DK161716B - LIQUID DETERGENT - Google Patents

Description

DK 161716 B

The present invention relates to liquid detergents and, more particularly, to such agents containing a polymer which promotes the release of dirt, which polymer is deposited on polyesters and polyester blend materials during washing thereof, and promotes the release therefrom of subsequently applied lipophilic dirt.

Preferably, the liquid detergent may contain an enzyme involved in cleaning together with a stabilizer for the enzyme, and it may also contain a textile softening compound such as a quaternary ammonium salt. The agents of the invention are surprisingly physically and functionally stable upon storage, even when containing an enzyme or enzymes and a fabric softener or fabric softener.

Liquid detergents have been used to wash household laundry items in washing machines and have often been applied to contaminated areas of the laundry, such as shirt collars, before washing. The use of copolymers of polyethylene terephthalate and polyoxyethylene terephthalate in detergents as substances that promote the release of dirt has been described in various 20 patents, some of which relate to liquid preparations. However, the liquid detergents described are not of the type to which the present invention relates, because the liquid detergents disclosed in the patents contain triethanolamine and / or ionizable water-soluble salts (in addition to 25 anionic detergents) which tend to cause separation of the liquid detergent and destabilize the polymer which promotes the dirt solubility by storage so that it becomes less effective to later promote the solubility of dirt.

In liquid detergents, enzymes tend to lose activity upon storage unless they are stabilized, such as by means of salts, e.g. sodium formate, glycols, e.g. propylene glycol, or other such materials. However, the said salts tend to destabilize textile plasticizers containing quaternary ammonium halide and the copolymer dirt solubilizers which are desirable components of the liquid detergents in question and such destabilization of

DK 161716 B

In the presence of lower alkanolamines or salts thereof, such as the triethanolamine (TEA), the presence of which should be avoided is particularly severe. It was therefore surprising that the liquid detergents in question could be prepared in clear and stable non-separating form, the various functional components therein being effective after storage at elevated temperatures.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a dirt-soluble, stable, aqueous liquid detergent containing 20-50% by weight of a non-ionic detergent or mixture of non-ionic and anionic detergents, 1-5% by weight of a polyethylene terephthalate-dirt-promoting polymer polyoxyethylene terephthalate having a total molecular weight of 15,000-50,000, the molar ratio of polyethylene terephthalate units to polyoxyethylene terephthalate units being in the range of 2: 1 to 6: 1, and the polyoxyethylene terephthalate having a molecular weight in the range 1GOG-10,000, and an aqueous medium the value is 6-9 and the dirt-soluble, stable, aqueous liquid detergent is characterized in that it contains at most 2% water-soluble ionizable salt which is not an anionic surfactant water-soluble salt.

Preferred liquid agents also contain enzymes and enzyme stabilizers, a fabric softener being preferably also present.

Although the various synthetic organic nonionic detergents 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 nonylphenol and oxo-type alcohols, it is highly preferred for obtaining of the best results that the nonionic detergent is a condensation product of ethylene oxide and higher fatty alcohol. In such products, the higher fatty alcohol has 10-20 carbon atoms, preferably 12-15 or 16 carbon atoms, and the nonionic detergent contains from 2

DK 161716B

3 or 3 to 20 or 30 ethylene oxide groups per molecule, preferably from 6 to 11 or 12. Most preferably, the nonionic detergent will be one in which the higher fatty alcohol has approx. 12-15 or 12-14 carbon atoms and containing from 6 to 7 or 11 to 11 moles of ethylene oxide, e.g. 7. Such detergents include "Alfonic" ® 1214-60C and "Neodol" ® 23-6.5 and 25-7.

Among their particular beneficial properties are, besides good cleaning performance, oily and greasy contaminant deposits on articles to be washed, and excellent compatibility with the present polymeric dirt-release agents, compatibility with soluble anionic detergents of the linear linear higher alkylbenzene sulfonate and higher ethoxylate sulfate, enzymes, enzyme stabilizers, textile softeners and other components of the present agents, as well as long-term viscosity stability in aqueous and aqueous-alcoholic solutions.

