NL8401065A - LIQUID DETERGENT WITH IMPROVED DIRT REMOVAL PROPERTIES. - Google Patents

Description

46.-i * VO 6216

Liquid detergent with improved dirt removal properties.

This invention relates to liquid detergents, in particular to detergents containing a soil removal promoting polymer that deposits on polyesters and polyester blends during washing thereof and promotes the removal of lipophilic contaminants thereafter applied. Preferably, the liquid detergent contains an enzyme to aid cleaning, as well as an enzyme stabilizer, while a tissue softening agent such as a quaternary ammonium salt may also be present.

The agents of the invention are physically and functionally stable as in storage mode, even when they contain the enzyme (s) and tissue softener (s).

Liquid detergents are used for washing household clear laundry in washing machines, often being applied to contaminated parts of the laundry, such as the collar of a shirt, before washing. The use of copolymers of polyethylene terephthalate and polyoxyethylene terephthalate in detergents to promote soil removal has been described in several patents, some of which relate to liquid preparations. However, the liquid detergents described are not of the type of the present invention because they contain triethanolamine and / or ionizable water-soluble salts (other than anionic detergents) which give rise to the liquid detergent being separated and destabilize said polymer upon storage so that it less effectively promotes dirt removal when used.

In liquid detergents, enzymes have been found to lose their storage activity unless they are stabilized, such as by salts, for example, sodium formate, glycols, for example, propylene glycol, or other such materials. However, said salts lead to destabilization of the quaternary ammonium halide fabric softeners and the copolymer which acts as the soil remover promoting agent, which are desirable components of the present liquid detergent compositions, and such destabilization of soil soil removal. The agent acts particularly strongly in the presence of lower alkanolamines or their salts, such as triethanolamine (TEA), the presence of which will be avoided. It was therefore surprising that the present liquid detergent compositions could be obtained in a clear and stable non-shearing form, with the various functional components thereof remaining effective even after storage at elevated temperature.

According to the present invention, a liquid detergent having improved soil removal properties comprises a detergent amount of nonionic detergent or a mixture of nonionic and anionic detergents, an amount of soil removal promoting the soil removal effective polymer of polyethylene terephthalate and polyoxyethylene terephthalate as well as an aqueous medium in which the pH is in the range of 6-9 and in which no more (2%) of a non- (anionic surfactant) water-soluble ionizable salt is present. Also included within the invention is a method of preparing the described compositions.

Preferably, such liquid compositions also contain enzymes and enzyme stabilizers, more particularly when the fabric softener is also present. Thus, a stable enzyme-containing liquid detergent comprises a detergent amount of a nonionic detergent, a detergent supplement that enhances the directness of the fluorescent tint enhancer, a higher fatty alcohol polyethoxylate sulfate detergent, to promote the soil removal effective amount of a soil removal promoting polymer of polyethylene terephthalate and polyoxyethylene terephthalate, an amount of enzyme sufficient to enzymatically hydrolyze proteinaceous and / or starchy impurities on the fabrics during washing with an aqueous wash solution of the liquid detergent, a stabilizing amount of a stabilizer for the enzyme or enzymes, with an aqueous medium, in which the pH is in the range of about 6-9 and in which no more than 2% water-soluble ionizable material is present other than the higher fatty alcohol polyethoxylate sulfate detergent. Likewise, a stable fabric-softening, soil-promoting, enzyme-containing liquid detergent comprises a detergent amount of a 8401065 * 3 nonionic detergent, a soil-promoting polymer of polyethylene terephthalate promoting soil-removing polymer. and polyoxyethylene terephthalate, a soft amount of a quaternary ammonium salt fabric softener, an amount of enzyme sufficient to enzymatically hydrolyze protein-like and / or starchy contaminants on fabrics during washing with an aqueous wash solution of the liquid detergent, a stabilizing amount of a stabilizer for the enzyme or enzymes, as well as an aqueous medium, in which the pff is in the range of about 6 to 9 and in which no more than 2% water-soluble ionizable material, such as salts and / or triethanolamine, is present .

While various synthetic organic nonionic detergent compositions with satisfactory physical properties can be used, including condensation products of ethylene oxide and propylene oxide with each other and with hydroxyl-containing bases such as nonyl phenol and oxo type alcohols, it has best results most preferably that the nonionic detergent is a condensation product of ethylene oxide and a higher fatty alcohol. In such products, the higher fatty alcohol contains 10 to 20 carbon atoms, preferably 12 to 15 or 16 carbon atoms, while the nonionic detergent contains 2 or 3 to 20 or up to 30 ethylene oxide groups per mole, for example 6 to 11 or 12 , contains. Most preferably, the nonionic detergent will be one in which the higher fatty alcohol contains about 12 to 15 or 12 to 16 carbon atoms and contains from 6 or 7 to 11 moles of ethylene oxide, e.g. 7. Such detergents include Alfonic 1214-60C, sold by Conoco Division of E.I.

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DuPont de Nemours, Ine., And Neodols ^ 23-6.5 and 25-7, available from Shell Cgemical Company. Among their particularly attractive properties, in addition to their good washing power with regard to oily and greasy contaminants present on the goods to be laundered, and their excellent compatibility with the present polymeric soil removal promoters, is the compatibility with soluble anionic detergents of the linear higher olefin benzene sulfonate and higher fatty alcohol polyethoxylate sulfate types, enzymes, enzyme stabilizers, fabric softeners and other components of the present invention, as well as the long term viscosity stability in aqueous and aqueous alcohol solutions .

The anionic detergent that can be used in the liquid detergents in the broader aspects of the invention is preferably a higher linear alkyl benzene sulfonate. or a higher fat alcohol polyethoxylate sulfate. Normally, water-soluble salts of such materials are preferred, such as the alkali metal salts, and usually the sodium salts thereof are preferred over the potassium salts. When the anionic detergent is a sodium higher alkylbenzene-10 sulfonate, the higher alkyl group will normally contain 10-18 carbon atoms, preferably 12-16 carbon atoms, most preferably 12 or 13 carbon atoms, such as 12. When such an anionic detergent has a higher fatty alcohol polyethoxylate sulfate. is, as is the case for the enzyme-containing liquids, in which the detergent increases the washing power and promotes an increase in the directness of the fluorescent tint enhancer present, the higher fatty alcohol will have 10 -20 carbon atoms, preferably 12-16 carbon atoms. and most preferably contain 12 - 13 or 12 - 15 carbon atoms and the polyethoxylate will have 1, 2 or 3 - 20 ethozylic groups, e.g. 3 - 10 thereof 20 and most preferably 3 - 6 or 7, e.g. 3, 6.5 or 7. Although not preferred, mixtures of such anionic detergents in the non-enzyme compositions can usually be used in ratios of 1 to 10: 1, such as 1: 2 to 2: 1.

.. Anionic detergents and surfactants will usually be omitted from the fabric softening liquid detergents.

The soil removal promoting polymer, which is an essential component of the composition of. This invention is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate which is soluble (preferably) or dispersible in water and which can be precipitated from washing water containing the detergent onto the synthetic organic polymeric fibrous materials, especially polyesters and polyester blends, to impart soil-removing properties thereto, while also leading comfortably to the wearer of the garments made of such material and not impeding or significantly reducing moisture transmission through such garments. Such polyesters also appear to possess anti-graying properties and often promote stain removal from substrates. They tend to keep the dirt, and in particular oily and greasy dirt, dispersed in the wash water during washing and rinsing so that it is not redeposited on the laundry. Useful products thereof are copolymers of ethylene glycol or other suitable sources of ethylene oxide units, polyoxyethylene glycol terephthalic acid or a suitable source of the terephthalic acid unit.

The copolymers can also be considered condensation products of polyethylene terephthalate, which can sometimes be referred to as ethylene terephthalate polymers and polvoxyethylene terephthalate. Although the terephthalic acid moiety is preferred as the sole dibasic unit in the polymer, it is within the invention to use relatively small amounts of isophthalic acid and / or orthophthalic acid (and sometimes other dibasic acids as well) to modify the properties of the polymer. The amounts of such acids or sources of such additional units fed into a reaction mixture, and the corresponding amounts in the final polymer, will normally be less than 10% of each of the total phthalic acid units present, and preferably less than 5% thereof.

