using a normal wash water concentration of the liquid detergent compositions, 0.18¾.

5 In the Tergotometer laboratory washing machine, three rectangular polyester double-knitted wipes, each with a size of 7.6 x 10.2 cm, are pre-washed together in 1 liter of washing water of 150 ppm. hardness, as CaCO 3, for 10 minutes at a temperature of either 21 ° C (cold water wash) or 38 ° C (hot water wash), as desired. After washing, the wipes are rinsed by hand for about 10 seconds and then dried and after drying, reflection readings are taken with a Reflectometer (e.g. Gardner XL20). The average reflection reading for the three wipes is taken as Rd (initial). The three wipes are then stained with three drops of dirty engine oil each and left to stand overnight. Reflection readings are again taken and the mean is Rd (stained). The prewash procedure is followed by washing the stained wipes and again taking reflections and averaging, identifying the average as Rd (washed). The percentage of soil removal obtained is calculated as follows.

Rd (washed) - Rd (spotted) - X 100

Rd (initially) - Rd (stained)

Instead of using the laboratory washing machine, a conventional kitchen machine can also be used, following the same procedure with the exception that the wipes can sometimes consist of a variety of tissue types, and are usually larger in size, e.g. 10.2 x 15.2 cm, the wash water-filled urn will be larger, e.g. 64.3 liters and the washing machine is set to a normal 10 minute wash cycle, with accompanying normal rinse and spin cycles. The liquid detergent composition loading in such tests is one bowl per wash step, which is 0.18% based on the wash water.

The percentage of soil removal for the composition of the invention of the preceding formula is 74.2% (21 ° C), while that for a control, an identical formula with the exception of the. 880 1 96 1 - 39.ƒ _ 39 _ replacement of the Tergitol nonionic detergent 24-L-60N with NeodoT 25-7 is only 54.4%. The difference is considered to be very significant and there is no other clear explanation for this except that the NRE and PET-POET copolymer interact unexpectedly and favorably and improve the soil removal promoting properties of the liquid detergent composition to provide oily contamination, which are particulate materials. such as dirty engine oil is significantly better removed from polyester and polyester blends by the liquid detergent composition of the invention than by similar compositions based on a broad-range ethoxylate nonionic detergents.

To ensure that the apparent "synergy * 1 does not stem from the fact that the Tergitol 24-L-60N is a soil depletion promoter, taken by itself, further 15 tests were conducted, the experimental and control tests as described above were repeated with the exception that alkaryl QCJ was omitted from the formulas In such cases, the percentage of soil removal for the double control (that based on Neodol 25-7} was 7.4% and the percentage of soil removal was 20%). for the Tergitol 24-L-60N formula without Alkaril QCJ 7.5%.

From the above data, it is clear that the NRE detergent alone does not promote soil removal more than the BRE detergent alone does, but that the combination of NRE and PET-POET copolymer significantly improves soil removal by the copolymer. Such an improvement is unexpected and significant. The differences in the cleaning of the wipes are apparent to untrained observers and no sensitive measuring instruments need to be used to verify these differences.

Practically the same results are obtained when the laboratory test with a conventional washing machine is repeated. However, when the washing temperature is changed from 21 ° C to 38 ° C, no clear difference in soil removal promotion is evident, but this may be due to the fact that at such higher wash water temperatures, the soil removal percentages are more than 90% and therefore at their maxima are.

. 8801 961. 40.

-40-

It is considered that in cases where the tissues are more heavily contaminated or stained than in the experiment described above, the NRE-QCJ formulas will significantly improve fluid removal than the BRE-QCJ formulas.

EXAMPLE IX

The laboratory washes of Example VIII were repeated, but the test wipes were nylon jersey and 65/35 polyester / cotton blend. In the 2 proeven0 tests, 56.6¾ of the dirt was released from the nylon by the composition of the invention, while the control composition released only 37.1%. The composition of the invention releases 57.4% of the soil from the copolyester / cotton blend while the control scores only 49.7%. The differences at 38 ° C are similar with the composition of the invention removing 56.3% of the stains from the nylon 15 compared to 47.8% for the control and removing 52.0% from the polyester / cotton blend compared to 35.9% for the audit. Furthermore, the differences in dirt removal are visible to the naked eye. The above example demonstrates that the unexpected improvement in the soil removal properties of the composition of the invention compared to a similar BRE composition is not limited to polyester fabrics but also applies to nylon and polyester / cotton blend fabrics.