The anionic detergent which can be used in the liquid detergents is preferably, within the broader aspects of the invention, a higher linear alkyl benzene sulfonate or a higher fatty alcohol-polyethylethoxyl acetate. Typically, water-soluble salts of such materials, such as the alkali metal salts, are preferred, and sodium salts are usually preferred over the potassium salts. When the anionic detergent is a sodium higher alkyl benzene sulfonate, the higher alkyl groups will usually contain 10-18 carbon atoms, preferably 12-16 carbon atoms, and most preferably 12-13 carbon atoms, e.g. 12. When such anionic detergent is a higher fatty alcohol polyethoxylate sulfate, such as in the case of the enzyme-containing liquids in which the detergent 30 increases purity and promotes an increase in the substantivity of fluorescent clarifier present, the higher fatty alcohol will contain 10-20 carbon atoms, preferably 12-16 carbon atoms and most preferably 12-13 or 12-15 carbon atoms, and the polyethoxylate will contain 1, 2 or 3-20 ethoxy groups, preferably 3-10 thereof and more preferably 3-6 or

DK 161716 B

4 7, e.g. 3, 6.5 or 7. Although not preferred, mixtures of such anionic detergents can be used in the non-enzyme-containing agents, usually in the ratio of 1:10 to 10: 1, such as from 1: 2 to 2: 1. Anionic 5 detergents and surfactants will normally be omitted from the textile softening liquid detergents.

The dirt solution promoting polymer which is an important component of the compositions of the invention is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate which is soluble (preferred) or dispersible in water and from wash water containing the detergent or detergents can be applied to the synthetic organic polymers. fibrous materials, especially polyesters and polyester blends, to impart these dirt release properties while remaining comfortable with a garment carrier made of such materials and not inhibiting or significantly inhibiting vapor transmission through such lining. equipment. Such polyesters have also been found to have antigen deposition properties, and often assist in removing stains from substrates. They tend to keep dirt, especially oily or greasy dirt, dispersed in wash water underneath washing and rinsing so that it is not re-deposited on the laundry. Such useful products are copolymers of ethylene glycol or another source of the ethylene oxide moiety, polyoxyethylene glycol and terephthalic acid or a suitable source of the terephthalic moiety. The copolymers can also be considered as condensation products of polyethylene terephthalate, which can sometimes be termed scan an ethylene terephthalate polymer, as well as polyoxyethylene terephthalate. Although the terephthalic acid moiety is preferred as the only dibasic acid moiety in the polymer, it is within the scope of the invention to use relatively small amounts of isophthalic acid and / or orthophthalic acid (and sometimes other dibasic acids as well) to modify the polymer's properties. The amounts of such acids or sources for such additional portions charged to any reaction mixture and the corresponding amounts in the

DK 161716 B

however, the final polymer will normally be less than 10% each of the total phthalic acid molecules and preferably will be less than 5% thereof.

The molecular weight of the polymer will range from 15,000 to 50,000, preferably from 19,000 to approx. 43,000 and more preferably from approx. 19,000 to approx. 25,000, e.g. ca. 22,000. Such molecular weights are weight averages of molecular weights as opposed to number averages of molecular weights, which in the case of the present polymers are often lower. In the polymers used, the polyoxyethylene will have a molecular weight in the range of about 1,000 to approx. 10,000, preferably from ca. 2,500 to approx. 5,000 and more preferably from 3,000 to 4,000, e.g. ca. 3400. In such polymers, the molar ratio of polyethylene terephthalate units to polyoxyethylene terephthalate units (0 0 0 0 o tOCH 2 CH 2 O-c / oV-Cl · and * (OCH 2 CH 2) n-0-C - <(Oycl · considered as such units) will be in the the range from 2: 1 to 6: 1, very preferably from 5: 2 to 5: 1 and even more preferably from 3: 1 to 4: 1, for example about 3: 1. The ratio of the ethylene oxide to phthalic acid molecule in the polymer 20 will be at least 10: 1 and often 20: 1 or more, with it being in the range of from 20: 1 to 30: 1 and more preferably being about 22: 1. as being essentially a modified ethylene oxide polymer, the phthalic acid molecule being only a minor component thereof, whether calculated on a molar or weight basis, It is considered surprising that with such a small amount of ethylene terephthalate or polyoxyethylene terephthalate in the polymer, sufficiently the polyester fiber substrate po adhesives (or other polymers to which it can adhere, such as polyamides) to be retained thereon during washing, rinsing and drying operations.