The molecular weight of the polymer is in the range of about 15,000 to 50,000, preferably about 19,000 to 43,000, most preferably about 19,000 to 25,000, for example about 22,000. Such molecular weights are weight average molecular weights, to be distinguished from number average molecular weights, which are often lower for the present polymers. In the polymers used, the polyoxyethylene will have a molecular weight in the range of about 1000 to 10,000, preferably about 2500 to 5000, most preferably 3000 to 4000, for example, about 3400. In such polymers, the molar ratio of polyethylene terephthate will be - to polyoxyethylene terephthalate units (when 0 0 0 f0CH2C5 ^ 0-C-yOV ~ C3 and f (OCE ^ C ^) ^ -OC-Cj- are considered as Comparative unit) in the range from 2: 1 to by 6: 1, most preferably 5: 2 to 5: 1, and even better 3: 1 to: 4: 1, for example about 3: 1. The amount of ethylene oxide relative to the phthalic acid unit in the polymer will be at least 10: 1 8401065 1 3 6 and often 20: 1 or more, and is preferably in the range from 20: 1 to 30: 1 and most preferably is about 22: 1. it is believed that the polymer can essentially be considered as a modified ethylene oxide polymer, the phthalic acid unit of which is id 5 is only a minor component, either calculated on a molar or weight basis. It is considered surprising that with such a small amount of ethylene terephthalate or polyethylene terephthalate in the polymer, the polymer is sufficiently similar to a polymer of the polyester fiber substrate (or other polymers to which it is adherable, such as polyamides) that it is washed thereon during washing. , rinsing and drying is maintained. However, as demonstrated by comparative experiments and various wash tests in which the soil removal was measured, the polymer described in the present detergent compositions is effectively deposable on washed synthetic agents, especially polyesters, making it easier to wash them free of oily contaminants with a liquid ionic detergent composition or other detergent product. It is contemplated that the increased hydrophilic state of the polymer due to the large amount of the hydrophilic ethylene oxide units contained therein may be responsible for the excellent soil removal properties (to remove lipophilic impurities) which imparts to the material on which it is deposited, which will also promote co-operation with the liquid nonionic detergent product components.

Various literature articles, texts and patents describe methods for the preparation of the present polymers, such as Journal, among others. of Polymer Science, vol. 3, p. 609-630 (1948) and vol. 8, p. 1-22 (1951). Although suitable methods of making the subject polymers are described in such references, it is believed that none of them disclose the particular polymers used in the present invention (but are commercially available as such) and none of them disclose the present detergent compositions . It is considered that such polymers are statistically obtained from polyethylene terephthalate and polyoxyethylene terephthalate units, such as by the reaction of polyethylene terephthalate (for example, spin grade) and polyoxyethylene terephthalate or by reaction of the ethylene glycol, polyoxyethylene glycol, 8401065 * 7 * col and its acid (or methyl ester) precursors. However, it is also within the scope of the invention to use more ordered copolymers, such as those made by reacting components of predetermined or known chain length or molecular weights to produce the so-called block copolymers or non-random copolymers. Graft polymers are also practically useful.

The materials described are available from various sources, the products of one of which will be described in more detail below. Useful copolymers for the preparation of the detergent composition of this invention are marketed by Alkaril Chemicals, Inc., and commercial products of that company which have been used successfully to prepare satisfactory soil removal promoting detergent compositions sold under the trademarks Alkaril QCJ and Alkaril QCF, 15 formerly Quaker QCJ and Quaker QCF. Products available in limited quantities from them, designated 2Q56-34B and 2056-41, have also been found to be acceptable. The QCJ product, which is normally supplied as an aqueous dispersion, of about 1.4 or 15% concentration in water, and which is preferably used to make the present liquid detergents, is also as an essentially dry solid (QCF} available. In both such types of products, the molar ratio of ethylene oxide to the phthalic acid unit is about 22 s -1. In a 16% dispersion in water, such as QCJ, the viscosity at 100 ° C is about 96 centistokes The 2056-41 polymer resembles a hard light brown wax and the hydrophilic-hydrophobic ratio therein is about 16 to 1, while the viscosity is about 265 centistokes The 2056-34B polymer appears to be a hard brown wax, with a hydrophilic: hydrophobic ratio of about 10.9: 1 while its viscosity, under the aforementioned conditions, is about 255 centistokes.

The higher the molecular weight of the polymer, the lower therein will be the hydrophilic: hydrophobic molar ratio which still leads to a satisfactory soil removal promotion by the detergent composition of the invention. 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 6-8 in distilled water at 5% concentration The molecular weights (weight average) are in the 8401065, range from 20,000 to -25,000 and the ethylene terephthalate: polyoxyethylene terephthalate units molar ratio is about 74:26. All of the trademarked products mentioned are water soluble in hot or hot water (at 40 - 705C) or at least readily dispersible, 5 «and have a property of a Jaoogo molecular weight, above 15,000, generally in the range of 19,000 to 43,000, often preferably 20,000 to 25,000, for example about 22,000.

The enzymes used in some of the compositions of the invention include both proteolytic and amylolytic enzymes, such as the alkaline proteases (subtilisin) and α-amylase. Preferred enzyme preparations that are useful are Alcalase 2.5L (2.5 Anson units per gram) and Termamyl 120L, both prepared by Novo Industri, A / S. However, suitable other proteolytic and amylolytic enzyme preparations can also be used. The said compositions are in liquid form and contain 5% active enzyme in combination with 65% propylene glycol and 30% water. In this description, the stated amounts refer to the active enzyme (s) in the preparations.

The stabilizer or a mixture of stabilizers for the enzyme is most preferably sodium formate or includes such a salt, but other water-soluble formates, such as potassium formate, may also be used, and also acetates, as well as other equivalent salts or mixtures of such salts and alkali metal formate.

The fabric softener, namely, the quaternary ammonium salt used in some of the liquid detergent compositions of the invention can be any suitable material that is stable in the present composition. In some instances, known imidazolinium halides with satisfactory stability may be used in place of the usual quaternary ammonium halides.

However, the quaternary ammonium halides are preferred. Such compounds will preferably be chlorides, although bromides and iodides are also useful. Of the four substituents on the quaternary nitrogen, at least one, and preferably two, is a long chain substituent such as a higher linear or fatty alkyl group, and most preferably two such substituents will have a higher fatty alkyl. to be. The chain length will usually be 10 to 20 carbon atoms, preferably 8 * 101065 * 12. 18 carbon atoms, with chain lengths of 12-14 carbon atoms or mixtures thereof, such as coconut (derived from coconut oil or an equivalent material) being most preferred. The other substituents on the nitrogen will be lower alkyl, usually 5 with 1-3 carbon atoms, of which methyl is most preferred.

Although other quaternary ammonium halides are useful, at least when they are only part of the quaternary emollient, dikocos dimethyl ammonium chloride is most preferred and most stable in the liquid detergent compositions herein. Such a product is available as a liquid containing 75% active ingredient, 14% isopropanol and 11% water.

The aqueous medium used comprises water and preferably also a lower alkanol. It is. desirably that the water be deionized water but city water with a hardness of up to about 300 parts per million, such as calcium carbonate (the hardness is usually formed by mixed magnesium-calcium ions) is useful, although it is preferred that their hardness content. less than 100 ppm to avoid any destabilization of the liquid detergent or separation of parts thereof. Some of the water may come from the starting materials, such as aqueous soil removal promoters, enzyme preparations, emollients, alkanols, and dyes. The lower alkanol can be ethanol, isopropanol or n-propanol, with ethanol being preferred. When ethanol is used it will normally be a denatured alcohol, such as 3A, containing a small amount of water plus denaturing agent. Also small amounts of compatible dissolved salts can be present in the aqueous medium, but normally will. this should be avoided as much as possible

Another liquid which it is desired to use in some of the present liquid detergents, such as those containing enzymes and fabric softeners, is a lower glycol, such as a glycol having 3-6 carbon atoms in its alkyl group. While such a composition can be used in hexylene glycol, it gives rise to instability on the other hand, so that propylene glycol is preferred.