EXAMPLE X

The test procedure of Example VIII was repeated using both aged and freshly prepared detergent compositions and washing in a laboratory washing machine with 38 ° C wash water. Using the freshly prepared liquid detergent compositions, the inventive composition loosens 92.4% of the soil from the polyester fabric while the control composition loosens 19.1%. Thus, the liquid detergent compositions under such conditions have substantially the same soil removal promoting effect. However, after accelerated aging of the detergent compositions for 1 week at 44 ° C, there is an exceptional difference where the experimental product removes 88.6¾ of the soil while the control removes only 81.2¾. It was thus found that the control deteriorates faster in soil removal promoting activity than the liquid detergent composition of the invention.

it

The stated experiment also demonstrates the importance of using NRE nonionic detergents instead of BRE detergents to preserve the soil removal promoting activity of this type of liquid detergent composition. It was previously known that PET-POET copolymers of the present type liquid detergent compositions (but based on BREs) are destabilized by triethanolamine, which is used in some liquid detergent compositions for its solubilizing effect on fluorescent brighteners, and it is known that ionizable salts sometimes exhibit such a destabilizing effect. Therefore, the triethanolamine (TEA) content of PET-POET-containing liquid detergent compositions was minimized or the TEA was completely omitted and the ionizable salt content was limited. Ordinarily, for good soil widening action in NRE-PET-POET liquid detergent compositions, the amount of TEA present should be limited to 1%, preferably less than 0.5%, and most preferably omitted.

With regard to the ionizable salts, their concentration should normally be limited to 10%, preferably 5%, and most preferably 1% or less. For the compositions of this application and of this example, the ionizable salt content is desirably also limited, preferably 5 or 10% ionizable salt (1% when sodium formate and anionic detergent are not counted) and 0.1 or 0.2% TEA (but omitting it altogether is 3ü preferred).

Although the data presented in this example pertains to studies at 38 ° C, it is believed to be representative of data obtained when the studies are conducted at higher and lower temperatures, such as 21 ° C. These data are also considered consistent with the results obtained after storage of the liquid detergent compositions for 6 months or a year or after accelerated aging for 1 or 2 months.

However, after extended periods of storage or storage at higher temperatures, the soil removal promoting activity will further decrease, so it is important that the products to be traded have the highest incipient soil removal promoting effects, so that even when such effects decline the soil promoting capacity to the consumer will be acceptable.

EXAMPLE XI

-] q When variations are made in the basic formulas of Examples VIII - X, replacing the Tergitol 24-1-60N with comparable NREs, such as 24-L-45N, 24-L “50N and 24-L-75N, essentially the same types of results are available. If NREs such as Shell 23-7P and Shell 23-7Z are also substituted, then at least in some such cases similar results are achievable. Some variations can also be made to the PET-POET copolymer, such as the increase in its weight-average molecular weight so that it ranges from 30,000 to 40,000, with the desired soil removal promoting activities still available. Instead of the aforementioned anionic detergents, others may be used, such as sodium lauryl sulfate and other comparable alkyl aryl sulfonates and alkyl sulfates. Various enzymes, enzyme stabilizers, copolymer stabilizers, cosolvents, fluorescent whiteners, dyes and perfumes can be used, all in accordance with the requirements of this application. Likewise, the amounts of the different components for the compositions of these examples, starting from Example VIII, can be varied, such as by plus or minus 10%, plus and minus 20% and plus and minus 30%, as long as 3Q are within the aforementioned trajectory quantities remain.

In such cases, the desired effects of the invention are still obtained.