DK 161716 B

deletions. Nevertheless, as shown by comparative experiments and various washing experiments in which dirt solution is measured, the polymer described in the present detergents is effective to be applied to washed synthetic materials, especially polyesters, to make them better able to be washed free of oily dirt by a liquid, nonionic detergent or other detergent-containing product. It is believed that the increased hydrophilicity of the polymer due to the large amount of hydrophilic ethylene oxide molecule moieties therein may be responsible for the excellent dirt release properties (to release lipophilic debris) it imparts to the material to which it is applied, and such properties can also help it to interact with the liquid non-ionic detergent product components.

Various literature articles, textbooks and patents deal with methods for the preparation of the polymers in question. an article in the Journal of Polymer Science, Volume 3, pages 609-630 (1948) and Volume 8, pages 1-22 (1951). Although suitable methods for preparing the disclosed polymers are disclosed in such printing presses, it is believed that none of them discloses the particular polymers used in the detergents of this invention (but such are commercially available) and none discloses the disclosed polymers. detergents. Such polymers can be considered to have been randomly formed from polyethylene terephthalate and polyoxyethylene terephthalate moieties which can be obtained by reaction of polyethylene terephthalate (e.g., spinning grade) and polyoxyethylene terephthalate or conversion of ethylene glycol and polyoxyethylene glycol (polyoxyethylene glycol) 30 methyl ester) precursors therefore. Nevertheless, it is also within the scope of the invention to use several ordered copolymers, such as those prepared by reacting components of predetermined or known chain lengths or molecular weights, to produce what could be termed block copolymers or non-random copolymers. copolymers.

DK 161716B

7

Graft polymers can also be used.

The described materials can be obtained from various sources and the products from one of the sources will be described in more detail here. Applicable copolymers for the preparation of the detergents of the invention are marketed by Alkaril

Chemicals, Inc., and commercial products of this company, which have been successfully used in the manufacture of satisfactory detergent-promoting detergents, are those sold under the trademarks "Alkaril" QCJ and "Alkaril" 10 QCF, formerly "Quaker" OCJ and "Quaker "QCF. Products obtained therefrom in limited quantities and designated as 2056-34B and 2056-41 have also been found to be acceptable. The QCJ product, which is usually delivered as an aqueous dispersion with a concentration of approx. 14 or 15% in water, and which is preferably used for the preparation of the aforementioned liquid detergents, is also obtained as a substantially dry solid (QCF). In both such product types, the molar ratio of ethylene oxide to phthalic acid molecule is approx.

22: 1st In a 16% dispersion in water, such as QCJ, the viscosity at 100 ° C is approx. 96 centistoke. The polymer 2056-41 is like a hard, light brown wax, and in it the hydrophilic: hydrophobic ratio is approx. 16: 1, the viscosity being approx. 265 centistoke. The polymer 2056-34B is similar to a hard brown wax with a hydrophilic: hydrophobic ratio of approx. 10.9: 1 and its viscosity under the same conditions as mentioned above is approx. 255 centistoke. The higher the molecular weight of the polymer, the lower the hydrophilic: hydrophobic molar ratio may be therein and still result in a satisfactory increase of the dirt solubility by the detergents. The QCJ and QCF polymers have melting points (according to differential thermal analysis) of approx. 50 - 60 ° C, a carboxyl analysis of approx. 5-20 or 6 equivalents / 10 g and a pH of 6 - 8 in distilled water at a concentration of 5%. The molecular weights (weight average) range from 20,000 to 25,000, and 8

DK 161716 B

the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units is approximately 74:26. All of the products sold under trademarks are water-soluble in hot or hot water (at 40-70 ° C) or are at least lightly dispersed and can be characterized as having a high molecular weight of over 15,000, generally in the range of 19,000 to 43,000, often preferably 20,000 to 25,000, e.g. ca. 22,000.