Various suitable adjuvants may be present in the liquid detergent compositions of the invention, such as fluorescent dyes, colorants (dyes and water dispersible pigments, such as ultramarine blue), bacteria, fungicides and perfume,

The concentrations of such components will usually be kept low, often less than 1% and preferably less than 0.7%. The perfume concentration will thus usually be less than 1%, and is preferably 0.2-0.6%, such as 0.4%. Fluorescent tint improvers or optical brighteners may be present in the liquid detergent in an amount of 0.02-2%, preferably 0.1-1%, and most preferably 0.2-0.5%. The percentages indicated are those of the commercially available materials. Such tint improvers are known as cotton improvers, bleach soluble improvers, polyamide improvers and polyester improvers and generally mixtures thereof are used making the detergent useful for the enhancement of a range of materials to be washed, including cotton and synthetic materials. Examples of such good hue enhancers are those identified as i TA; DM; DMEA; DDEA; DMDDEA; BS; NTS; BEI; AC; DP; BBO; FOREST; and NTSA, in a well-known article entitled Optical Brighteners and Their Evaluation by Per S. Stensby, published in Soap and Chemical Specialties in April, May, July, August, and September, 1967. A further discussion of fluorescent tint enhancers can be found in an article entitled Optical Bleaches in the Soaps and Detergents by FGVillaume, which appeared in The Journal of the American Oil Chemists' Society (October 1958), volume 35, no. 10. pp. 558-56. Useful fluorescent tint enhancers are sold under the trade names: Calcofluor White ALF 25 (American Cyanamid); ALF-N (American Cyanamid); SOF A-2001 (CIBA); 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 tint improvers are normally present in the form of their water-soluble salts, but they can also be used in the corresponding acidic forms. Most materials are useful for enhancing the shade of cotton and consist of the stilbene sulfonic acid (or salt) or amino stilbene types, referred to herein as stilbene enhancers, the preferred enhancer being Tinopal 5BM Extra Gec., From CIBA-Geigy. For a fabric softening detergent, the preferred amount of the improver is 0.05-025%, especially 0.05-0.15%, e.g. 0.1%. Dyes such as Polar Brilliant Blue will be present in an amount of 0.001 - 0.03%, 8401065 11 S% preferably 0.002 - 0.2% based on the liquid detergent, e.g. 0.025¾ or 0.01%, if present. The various auxiliary materials are chosen so that they are compatible with the other components of the composition and do not give rise to sizing or settling. Since water-soluble ionizable salts, whether inorganic or organic, are generally incompatible with soil removal promoters, their presence is usually avoided. The best salts to avoid include sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, airanonium chloride and ammonium sulfate, but these are only examples of such salts. Although sodium formate must also be omitted from many liquid detergents, surprisingly a limited amount thereof has been found to be compatible with the other components of the present composition in combination. The presence of ionizable compound types, such as triethanolamine (TEA), diethanolamine, ethanolamine, diSopropanolamine, n-propanolamine and of the lower mono-, di-, tri- and mixed lower alkanolamines with 2 - 4 carbon atoms per alkanol unit should be avoided since 2, as well as the salts mentioned, destabilize the polymer promoting the soil removal and / or the liquid detergent. It appears that TEA gives rise to most of the destabilization and separation of the polymer. In this specification, such ionizable compound types, which may form salts, are to be counted as parts of the allowable amounts of such salts which may be present. In general, it is desirable to avoid the presence of auxiliaries other than dyes, perfumes, fluorescent tint improvers, antioxidants and any neutralizing agents which can be used to adjust the pH of the liquid detergent in the stable range. It is preferred that with the optional use of a neutralizing agent, usually to raise the pH of the liquid detergent mixture, this agent is alkali metal hydroxide such as sodium hydroxide, in aqueous solution at a concentration of 5-40%, e.g. 15 - 25%. In particular, triethanol-35 amine salts and free triethanolamine should be avoided.

8401065 t s 12

The correct viscosity of the liquid detergent will generally be in the range of 50-500 centipoises, and is preferably 100-200 centipoises, the viscosity being adjustable by the amount of lower alkanol within the given range. to change. The liquid detergent will be easy to pour but will have a desired "firmness". Its pH will be in the range of 6-9, and is preferably 6.1-7.9, especially 6.5-7.5.

In the liquid detergent compositions of the invention with improved soil removal properties, which have increased stability upon storage so that the soil removal promoting polymer and enzyme (s) will not deteriorate and will not separate from the rest of the composition the amounts of the various components are as will be indicated below. All of the various components mentioned, although indicated in singular, also include mixtures. The amounts of the following components are directed to the invention in its most general form, respectively. the enzyme-containing product and the enzyme-softening agent-containing product.

The nonionic detergent (including mixtures thereof) or a mixture of nonionic and anionic detergents (both of the synthetic organic type) are in the range of 25 - 50¾ of the product, preferably 20 - 40¾ for the non-ionic detergent and 3 -15¾ for the anionic detergent. Most preferably, the amounts of such detergents are resp. 25 - 35¾ and 5 - 10¾¾ e.g. resp. about 32¾ and about 71. The moisture-promoting polymer is present in amounts of 0.5 - 10% a, preferably 1 - 6¾, and in particular bl - 31, e.g. about 2%. The lower all canoe! content will be 3-15¾, and is preferably 5-12¾30 and especially 6-101, such as about 8%, while the water content, when the lower alkanol is present, will be about 30-60¾, and preferred is 35 - 55¾, while if no lower alkanol is present, such ranges may be increased due to the replacement of the lower alkanol with water. The amounts of the ionizable water-soluble salts, both organic and inorganic, should be kept low, usually not more than 1% of the liquid detergent, preferably less than 0, 5 ¾ and in particular less than 0.3,, wherein the triethanolamine content will also be limited in order to avoid separation of the polymer promoting the soil removal, the desired limits being 0.5%, preferably 0.2% and in particular be 0%. In some cases the salinity will be kept within limits lower than the permitted alkanolamine content because some salts may be even more damaging to the product stability than the alkanolamines. Of course, the content of anionic detergent present, which can be considered an ionizable salt, will not be included in the limits of such a salt present because it does not appear to have the same type of destabilizing effect on the present compositions. While suitable adjuvants may be present in the liquid detergent such as the colorant, perfume and fluorescent tint enhancer, as mentioned previously, the amounts of such adjuvants will normally be minimized, and they are usually less than 2%, preferably less than 1% and most preferably less than 0.8%, even though the dye and improver are not destabilizing.

For the enzyme-containing product (without softener), the synthetic organic, nonionic detergent content will normally be in the range of 25-40% of the product, and is preferably 28-36%, most preferably 30-34% , such as .32%. The fatty alcohol alkoxy-25 sulfate content will usually be 1 - 8%, and is preferably 2 - 7%, and most preferably 2 - 6%, such as 3% or 5%. The fluorescent tint enhancer content is in the range of 0.02-2% and is preferably 0.1-1%, e.g. 0.2% or 0.4%. The percent active ingredient of the improver can often be 0.01 to 1%, such as 0.01-30 0.1%. The soil removal promoting polymer content will be about 0.5-5%, and is preferably 0.8-3%, and most preferably 0.8-2.5%, such as about 1% or 2% (at an active component base). The total enzyme content will usually be in the range from 0.0005 to 0.15% and is preferably 0.025 - 0.1%, the protease content of which is 0.005 - 0.1% and the amylase content, if present, 0.005 - 8401065 14 0.05¾. Preferred levels of the enzymes are resp. 0.01 - 0.1% and 0.01 - 0.03%. Most preferably, the percentage of protease is 0.02-0.05%. Specific formula percentages are, respectively, about -0.03% and: 0.02%. The stabilizer for the enzymes, usually an -al potassium-5 metal salt of a low diphatic acid with 1-3 carbon material atoms, such as sodium formate, will normally be substantially present in an amount of 0.2-2%, preferably 0.05-1.5%, and most preferably 0.7-1.3%, eg 1%. The lower al canoe content will be 3-12%, and is preferably 4-9%, most preferably 5-8%, e.g. 5.5 or 7.5%.

The water content will be about 40-65%, and is preferably 46-52%, especially 50-60%, e.g. about 54 or 55%.

The content of ionizable water-soluble salts, whether organic or inorganic, should be kept low, less than 2%, usually no more than 1% of the liquid detergent, preferably less than 0.5%, and most preferably less than 0.3%, wherein the triethanolamine content will also be limited to prevent separation of the polymer promoting the soil removal, the desired limits being 0.5%, preferably 0.2%, and most preferably 0% . In some cases, the salinity will be maintained at values below the limits for the allowed canoe! content because some salts can be even more damaging to product stability than alkanolamine. However, in the present compositions, the levels 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, with the detergent product. and the polymer which promotes dirt removal is compatible, so that no polymer separation will occur.