. 88 0 1 96 1 43

Claims (18)

1. Detergent composition with improved soil removal promoting properties in cold water washing of polyester-containing fabrics contaminated with oily contaminants, which improved soil removal is caused by the presence of precise ethoxylate (NRE) therein ionic detergent and a soil removal promoting polyethylene terephthalate polyoxyethylene terephthalate (PET-POET) copolymer instead of broad-range ethoxylate (BRE) nonionic detergent and PET-POET copolymer comprising a detergent effective amount of such NRE- type of a nonionic detergent, which is a polyethoxylated lipophilic substance, ethoxylated with an average of 5-10 ethylene oxide groups per mole, wherein at least 70% of the ethylene oxide is present in polyetoxy groups with 4-12 ethylene oxides, as well as a soil removal promoting amount of a PET-POET copoly-15 more dirt removal order resource. The composition of claim 1, which is either in finely divided solid or liquid form. 3. The composition of claim 2, which is in finely divided form and comprises a builder effective amount of a builder for the nonionic detergents. Finely divided composition according to claim 3, characterized in that the nonionic detergent is a condensation product of a higher fatty alcohol and ethylene oxide, the ethylene oxide being present in polyetoxy groups with an average of 6-9 ethylene oxide groups per 25 mol, and wherein at least 70% of the ethylene oxide present in higher fatty alcohol ethoxylates having 5-10 ethylene oxide groups per mole, the builder an inorganic builder, and the PET-POET copolymer has a weight average molecular weight in the range of 15000-50000. Finely divided composition according to claim 4, characterized in that. the higher fatty alcohol of the nonionic detergent contains 12-14 carbon atoms and is saturated, and the builder is selected from the group consisting of sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium silicate, ion exchange zeolite c 8801 961-4-4 - and mixtures thereof the polyoxyethylene or polyoxyethylene terephthalate of the PET-POET copolymer has a molecular weight in the range of 1000 to 10000 and a stabilizing amount of a polyacrylate stabilizer for the PET-POET copolymer is present in the detergent composition, which prevents decomposition of the copolymer and the associated loss of soil wicking ngs promoting activity which would otherwise occur as a result of storage at elevated temperatures and in the presence of alkaline materials. 6. A composition according to claim 5, characterized in that more than 85% of the ethylene oxide content of the narrowly ethoxylate nonionic detergent in C 1 -14 4% fatty alcohol polyethoxylates with 4-12 ethylene oxide groups per mol is present and the nonionic detergent constitutes 10-35% of the composition, the builder constitutes 30-75% of the composition, the PET-POET copolymer constitutes 0.5-10% of the composition, the polyacrylate sodium polyacry is late and constitutes 0.1-5% of the composition and the amount of sodium polyacrylate is 1/6 to 1/2 of the amount of PET-POET copolymer. 7. A composition according to claim 6, characterized in that more than 85% of the ethylene oxide present in the higher fatty alcohol is narrowly ethoxylate nonionic detergent in such detergent as polyethoxy groups having 5-10 moles of ethylene oxide per mole of such nonionic detergent active. . A finely divided composition according to claim 3, characterized in that the percentages of narrowly ethoxylate nonionic detergent, soil wicking promoter PET-POET copolymer and builder in the ranges of 10-35%, 0.5- 10% and 30-75% and the builder 30-75% al potassium metal tripolyphosphate and 0-10% 30 water soluble al potassium metal (M) silicate with an M20: SiO2 ratio in the range of 1: 1.6 - 1: 3, wherein such percentages and the M 2 O: SiO 2 ratio are by weight of the anhydrous material and on a final composition basis. A composition according to claim 7, consisting of a mixture of spray dried sodium tripolyphosphate base particles with or without sodium silicate, wherein the base particles contain the tightly .660 1 96 1 - 45 - ψ - 45 - ethoxylate nonionic detergent and solidified melt particles of PET-POET copolymer and polyacrylate stabilizer for such a copolymer. 10. A finely divided composition according to claim 3, characterized in that the percentages of narrowly ethoxylate nonionic detergent, soil removal promoting PET-POET copolymer and builder are in the ranges of 10-35%, 0.5- 10% and 30-75% and the builder comprises 15-40% of the ion-exchange zeolite, 10-30% sodium carbonate and 5-20% sodium bicarbonate, 10 such percentages being by weight of anhydrous material and final composition basis. 