The enzymes used in some of the disclosed agents include both proteolytic and amylolytic enzymes such as the alkaline proteases (subtilisin) and α-amylase.

For preferred enzyme preparations,. which can be used include "Alcalase" 2.5L (2.5 Anson units per gram) and "Thermamyl" 120L, both manufactured by Novo Industri A / S. However, other suitable proteolytic and amylolytic enzyme preparations may also be used. Said agents are in liquid form and contain 5% active enzyme in combination with 65% propylene glycol and 30% water. The relative amounts mentioned herein apply to the active enzyme or enzymes 20 in the compositions.

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

The quaternary ammonium salt textile softener used in some of the liquid detergents of the invention may be any suitable such material which is stable in the present compositions. In some cases, known imidazolinium halides of satisfactory stability may be used in place of the usual quaternary ammonium halides. The quaternary ammonium halides are, however, preferred 9

DK 161716 B

lertid. Such compounds will preferably be chlorides, although bromides and iodides may be useful. Of the four substituents on the quaternary nitrogen atom, at least one and preferably two will be a long chain substituent such as 5 higher linear alkyl or fatty alkyl, and more preferably two such substituents will be higher fatty alkyl. The chain length will usually be 12-20 carbon atoms, preferably 12-18 carbon atoms, with chain lengths of 12-14 carbon atoms or mixtures thereof, such as coconut alkyl (derived from coconut oil or the equivalent of raw materials), being the most preferred. The other substituents on the nitrogen atom will be lower alkyl, usually having 1-3 carbon atoms, and of such is the most preferred methyl. Although other quaternary ammonium halides may also be useful, at least when forming only one of the quaternary softeners, the most preferred and the highest stability of the liquid detergents in question is thus dicocosimethyl ammonium chloride. Such a product can be obtained as a liquid comprising 75% active ingredient, 14% isopropanol and 11% water.

The aqueous medium used contains water and preferably also a lower alkanol. The water is suitably deionized water, but urban water with a hardness content of up to approx. 300 ppm, calculated as calcium carbonate (the hardness is usually 25 mixed magnesium and calcium ions) can be used, although it is preferred that the hardness content is less than 100 ppm to help avoid any destabilization of the liquid detergent or separations. of parts thereof. Some water may be derived from the starting materials, such as aqueous dirt solution promoters, enzyme preparations, plasticizers, alkanols and dyes. The lower alkanol may be any of ethanol, isopropanol or n-propanol, but ethanol is very preferred. When ethanol is used, it will usually be a denatured alcohol such as 35A containing a small amount of water plus denaturing agent.

DK 161716B

10 means. Small amounts of compatible dissolved salts may also be present in the aqueous medium, but usually such salts will be avoided to the extent possible.

Another liquid which can be conveniently used in some of the liquid detergents in question, such as those containing enzymes and textile softeners, is a lower glycol such as a glycol having 3-6 carbon atoms in its alkyl group. Although hexylene glycol can be used in some compositions, in others it can promote instability, which is why propylene glycol is preferred.

Various suitable adjuvants may be present in the liquid detergents of the invention, such as fluorescent dyes, dyes (organic dyes and water dispersible pigments, such as ultramarine blue), bactericides, fungicides and perfumes. The concentrations of such components will usually be kept low, often less than 1% and preferably less than 0.7%. Thus, the perfume concentration will usually be less than 1%, preferably 0.2-0.6%, e.g. 0.4%. Fluorescent clarifiers or optical bleaching agents may be present in the liquid detergent in an amount of 0.02-2%, preferably 0.1-1% and more preferably 0.2-0.5%. The percentages given are counted as percentages of the commercially supplied materials. Such clearing agents are known as cotton clearing agents, soluble bleaching clearing agents, polyamide clearing agents and polyester clearing agents, and generally mixtures thereof are used to make the detergent useful for clearing a wide variety of materials being washed, including cotton and synthetic fabrics. Examples of such good clarifiers are those designated as: TA, DM, DMEA, DDEA, DMDDEA, BS, NTS, BBI, AC, DP, BBO, BOS and NTSA in a well-known article entitled Optical Brighteners and their Evaluation of Per S.Stensby, published in Soap and Chemical Specialties in April, May, July, August and September 1967.