For the enzymatic and softening liquid detergents, the synthetic organic non-ionic detergent content (which includes blends) is in the range of 10 - 35% of the product, preferably 15 - 30% and most preferably 20 - 25% , like 22%. The moisture removal promoting polymer content will be about 0.5-5%, and is preferably 0.7-2%, and most preferably 0.8-1.5%, such as about 1% (on an active component base). The content of the quaternary compound will be 1 - 10¾, and is preferably 3 - 8%, and most preferably 3 - 61, e.g. 4.5¾. The enzyme content can range from 0.005 - 0.15%, and is preferably 0.025 - 0.05%, the protease content of which is 0.05 - 0.1% - and the amylase content, if present, 0.085 - 1) .05%. Preferred levels of the enzymes are resp. 0.01 - 0.05% and 0.01 - 0.025%. More specifically, all the protease content ranges from 0.015 to 0.04%. Specific formula percentages are resp. about 0.023 and 0.015%. The stabilizer for the enzymes, lower aliphatic acid salt, such as sodium formate, will usually be present in an amount of 0.2-2%, preferably 0.5-1.5% and especially 0.7-1.3 %, such as 1%. The lower al canoe content will be 1 - 10%, and is preferably 1.5 - 3%, and most preferably 2 - 2.5%, such as 2 or 2.2%. The lower glycol content is 2-10%, preferably 3-8%, and most preferably 4-15%, such as 6%. The water content is about 40-80%, preferably 50-70%, most preferably 60-65%, e.g. about 63%.

The levels of ionizable water-soluble salts, whether organic or inorganic, should be kept low, usually not more than 1% of the liquid detergent, preferably less than 0.5%, and most preferably less than 0.3%, wherein the triethanolamine content will also be limited to prevent separation of the soil removal promoting polymer, the desired limits being 0.05%, preferably 0.2%, and most preferably 0%. In some cases, the salt content will be kept below 25 limits of the permitted alkanolamine content because such salts can be even more damaging to product stability than the alkanolamine. However, in the present compositions, the levels of water-soluble alkali metal-lower carboxylate, such as sodium formate, may be up to 2% because such components stabilize the enzymes and are compatible with the detergent product at such concentrations, especially at about 1% or less. .

The liquid detergent compositions of the invention can be prepared by mixing the various components thereof with the aqueous medium, which preferably contains at least a portion of the lower alkanol, until dissolved (or satisfactorily dispersed) therein ), or the different components can be selectively dissolved in parts of the water and / or the lower alkanol and / or the low glycol, and / or the liquid polymer removal promoting polymer preparation, * and / or the liquid enzyme preparation, after which the different liquid fractions can be mixed together. In most cases, it is preferable to adjust the pH of the liquid within the range of 6.1-7.9, most preferably 6.5-7.5 by adding an appropriate neutralizing agent (non-triethanolamine). that there will be no destabilizing effect on the polymer removing the enzyme, the enzyme (s), the softener, or the softening liquid product, so that the latter will not be deteriorated and will not separate from the liquid detergent upon storage, especially when stored at elevated temperature.

The preferred neutralizing agent is an aqueous solution of sodium hydroxide, which will normally contain between 10 and 40% sodium hydroxide, and preferably 15-25%, although sometimes more dilute concentrations are desired. The viscosity of the product can then be adjusted by adding alkanol and / or water.

The liquid detergent composition according to the invention can be used for washing (and treating) synthetic laundry containing scissors, such as polyester, e.g. Dacron, normally as used in washing with other liquid detergents. However, because of its fumigation-promoting effect, less of the present product can be used, while in many cases the cleaning and softening effects will be better. Different concentrations of the liquid detergent can be used, normally about 0.02 or 0.04 to 0.3 or 0.6%, preferably 0.05 or 0.1 to 0.15 or 0.3%, the concentration generally is about 1/2 cup per wash in a top loading machine for the product containing an emollient, and about 1/4 cup per wash for the other two types of products. Generally it is advised about 1/4 use up to 1/2 cup (about 60 or 120 cm3) of the liquid detergent per standard wash volume (about 64 dm3 .35 for a top washing machine), giving a concentration of 8401065 17 of about 0.1 or 0.2¾ of the liquid detergent is in the wash water. About the same concentration can be used when washing is performed in a front loader machine, although less heat is used (so that less detergent composition is used}.

5 Normally about 3 - 3.5 kg laundry will be loaded in the machine.

The washing water temperature will preferably be at least 49 ° C, but good washing treatment by the polymer promoting the soil removal, the enzymes and the softening agent in the liquid detergent can be reached at temperatures in the range of about 40 - 80 ° C, preferably 45 - 70 ° C. The dry weight of the materials to be washed and treated is usually about 5 to 15 or 20% of the weight of the aqueous washing medium, preferably about 5 to 10% thereof. The washing will be carried out with stirring for a period of from about 5 minutes to half an hour or an hour, often from 10 to 20 minutes.

The laundry is then rinsed, usually several times, and dried as in, for example, an automatic spin dryer.

Preferably, the first washing of the material will be carried out when the material is not too dirty, so that the dirt-promoting polymer is deposited on as clean a surface as possible. However, this is not necessary and improvements in the cleaning of later soiled materials and wipes will be observed if no special attempts have been made to perform the first wash with a cleaner substrate. To a certain limit, sometimes about three or five treatments, multiple washes with the liquid detergent of this invention will enhance the soil removal properties of the treated material.

When polyester and polyester / cotton blend fibers are washed in the manner described for the compositions of this invention, and then are soiled or stained with contaminated engine oil and washed with a detergent according to the invention or other commercial detergent (often of the compound type), significant removal of the lipophilic soil is noted, compared to similar treatments in which the liquid detergent used does not initially contain the polymer promoting the soil removal 8401065; -v 18. In other comparisons, when significant amounts of water-soluble ionizable salt, such as sodium sulfate, or more than 1% triethanolamine or a salt thereof, are present in the liquid detergent, it is found that storage at elevated temperature 5 (43 ° C) C) for 1 weeks, thereby simulating longer storage at room temperature * phases are separated from the liquid detergent composition, thereby deteriorating the soil-promoting properties of the polymer contained therein, as well as the enzymatic and softening activity, when such materials are in the be present. If the enzyme stabilizer is omitted, the enzymatic action on storage deteriorates considerably. Thus, the compositions of this invention are important because they are stable, and for the intended purposes, improving soil removal, cleaning effects and softening the washed fabrics are more effective and also result in a more attractive liquid detergent composition that does not curdle on storage.

The following examples illustrate the invention without limiting it. Unless otherwise indicated, all parts are by weight and all temperatures are in ÖC.

Example I

Component%

Neodol .23-6.5 (condensation product of approximately 32.0 6.5 moles ethylene oxide and a higher fat alcohol with an average 12-13 carbon atoms per mole) linear sodium dodecylbenzene sulfonate (LDBS) 7.0 sodium sulfate (accompanies the .LDBS ) 0.2 soil removal promoting polymer (a copolymer 14,330 of polyethylene terephthalate and polyoxyethylene terephthalate having a molecular weight of about 22,000 with the polyoxyethylene having a molecular weight of about 3,400, the molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate- units is about 3: 1 and 8401065 t 19 the amount of ethylene oxide relative to the phthalic acid unit in the polymer is about 22: 1, sold by Alkaril Chemicals, Inc. as iAlkaril 'QCJ, in the form of a 14¾ * dissolve 5 in water) denatured ethanol (3A) 8.0 fluorescent tint enhancer (Tinopal 5BM, Extrawee.) 0.24 dye (polar brilliant blue) 0.01 perfume 0.4 10 delonised water q.s.

100.00

The liquid detergent composition is made by mixing an amount of the water with the nonionic anionic detergents, followed by addition of the soil removal promoting polymer, the ethanol, the fluorescent tint enhancer, dye and any residual water. An acid or base (NaOH is preferred) can then be used to adjust the pH in the desired range if desired. In the above example, the pH is

7.8 (not diluted). 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, the amount used being small, e.g. about 0.2¾ or less NaOH. The amount of perfume desired for the composition is then added. The product prepared is examined by storing it at 43.3 ° C for 2 weeks, after which it is observed that it is still in a single phase, essentially the same as the product produced.

Shortly after preparing the liquid detergent, it is used to wash a sample of clean fabrics, including some polyester materials as well as other materials of 65¾ polyester and 35¾ cotton. The washing concentration is 0.1% by weight of the liquid detergent based on the weight of the wash water, and the washed wipes make up about 5% by weight, based on the wash water. After washing in a standard test washing machine, using the standard conditions previously described, wipes are rinsed and dried.

8401065 • ♦ 20

Each test cloth is then contaminated with approximately 3 drops of standard type dirty motor oil used for such an examination and washed in the same type of machine with a commercially available detergent ™: Wipes used as controls 5 are not pre-treated with the present liquid detergents. The temperatures during the washing treatment and the subsequent washing are the same in all these cases, namely 49 ° C, which temperature is regarded as an optimum temperature for the treatment.