11. A composition according to claim 7, consisting of a mixture of spray-dried base particles of hydrated zeolite A, sodium carbonate and sodium bicarbonate, in which the substantially ethoxylate nonionic detergent substance is absorbed in the base particles, and particles of a solidified melt of PET- POET copolymer and polyacrylate stabilizer for such a copolymer. 12. A composition according to claim 2, characterized in that it is in liquid form and comprises water as the medium for the NRE and PET-POET 20 copolymer. Liquid composition according to claim 12, characterized in that the NRE is a higher fatty alcohol ethoxylate condensation product of a higher fatty alcohol and ethylene oxide, the higher fatty alcohol containing 12-16 carbon atoms and the ethylene oxide in the polyethoxyethanol groups having an average of 4- 10 etoxy groups per mole is present, with at least 80% of the NRE higher fatty alcohol ethoxylates having etoxy contents in the range of 4-10 ethoxy groups per mole, the PET-POET copolymer is a weight average molecular weight in the range of 15000 to 50000 and the amounts of such NRE, PET-POET copolymer and water in said liquid detergent composition are in the ranges of 10-30%, 0.2-3% and 50-85%, respectively. Liquid composition according to claim 13, characterized in that the NRE is a condensation product of a saturated higher fatty alcohol with 12-15 carbon atoms and an average of 5-9 moles ethylene oxide per mole of such higher fatty alcohol, in polyethoxyethanol groups, at least 85 % of the NRE higher fatty alcohol c 8801961-46 etoxylates with etoxy contents. is in the range of 4-10 ethylene oxide groups per mole, and the polyoxyethylene of the polyoxyethylene terephthalate of the PET-POET copolymer has a molecular weight in the range of 1000 to 10000. A liquid composition according to claim 14, which comprises 12-20% of an NRE which is a condensation product of a saturated higher fatty alcohol with 12-14 carbon atoms and an average of 6-8 moles ethylene oxide per mole of such higher fatty alcohol, in polyethoxyethanol groups, wherein at least 90% of the NRE is higher fatty alcohol ethoxylates with ethoxy contents in the range of 4-10 ethylene oxide groups per mole, 0.5 to 2% PET-POET copolymer, an amount sufficient for whitening purposes in the range of 0.05 up to 2% of a fluorescent whitener, a fluorescent whitener, substance-enhancing amount of an anionic sulfate-15-phosphate and / or sulfonate detergent, within the range of 1-10%, an enzymatic amount within the range of 0.1 to 5% of an enzyme, a stabilizing amount within the range of 0.5 to 6% of a stabilizer or a stabilizing system for the enzyme, a co-solvent amount within the range of 3 20 to 15% of a polar organic co-solvent for the non-aqueous components of the liquid detergent composition, 60-80% water with optional auxiliary residues. Liquid composition according to claim 15, characterized in that the NRE is a condensation product of a saturated higher fatty alcohol with 12-14 carbon atoms and an ethylene oxide, with an average of about 7 moles of ethylene oxide per mole of such higher fatty alcohol, the PET-POET copolymer has a molecular weight in the range of 19000 to 43000, the fluorescent whitener is a stilbene whitener, the substantivity of the fluorescent whitener enhancing anionic sulfate and / or sulfonate detergent is an alkali metal higher alkyl benzene sulfonate, wherein the higher alkyl contains 12-18 carbon atoms, the enzyme is a mixture of proteolytic and amylolytic enzyme, the enzyme stabilizer comprises an alkali metal lower carboxylic acid with 1-3 carbon atoms, the polar organic co-solvent is a lower alkanol, the water softened water with a hardness of less than 50 ppm if CaCO is ^, <880 1,961. 47. \ * r _ 47. the auxiliaries include perfume and colorant and the amounts of such components in the liquid detergent composition in the range of 14-18%, 0.7-1.5%, 0.05-0.3%, respectively. 2-5%, 0.3-3%, o, c5-0.3%, 2-4%, 4-10%, 65-75% and 0.2-2%, in which liquid detergent composition the pH is in the range of 7.3-8.1 and the viscosity is in the range of 65-115 centpoises at 25 ° C and the PET-POET soil release promoter copolymer is stable in storage. Liquid composition according to claim 12, which is free from triethanolamine and triethanolamine salts and comprises no more than 10% ionizable salts. 18. A method of washing laundry and imparting moisture removal promoting properties thereto comprising repeatedly washing such laundry in wash water containing a soil removal promoting amount of a soil removal promoting detergent composition according to claim 1. .8801961