DK 161716 B

n

Further mention of the fluorescent detergents can be found in an article entitled Optical Bleaches in the Soaps and Detergents by F.G. Willaume, found in The Journal of the American Oil Chemists' Society (October 1958), Volume 5 35, No. 10, pages 558-566. Useful fluorescent detergents are sold under the trade names: "calcofluor White Alf", "ALF-N", "SOF A-2001", "CWD", "Phorwite RKH", "CSL", powder, acid, "FB 766", "Blancophor PD "," UNPA "," Tinopal RBS "and" RBS 200 "The various clarifiers are usually present in the form of water-soluble salts thereof, but can also be used in the corresponding acid forms. Most such materials can be used to clear cotton and are of the types benzene sulfonic acid (or salt) or aminostiben, herein referred to as stilbenes, and one such preferred clarifier is 15 "Tinopal" 5BM Extra Cone. For the fabric softening detergent, the preferred clarifier content will be from 0, Staining agents such as Polar Brilliant Blue will range from 0.001 to 0.03%, preferably 0.002-0.2%. of the liquid detergent, e.g.

20 0.0025% or 0.01%, if present. The various excipient materials will be selected for compatibility with other recipe components and for obtaining non-separating and non-settling properties. Because water-soluble ionizable salts, whether inorganic or organic, are generally incompatible with dirt solvents, their presence will usually be avoided.

Such salts which are desired to be avoided include sodium sulphate, potassium sulphate, sodium chloride, potassium chloride, ammonium chloride and ammonium sulphate, but these are only examples of such salts. Although sodium form should also be omitted by many liquid detergents, a limited amount thereof has surprisingly been found to be compatible with the other components of the present invention,

DK 161716B

The presence of ionizable substances such as triethanolamine (TEA), diethanolamine, ethanolamine, diisopropanolamine, n-propanolamine and the lower mono-, di-, tri- and mixed lower alkanolamines having 2-4 carbon atoms 5 per liter. alkanol molecule moiety will be avoided because, like the salts mentioned, they destabilize the dirt solution promoting polymer and / or liquid detergent. Of these, TEA turns out to be the most destabilizing as it causes severe separations of the polymer. In this specification, 10 such salable ionizable substances must be counted as part of the permissible amounts of such salts that may be present. In general, it will be desirable to avoid the presence of auxiliaries other than colorants, perfumes, fluorescent brighteners, antioxidants and any neutralizing agents which may be used to adjust the pH of the liquid detergent to the stable range. It is preferred that any neutralizing agent which may be used, usually to increase the pH of the liquid detergent mixture, should be an alkali metal hydroxide, such as sodium hydroxide, in aqueous solution having a concentration of from 5 to 40%, e.g. . 15 - 25%. In particular, triethanolamine salts and free triethanolamine must be avoided.

The liquid detergent produced will have a desired viscosity, often in the range of 50 to 500 centipoise, preferably 100 to 200 centipoise, and the viscosity can be adjusted by modifying the amount of lower alkanol within the range indicated. The liquid detergent will be easy to pour, but will have a desirable "body". Its pH will range from 6 to 9, preferably 6.1 to 7.9, and often more preferably from 6.5 to 7.5.

The dirt solution promoting liquid detergents of the invention have improved storage stability so that the dirt solution promoting polymer and the enzyme or enzymes are not degraded and do not separate from the rest of the agent, and 13

DK 161716 B

the quantities of the various components will be as indicated below. All of the various components mentioned, although listed in singular, also include mixtures. The quantities of the following components are mentioned in the broad sense according to the invention for the enzyme-containing product and the enzyme- and plasticizer-containing product, respectively.