In some tests, the subsequent washing is carried out with the liquid detergent according to the invention. In all tests, the treated wipes are significantly whiter to the eye and according to the reflectometer test than the control wipes, demonstrating that the soil removal promoting component of the liquid detergent composition effectively removes such applied contaminants during subsequent wash steps. of the wipes. It is also noted that the graying of the unpolluted parts of the fabrics by the removed dirty engine oil (as initially applied) is reduced when the dirt removing polymer is applied to the fabric prior to the test and application of the engine oil. applied. Thus, the liquid detergent containing the soil removal promoting polymer, in addition to promoting soil removal, also promotes its suspension, thereby preventing 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 given above, replacing some of its water, it appears that the detergent is washed after 2 weeks of storage at 43.3 ° C. The separation also takes place under conditions that the triethanolamine is absent but 5% sodium sulfate is present in the formula. Also, when the triethanolamine is present, the soil scrubbing action of the liquid detergent is significantly reduced, compared to the experimental composition of this invention after 2 weeks of elevated temperature aging at 43.3 ° C, followed by the study previously described. Storage at room temperature also leads to such a reduction in the soil removal promotion activity of the composition containing triethanolamine compared to the experimental formula.

When the amount of the soil removal promoting polymer is lowered to 1% or increased to 3%, the same results as mentioned above are obtained, with the modifications that the 3% removal polymer composition is more effective than the 2 % formula for promoting the removal of fluids according to the tests described, the 1¾1s formula being slightly less effective, although at 1% and 3¾ concentrations, respectively. good and excellent results are obtained.

When similar tests are performed using other lipophilic impurities, such as corn oil (red), butter, shoe paste, lipstick, mayonnaise and barbecue sauce, similar results are obtained, with the greatest improvements of the experimental composition over the control obtained with respect to the corn oil, lipstick and dirty motor oil. The removal is 100¾ for the corn oil, butter, mayonnaise and barbecue sauce stains and almost 100% for lipstick. Similar results are obtained when the test fabrics are single knitted dracon, double knitted dacron and dacron / cotton blends and they are also obtained at treatment temperatures above 32 ° G. Such results are also obtained when a commercial or household top load or side load washing machine is used in place of the laboratory test washing machine.

Example II

In the first formula of Example I, the linear sodium dodecylbenzene sulfonate is replaced by the corresponding tridecylbenzene sulfonate and in another case by Neodol 25-3-5, which is the sodium salt of a sulfated condensation product of approximately 3 moles of ethylene oxide with is a higher fatty alcohol with an average of 12-15 carbon atoms per mole, while the nonionic detergent is replaced in both cases by Neodol 25-7. When the resulting compositions are tested for increased temperature stability and storage stability, as described in Example 1, equally good results are obtained. When more than 0.5% triethylamine amine is present in the composition instead of an equal amount of water and / or when 21 sodium sulfate or other water-soluble ionizable salts. are present, as mentioned, a separation of the components of the liquid detergent is observed. When the liquid detergents 5 according to this example are used for washing polyester fabrics of the types alder mentioned in example 3, after which the fabrics are contaminated and washed subsequently, an improved lipophilic soil removal is obtained, compared to the controls which do not contain the soil removal promoting polymer of the type used in the formulas of this example. Also, when more than 0.51 triethanolamine and / or 21 water-soluble ionizable salt, such as sodium sulfate, is present in each of the formulas, after elevated temperature or room temperature, aging for a period of respectively. 2 weeks and 3 months, if the quenched composition is shaken to disperse the various components thereof and then used as described previously, the soil removal effect thereof is still significantly reduced, compared to the experimental formulas which are neither do not contain triethanolamine or any such salt.

Example III

The first formula of the invention as given in Example I is modified by replacing its anionic detergent with Neodol 25-7 so that the product contains 391 nonionic detergent and also replacing the ethanol with deionized water. The product does not curdle on storage and has the same soil removal properties as those of the products of the invention of Examples 3 and 31. Also, the experimental product is stable during accelerated aging at elevated temperature storage and for extended periods at room temperature storage, while on the other hand, a comparable product containing 11 triethanolamine and / or 21 sodium sulfate will curdle. Likewise, such comparable products do not promote the removal of deposited lipophilic impurities to the extent achievable with the experimental products of this example.

8401065% t zz

Example IV

When the contents of the various experimental formulas of this invention, as indicated in Examples 1 - III, are varied to a degree of + 10% and ± 25%, amounts of the different materials within the ranges mentioned in the application areas are maintained, and when in such compositions instead of the QCJ soil removing polymer (aqueous solution), "2% QCF (Alkaril Chemicals CAS 9016-88-0) and 12.3% water are substituted, the QCF first When dissolved in water, good dirt-removing properties also arise, as well as those described in Examples I-III, in which the products are stable and do not curdle on storage.

This is also the case when the fluorescent liquid, colorant and perfume are omitted from the formulas of this example. Furthermore, when triethanolamine or an ionizable salt in such formulas are present outside the given limits, the product becomes less stable and less effective in soil removal during washing.

In other variations in this example, the nonionic detergent is a mixture of equal parts Neodol 25-7 and Neodol 91-6 and 20 is the anionic detergent Neodol 45-2.25-S. Equal results as stated in Examples I - III are obtained with both top loaders and side loaders, commercial or household washing machines. This also applies when pH adjustments are made with potassium hydroxide as well as with sodium hydroxide or potassium hydroxide to a pH of 7.0, 6.6 and 7.4. Normally, at such a pH setting, less than 1% sodium hydroxide solution, preferably less than 0.5% thereof, and most preferably less than 0.2% thereof, will be consumed. In some cases, the sodium hydroxide may be added as an ingredient of the composition in an amount such that the desired pH control (based on experience with the compositions) is obtained, but it is still preferred to add it before the perfume, although this is not strictly necessary. Although a 20% sodium hydroxide solution concentration is often more preferred, other concentrations can also be used.

8401065 24

Example V

Component Percentage

Neodol 25-71 32.0

Neodol 45-2.25S2 3.0 5 Alkaril QCJ soil removal promoting polymer (151) Ί3.4 denatured ethanol (3A) .5.5 sodium formate .1.0

Alcalase 2.5L3 0.6

Termamyl 120L ^ 0.4 10 Tinopal 5BM5 0.27 Dye (Polar Brilliant Blue) 0.0025 Perfume 0.4 De-toned Water q.s.

100.00 1. Condensation product of approximately 7 moles of ethylene oxide and a higher fatty alcohol with an average of 12-15 carbon atoms per mole.

2. Sodium salt of the sulfuric acid ester of the non-ionic condensation product of a higher fatty alcohol with an average of 14-15 carbon atoms, with 2.25 mol ethylene oxide.

20 3. Proteolytic enzyme sold by Novo Industri, A / S (5% enzyme active component, 65% propylene glycol 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 fluorescence tint enhancer sold by CIBA-Geigy.

The liquid detergent is made in the manner of Example 1, by mixing a portion of the water with the anionic and non-ionic detergents, followed by addition of the soil removal promoting polymer, the ethanol, the fluorescent tint enhancer (sometimes dissolved in ethanol or ethanol-water solutions), enzymes, sodium formate (dissolved in some water), dye, and any residual water. Then, if desired, an acid or base (NaOH is preferred) can be used to adjust the pH in the desired range, e.g. 7, to set. When the .pH is lower than desired, the aqueous solution of sodium hydroxide (20%) is used to raise it to the desired level. The amount used is small, e.g.

8401065 0.25 or less NaOH. Then the determined amount of perfume is added. The product obtained is examined by storing it at 43.3 ° C for a week, after which it is found - upon observation - to be a clear light blue "liquid in a single stable" phase, essentially the same - to the made composition. The protease activity is better than that of a liquid control detergent - containing 1% sodium dodecylbenzene sulfonate, 2.8¾ triethanolamine (TEA) and no alcohol ether sulfate, and much better than in other formulations equal to the control but not sodium formate in one case and no TEA in the other. When both the formate and TEA are omitted from the control formula (in these cases the differences are supplemented by water), both the protease and amylase activities are drastically reduced. The control and the first two variations are unstable on storage as evidenced by the settling of the polymer.

Shortly after making the liquid detergent, it is used for washing a sample of clean fabrics, including polyester materials as well as others consisting of 65¾ polyester and 35¾ cotton. The washing conditions are the same as those in Example I 20 and the results are almost the same, except that an additional enzymatic cleaning action is obtained. Such desirable activities are achieved despite the presence of the sodium formate liquid and any other salts.

When 2.8 ¾ triethanolamine or a TEA salt is present in the liquid detergent of the aforementioned composition to replace some of its water, the detergent appears after storage for one week at 43.3® C to be separated in layers. The screening also takes place when the triethanolamine is absent and the sodium sulfate composition is present in the composition. Storage at room temperature also results in such layer separation and a corresponding reduction in the soil removal promoting activity of the compositions containing the indicated amounts of triethanolamine and / or sodium sulfate compared to the experimental composition.

35. Examination of the liquid detergent for enzymatic cleaning performance 8401065 26 gives satisfactory results, indicating that the proteolytic and amylolytic enzymes in the stable liquid detergent are "functionally effective. This result is achieved despite the" fact, enzymes - are often unstable in liquid wash systems, especially at elevated temperatures.

Example VI

In a modification of the composition of Example V, when the amount of Neodol 45-2.25S is increased to 5%, the amount of ethanol is increased to 7.5%, 0.01¾ polar brilliant blue dye is used instead of 0 0.0025% and the improver is replaced with 0.24% Tinopal 5BM and 0.1% Phorwite BHC, a stable liquid detergent with improved soil removal properties, enzymatic effectiveness and washing power equal to that of the composition of Example V or better. The liquid detergent is bright blue and may be of light color in the absence of dye, so it is desirable to use this boron to be colored using other dyes. Instead of the stated tint enhancer system, equivalent amounts of Tinopal RBS-200, Tinopal 4226 (CIBA-Geigy) or Phorwite RKH (Mobay Chemical Compnay) and mixtures thereof can be substituted. In all these cases, the directness of the fluorescent tint enhancer is enhanced by the presence of the higher fatty alcohol ethoxylate sulfate and unlike other anionic detergents, such as linear sodium dodecylbenzene sulfonate, the fatty alcohol ethoxylate sulfate does not cause destabilization of the polymer soil improver in the presence of enzyme. and enzyme stabilizer.

Example VII

The composition of Example V is changed so that 5% Neodol 25-3S is present instead of the 3% Neodol 45-2.25S. It ΟΠ

made product is stable and clear after storage at elevated temperature while the Alcalase and Termamyl stabilities are equal to those for the first control mentioned in Example V. However, when 2.8% TEA is also present in the composition, the product becomes unstable, wherein the QCJ soil removing polymer after storage at 43 ° C

gr flocculated for 1 week.

8401065 27

Example VIII

The contents of the various experimental compositions of this invention in Examples V-VII are varied by ± 10% and ± 25% while maintaining the amounts of the different materials within the ranges mentioned herein. In such compositions, in place of the QCJ debris removing polymer (aqueous solution), 2% QCF (Alkaril Chemicals CAS 9016-88-0) and 11.4% water are substituted, with the QCF being first dissolved in the water. Also, other enzymes, stabilizers, alcohols and dyes, as specified herein, can be used within the given ranges of amounts.

The detergent compositions obtained are clear, stable and non-scuffing and have improved soil removal, cleaning and tint enhancing properties such as those described in Examples V-VII. This is also the case when the fluorescent dye, colorant and perfume are omitted from the compositions of this example. Likewise, when triethanolamine or an ionizable salt is present in such compositions outside the stated limits, and when other anionic detergents, such as sodium higher alkylbenzene sulfonates, are substituted for the alcohol ethoxylate sulfate, the product becomes less stable and less effective in soil removal during washing, while if the sodium formate is omitted the effect of the enzyme is lost after only a few days of storage at elevated test temperature.

In other 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, using the same total amount and obtaining a stable effective product. Also, the alcohol ethoxylate sulfate can be an equal mixture of Neodolen 25-3S and 45-2.25S to give good results. With such variations, the results noted previously in Examples V - VII are achievable with both test washers and household and commercial washers, which are either top loaders or side loaders. This is also the case when pH adjustments are made with potassium hydroxide and also when such adjustments made with sodium hydroxide or potassium hydroxide are aimed at pH's of 6.6, 7.4, 7.9 and 8.6. Normally, at such pH settings, less than% of sodium hydroxide solution, preferably less than 0.5% thereof, and most preferably 0.2% thereof, will be used. In some instances, the sodium hydroxide may be added as the constituent of the composition in an amount known to provide the desired pH control (based on the experience of the composition) but it does it is always preferable to add the sodium hydroxide before the perfume, although this is not strictly necessary. Although a 20% sodium hydroxide solution concentration is also often preferred, other concentrations may also be used.

From Examples V-VIII and the foregoing description it can be seen that the present invention comprises a stable and attractive liquid detergent containing various components which would have been expected to adversely affect the stability of the final product. Surprisingly, a stable product is obtained according to the invention. Such a product has the desired soil removal, soil decomposing, fluorescent tint enhancing (when the tint enhancer is present) and detergent properties. Various components of the compositions of the invention have a double effect therein. The alcohol ethoxylate sulfate promotes washing performance and makes the substrates (laundry fibers) more direct so that the fluorescent tint enhancers are more effective. The sodium formate, which is an enzyme stabilizer, does not destabilize the soil remover as one would expect. The various components of these liquid detergents work together to produce a surprisingly attractive, stable and effective detergent composition. Thus, it is apparent that the present compositions represent a non-predictable advance in the art of making stable products that are attractively clear (translucent or translucent), although in some cases also opalescent and semi-translucent or make creamy products on purpose.

8401065 29

Example XX

Component Percentage

Neodol 25-7 22.0

Alkaril QCO promotes soil removal: polymer (15¾) 5.7 5 Adogen 452® £, 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 (Polarized Blue) 0.0025 Perfume 0.4 Deionized Water q.s.

100.00 15 6. Di-coconut dimethylammonium chloride, sold by Sherex Industries (contains 75% active ingredient, 14% isopropanol and 11% water).

The liquid detergent composition is made in the same manner as described in Examples V-VIII but including the fabric softener and omitting the anionic detergent. The product is examined by storing it at 43.3 ° C for one week, after which it is observed to be a clear light blue liquid in a stable single phase, essentially the same as during the preparation. The protease activity is 70% of the value in the preparation of the liquid detergent, while the amylase activity is 85% of its initial value.

Shortly after the liquid detergent has been made, it is used to wash a sample of clean fabrics, including some polyester materials as well as other materials of 65% polyester and 35% cotton. The washing concentration and other washing conditions are the same as in Example V; the results are essentially the same except for the improved fabric softening obtained according to this example. It was also found that when 2% or 3% triethanolamine or TEA salt is present in the liquid detergent of the above formula, replacing part of its water, the detergent in layers after 2 weeks of storage at 43.3 ° C 8401065 30 was found to be separated. This separation also takes place when the triethanolamine is absent and 5¾ sodium sulphate is present in the composition. When the triethanolamine is present, the removal of sulfur promotes the effect of the "Liquid detergent sig-5" - backwards * Storage at room temperature also leads " to such a reduction in soil depletion promoting activity of compositions containing the indicated amounts of triethanolamine and / or sodium sulfate compared to the experimental formula When the amount of the soil depletion promoting poly-10 is more reduced to 0.8¾ or increased to 21, the same types of results as indicated above are obtained.

Tests with the liquid detergent in tissue softening and enzymatic cleaning performance are satisfactory, which indicates that the quaternary ammonium halide and the proteolytic and amylolytic enzymes in the stable liquid detergent are functionally effective. This is the case despite the fact that enzymes and quaternary ammonium halides are often unstable in liquid detergent systems, especially at elevated temperatures. When propylene glycol is replaced by higher glycols, such as those with 8 to 12 carbon atoms, a two-phase separation of the product will occur. In the particular formula, complete replacement of propylene glycol with hexylene glycol will also cause phase separation although hexylene glycol and amylene glycol are considered useful glycol components of the present type liquid detergent when used in small amounts and together with lower glycols such as propylene glycol . Also, if the di-coco dimethyl ammonium chloride is replaced by di-hydrogenated tallow dimethyl ammonium chloride, the liquid detergent will also separate into two phases, in particular in the presence of the hexylene glycol (replacing propylene glycol). However, it is again pointed out that in certain cases the di-hydrogenated tallow dimethyl ammonium chloride can be used in a stable product by decreasing the amount added and mixing it with di-coconut dimethyl ammonium chloride or other di-higher alkyl di- lower alkyl-35 quaternary ammonium halides in which the higher alkyl groups contain 12 - 14 8401065 ΛΓ * 31 carbon atoms and the lower alkyl groups contain 1 or 2 carbon atoms. As an alternative, a more hydrophilic quaternary ammonium halide, such as di-tallow dimethylammonium chloride, which has a higher degree of unsaturation and thus is more tolerant of 5 electrolytes, can be used successfully.

Example X.

When, in the first formula of Example IX, nonionic detergent is replaced with Neodol .23-6.5, 0.01¾ polar brilliant blue is used as the dye instead of 0.0025¾ and a stil-10 leg fluorescent tint enhancer is present, e.g. Tinopal RBS-2Q0, Tinopal 5BM or Tinopal 4226 (all sold by CIBA-Geigy), or Phorwite RKH or Phorwite BBP (sold by Mobay Chemical Co.) and a quantity of 0.12 »creates a stable and effective product that functions like that of Example IX but has a greater whitening power due to the presence of the tint enhancer which is stable in the product. The product of this example also has an attractive clear appearance and is stable on storage.

Example XI

The contents of the experimental compositions of Examples IX and X were varied to an extent of ± 10% and ± 25%, keeping the amounts of the different materials within the ranges mentioned in this application. In such compositions, 1% QCF (Alkaril Chemicals CAS 9016-88-0) and 5.7% water are used instead of the QCJ debris polymer (aqueous solution), where the QCF is first dissolved in the water. Also, other enzymes, stabilizers, fabric softeners, glycols, alcohols and dyes, as described herein, can be used within the stated limits. The detergent compositions obtained are clear, stable and non-scuffing and have good soil removal promoting softening, cleaning and tint enhancing properties, such as those described in Examples IX and X. This is also the case when using the fluorescent dye, colorant and perfume. from the compositions of this example. When triethanolamine or an ionizable salt in such compositions outside of the indicated 8401065

J

When limits are present, the product also becomes less stable and less effective in promoting soil removal during washing, while, when the sodium formate and glycol are omitted, the effect of the enzyme after only a few days of storage. 5-the increased test temperature will go,

In other variations in this example, the nonionic detergent is a mixture of equal parts of Neodol 23-6, 5 and Neodol 25-7, using the same total amount. The results as previously reported in Examples IX and X are attainable on both top 10 and side load type washing machines as well as household and commercial washing machines. This also applies when the pH adjustments are made with potassium hydroxide and when such adjustments made with sodium hydroxide or potassium hydroxide are aimed at a pH value of 6.6, 7.4, 7.9 and 8.6.

Examples IX-XI and the preceding examples, as well as the description, show that the present invention provides a stable and attractive liquid detergent regardless of the fact that it contains various components which would have been expected to provide stability. of the final product would be adversely affected. Surprisingly, however, a stable product is obtained which has the desired soil removal promoting, fabric softening, soil decomposing and detergent properties. Some of the components of the composition of the invention have a double lift. The propylene glycol can e.g. solubilize the lipophilic materials in the composition while promoting the stabilization of the enzymes. The sodium formate, which is an enzyme stabilizer, does not destabilize the soil remover as one would expect. While some quaternary ammonium halides and some glycols may destabilize liquid detergent compositions, such as those of the invention, this is not the case with the subject materials. This is surprising because hydrophobic quaternary ammonium halides, which are normally flocculated from electrolytes from a solution, are stable in the liquid detergent compositions of the invention. It thus appears that the present compositions represent an unpredictable advance in the art of making stable liquid detergent compositions.

8401065

Claims (17)

1, Liquid detergent with virus removal promoting properties comprising a detergent amount of a nonionic detergent or a mixture of nonionic and anionic detergents, a soil removal promoting amount of a soil contamination promoting polymer of polyethylene terephthalate and polyoxyethylene -lendephephthalate and an aqueous medium in which the pH is in the range 6-9 and in which no more than 2% of a water-soluble ionizable salt other than an anionic surfactant water-soluble salt is present. Liquid detergent according to claim 1, characterized in that the amount of the non-ionic detergent or a mixture of non-ionic and anionic detergents is in the range of 25 - 50%, the amount of the polymer promoting the soil removal is within the range is from 0.5 to 10%, and the soil-promoting polymer is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate with a molecular weight in the range of about 15,000 - 50,000, the polyoxyethylene of the polyoxyethylene terephthalate has a molecular weight in the range of about 1000 to 10,000, while the molar ratio of ethylene terephthalate-20 to polyoxyethylene terephthalate units is in the range of 2: 1 to 6: 1. 3. Liquid detergent according to claim 2, comprising 20 - 40% of a non-ionic detergent, which is a condensation product of a higher fatty alcohol with 10 - 20 carbon atoms and 3 - 20 moles ethylene oxide per mole of the higher fatty alcohol, 3 - 15% of an anionic detergent selected from the group consisting of linear sodium higher alkyl benzene sulfonate where the higher alkyl group contains 10-18 carbon atoms, and sodium higher fatty alcohol polyethoxylate sulfate where the higher fatty alcohol contains 10-20 carbon atoms and the poly 30 ethoxy consists of 3-20 ethoxy groups, as well as 3-15% of a lower al canoe! with 1 - 3 carbon atoms. Liquid detergent according to claim 3, characterized in that the nonionic detergent 8401065 is a condensation product of a higher fat alcohol with 12-15 carbon atoms and 6-11 moles ethylene oxide per mole of the higher fatty alcohol, anionic detergent is linear sodium-higher alkylbenzene sulfonate, wherein the high alkyl group contains 12-13 carbon atoms, the polymer promoting the soil removal has a molecular weight in the range of 19,000-25,000, the polyoxyethylene of the polyoxyethylene terephthalate has a molecular weight in the range 3,000-4,000, the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the poly-10 is in the range 3: 1 to 4: 1, and the molar ratio of ethylene oxide to the phthalic acid unit therein from 20: 1 to 30: 1, the low is already canoe! ethanol, the content of water-soluble ionizable salt other than the anionic surfactant water-soluble salt is less than 0.5%, the liquid detergent contains less than 0.2% triethanolamine and the amounts of the nonionic detergent, the anionic detergent, the soil removal promoting polymer, the alcohol and the water within resp. the areas are 25 - 35%, 5 - 10%, 1 - 6%, 5 - 12% and 30 - 60%. Liquid detergent according to claim 4, consisting essentially of about 32% nonionic detergent which is a condensation product of a higher fatty alcohol with 12-15 carbon atoms and about 7 moles ethylene oxide per mole of the higher fatty alcohol, about 7% sodium dodecylbenzene sulfonate, about 2% of the soil removal promoting polymer having a weight average molecular weight of about 22,000, wherein the polyoxyethylene of the polyoxyethylene terephthalate has a molecular weight of about 3,400, the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units of about 3: 1, and the molar ratio of ethylene oxide to the phthalic acid unit therein is about 22: 1, about 0.2% of a fluorescent tint enhancer, about 8% ethanol and about 51% water, the pH being about 7.8 , which liquid detergent does not contain triethanolamine and wherein the content of a water-soluble ionisable Otherwise, anionic surfactant water-soluble salt which may be present is less than 0.3%. 6. Method for preparing a dirt removal promoted- 8401065 - * - -.- 11 id- ------------— ----------- I .rrr - - ··, - ------- ----- ----- efficient liquid detergent comprising mixing together a detergent amount of a nonionic detergent or a mixture of non- ionic and anionic detergents and a soil removal promoting amount of a soil removal promoting poly-inferior polyethylene terephthalate and polyoxyethylene terephthalate in an aqueous medium and mixing an aqueous neutralizing agent with such mixture to adjust the pH of the detergent set the range from 6.1 to 7.9, which detergent after such neutralization does not contain more than 1% water-soluble ionizable salt other than an anionic surfactant water-soluble salt. 7. Process according to claim 6, characterized in that the liquid detergent comprises 25 - 351 of a non-ionic detergent containing a condensation product of a higher fatty alcohol with 12 - 15 carbon atoms and 6 - 12 moles ethylene oxide per mole of the higher fatty alcohol 5 ~ 15 10¾ of an anionic detergent which is a linear sodium-higher alkyl benzene sulfonate, the higher alkyl group containing 12-13 carbon atoms, is 1-6¾ of a soil removal promoting polymer having a molecular weight ranging from 19,000 to 25.Q00 and wherein the polyoxyethylene of the polyoxyethylene terephthalate has a molecular weight in the range of 3,000 to 4,000, the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units is in the range from 3 to 1: 4: 1, and the mole ratio of ethylene oxide to its phthalic acid unit thereof is 20: 1 to 30: 1, 5 - 12¾ ethanol, 0.1 - 0.5¾ of a fluorescent tint enhancer, and 30 - 60¾ water, wherein the content of the water-soluble ionizable salt other than an anionic surfactant water-soluble salt is less than 0.5¾ and • bethterter: of triethanolamine is less than Q, Z% », the neutralization being carried out with an aqueous solution of sodium hydroxide. Stable dirt-removing enzyme-containing liquid detergent according to claim 1, comprising a detergent amount of a nonionic detergent, an additive to the detergent and an amount of a higher fatty alcohol polyethoxylate sulfate detergent increasing the directness of the fluorescent tint improver. removal promoting amount of a dirt removal 8401065 * V -.- Jgi * · * ,. Polymeric polymer of polyethylene terephthalate and polyoxyethylene terephthalate, an amount of enzyme sufficient to enzymatically hydrolyze proteinaceous and / or starchy impurities on fabrics during washing thereof with an aqueous wash solution of the liquid detergent. and stabilizing amount of a stabilizer for the enzyme (or enzymes) as well as an aqueous medium in which the pH is in the range of about 6-9 and in which no more than 2% water-soluble ionizable material other than the higher fatty alcohol polyethoxylate sulfate detergent is present. Liquid detergent according to claim 8, characterized in that the amount of the non-ionic detergent is in the range of 25 -40%, the higher fatty alcohol polyethoxylate sulfate is a sodium salt of which 1 - 8% is present, the dirt removal the promoting polymer is a polymer of polyethylene terephthalate and polyoxyethylene-15 terephthalate having a molecular weight in the range of about 15,000 to 50,000, the polyoxyethylene of the polyoxyethylene terephthalate having a molecular weight in the range of about 1,000 to 10,000 , and the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate units is in the range of 2: 1 to 6: 1, of which 0.5 - 5% is present, the enzyme comprising a proteolytic enzyme of which 0.005 - 0.1 % is present, as well as 0.2 - 2% stabilizer for the enzyme is present, 10. Liquid detergent according to claim 9 comprising 28 - 36% of a non-ionic detergent, which is a condensation product of a higher fatty alcohol with 10-20 carbon atoms and 3 - 20 moles ethylene oxide per mole of the higher fatty alcohol, 2 - 7% sodium higher fatty alcohol polyethoxylate sulfate wherein the higher fatty alcohol contains 10-20 carbon atoms and the polyethoxylate contains 1-20 ethoxy groups per .mol, 0.02 -2% fluorescent tint enhancers, 0.01-1.1% proteolytic enzyme, 0.005-0.05% amylolytic enzyme, 0.5-1.5% of a stabilizer for the enzyme and 3-12% of a lower alkanol. Liquid detergent according to claim 10, characterized in that the non-ionic detergent is a condensation product of a higher fatty alcohol with 12-15 carbon atoms and 6-11 mol ethylene oxide per 35 mol of the higher fatty alcohol, the higher fatty alcohol polyethoxylate 8401065 ir - is the compound in which the alcohol contains 10-15 carbon atoms and in which 1-5 ethoxy groups per mole are present, the fluorescent tint enhancer is a stilbene enhancer, the soil removal promoting polymer has a molecular weight in the range of 3 19,000-25,000 * the polyoxyethylene of the polyoxyethylene terephthalate has a molecular weight in the range of 3000-4000., the mole ratio of ethylene terephthalate to polyoxyethylene terephthalate units in the range of 3: 1 to 4: 1 and the molar ratio of ethylene oxide to the phthalic acid unit contained therein is 20: 1 to 30: 1, the enzyme stabilizer is sodium formate, the 1a you alkam! ethanol, and the amounts of the nonionic detergent, the higher fatty alcohol polyethoxy sulfate, the fluorescent tint enhancer, the soil removal promoting polymer, the proteolytic enzyme, the amylolytic enzyme, sodium formate, ethanol and water, respectively. within the ranges 30 - 34%, 2 - 6%, 0.1 - 1%, 0.8 - 3%, 0.02 - 3.05%, 0.01 - 0.03%, 0.7 - 1 , 3%, 4-9% and 46-32%. 12. 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 with 12-15 carbon atoms and about 7 moles ethylene oxide per mole higher fatty alcohol about 5% sodium higher fatty alcohol polyethoxylate sulfate in which the higher fatty alcohol contains 12-15 carbon atoms and the ethoxylate is about 3 moles ethylene oxide per mole of the higher fatty alcohol, about 0.3% stilbene fluorescent tint enhancer, about 2% of the the soil removal promoter polymer having a weight average d molecular weight of about 22,000, wherein the polyoxyethylene of the polyoxyethylene terephthalate has a molecular weight of about 3400, the mole ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the polymer is about 3: 1, and the molar ratio of ethylene oxide to the phthalic acid unit therein is about 22: 1, about 0.03% of n a proteolytic enzyme, about 0.02% of an amylolytic enzyme, about 1% sodium formate, about 5.5% ethanol, about 0.4% perfume and about 54% deionized water. 13. Stable fabric softening, soil removal promoting enzyme-containing liquid detergent according to claim 1, comprising an 8401065 & * 5. Detergent amount of a nonionic detergent, a soil removal promoting amount of a soil removal promoting polymer of polyethylene terephthalate and polyoxyethylene terephthalate, a fabric softening amount of quaternary ammonium 5 halide fabric softener, an amount of enzyme, sufficient to enzymatically hydrolyze proteinaceous and / or starchy impurities on fabrics during washing with an aqueous washing solution of the liquid detergent, a stabilizing amount of a stabilizer for the enzyme (the enzymes ) as well as an aqueous medium in which the pH is in the range of about 6-9, and in which no more than 2% of a water-soluble ionizable material is present. Liquid detergent according to claim 13, characterized in that the amount of the non-ionic detergent is in the range of 10 -15%, the dirt-promoting polymer is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate having a molecular weight in the range from about 15,000 to 50,000, wherein the polyoxyethylene of the polyoxyethylene terephthalate has a molecular weight in the range from about 1000 to 10,000, and the mol-20 ratio of ethylene terephthalate to polyoxyethylene terephthalate units in the range of 2: 1 to 6: 1, of which 0.5 - 5% is present, the quaternary ammonium halide is a di-higher alkyl dimethyl ammonium halide, of which 1 - 10% is present, the enzyme comprises a proteolytic enzyme, of which 0.005 - 0.1 % is present, and 0.2 -25% of the stabilizer for the enzyme is present. Liquid detergent according to claim 14, characterized in that it comprises 15 - 30% nonionic detergent, which is a condensation product of a higher fatty alcohol with 10 - 20 carbon atoms and 3 - 20 moles of ethylene oxide per mole of higher fatty alcohol 3-8% quaternary ammonium halide, which is a chloride and the higher alkyl groups contain 12-18 carbon atoms, 0.005-0.05% proteolytic enzyme, 0.005-0.05% amylolytic enzyme, 0.5-1 .5% of a stabilizer for the enzymes and 1-10% of a lower alkanol. 16. Liquid detergent according to claim 15, characterized in that the non-ionic detergent is a condensation product of a higher fatty alcohol with 12-15 carbon atoms and 6-11 moles ethylene oxide per 8401065 moles of the higher fatty alcohol, the dirt-containing polymer has a molecular weight in the range of 19,000-25,000, the polyoxyethylene of the polyoxyethylene terephthalate has a molecular weight in the range of 3,000-4,000, the molar ratio of ethylene terephthalate 5 to polyoxyethylene terephthalate units in the range of 3: 1 to 4: 1, and the mole ratio of ethylene oxide to the phthalic acid unit therein is 20; 1 to 30: 1, the guaternary ammonium halide is di-coconut dimethyl ammonium chloride, the enzyme stabilizer is sodium formate, the lower alkand is ethanol, 2 - 8% propylene-10 glycol is present, and the amounts of the nonionic detergent are the soil removal promoting polymer, the fabric softener, the proteolytic enzyme, the amylolytic enzyme, sodium formate, ethanol, propylene glycol and water within resp. the following areas are: 20 - 2556, 0.8 - 1.5%, 3 - 6%, 0.015 - 0.03%, 0.01 - 0.025%, 15 0.7 - 1.3%, 1.5 -3%, 3 - 8% and 50 - 70%. Liquid detergent according to claim 16 which is clear and essentially consists of about 22% of a nonionic detergent which is the condensation product of a higher fatty alcohol with 12-15 carbon atoms and about 7 moles of ethylene oxide per mole of the higher fatty alcohol-2q hollow, about 1% of a soil release promoter polymer having a weight average molecular weight of about 22, 000, wherein the polyoxyethylene of the polyoxyethylene terephthalate has a molecular weight of 3400, the mole ratio of ethylene terephthalate to polyoxyethylene terephthalate units of the polymer is about 3: 1, and the mole ratio of ethylene oxide to the phthalic acid unit therein is about 22: 1, about 4.5% of di-coco dimethylammonium chloride, about 0.023% of a proteolytic enzyme, about 0.015% of an amylolytic enzyme, about 1% sodium formate, about 256 ethanol, about 6% propylene glycol, about 0.4% perfume, and about 63% deionized water ter. 8401065