The nonionic detergent (which includes mixtures thereof) or a mixture of nonionic and anionic detergents (both of which are of the synthetic organic type) will range from 25 to 50% of the product, the amount preferably will be from 20 to 40% for the nonionic detergent and 3 - 15% for the anionic detergent. More preferably, the amounts of such detergents will be 25-35% and 5-10%, e.g. respectively approx. 32% and approx.

7%. The dirt solution exfoliating polymer will be 1-5% and preferably 1-3%, e.g. ca. 2%. The lower alkanol content will be from 3 to 15%, preferably 5 to 12% and more preferably 6 to 10%, e.g. ca. 8% and the water content when lower alkanol is present will be approx. 30 to 60%, preferably 45 to 55%, and if no alkanol is present, such intervals will be increased to allow replacement of the lower alkanol with water. The contents of ionizable water-soluble salts, whether organic or inorganic, should be kept low, usually not constituting more than 1% of the liquid detergent, preferably less than 0.5% and more preferably less than 0.3%. and the triethanolamine content will similarly be limited to avoid separation of the dirt solution-promoting polymer, with the desired limits being 0.5%, preferably 0.2% and most preferably 0%. In some 30 cases, the salt content will be kept at limits lower than the permissible alkanolamine content, because some salts may be even more detrimental to product stability than the alkanolamines. The content of anionic detergent present, which may be considered as an ionizable salt, 14

DK 161716 B

will, of course, not be included within the limiting amounts of such salt because it does not appear to have the same type of destabilizing effect on the agents in question. Although suitable adjuvants may be present in the liquid detergent such as the dye, perfume and fluorescent detergent mentioned above, the contents of such adjuvants will usually be minimized, usually being less than 2% , preferably less than 1% and more preferably less than 0.8%, but the dye and clarifier are not destabilizing.

For the enzyme-containing product (without plasticizer), the content of the synthetic organic non-ionic detergent will usually range from 25 to 40% of the product, preferably from 28 to 36% and more preferably from 30 to 34%, e.g.

32%. The fatty alcohol alkoxylate sulfate content will usually be from 1 to 8%, preferably 2 to 7% and more preferably 2 to 6%, e.g. 3 or 5%. The content of fluorescent brightening agent ranges from 0.02 to 2% and preferably from 0.1 to 1%, e.g. 0.2 or 0.4%. The percentage of the active ingredient of the clarifier may often be 0.01 - 1%, such as 0.01 - 0.1%. The content of dirt solution promoting polymer will be approx. 0.5 to 5%, preferably 0.8 to 3% and more preferably 0.8 to 2.5%, e.g. ca. 1% or 2% (calculated as active ingredient). The total enzyme content will usually range from 0.0005 to 0.15%, preferably 0.025 - 0.1%, of which the protease content is from 0.005 to 0.05% and the amylase content if amylase is present from 0.005 to 0.05%. Preferred contents of the enzymes are 0.01 - 0.1% and 0.01 - 0.03%, respectively. More preferably, the percentage of protease is from 0.02 to 0.05%. Specific prescription percentages are approx. 0.03% and 0.02%. The stabilizer for the enzymes, usually an alkali metal salt or a lower aliphatic acid having 1-3 carbon atoms such as sodium formate,

DK 161716 B

will usually be from 0.2 to 2%, preferably 0.5 to 1.5% and more preferably 0.7 to 1.3%, e.g. 1%. The lower alkanol content will be from 3 to 12%, preferably from 4 to 9% and more preferably 5-8%, e.g. 5.5 or 7.5%. The water-5 content will be from approx. 40 to 65%, preferably 46 to 62% and more preferably 50 to 60%, e.g. ca. 54 or 55%.

The contents of ionizable, water-soluble salts, whether organic or inorganic, should be kept low, below 2%, usually not being higher than 1% of the liquid detergent, preferably less than 0.5% and more preferably similarly, the content of triethanolamine will be limited in order to avoid separation of the dirt solution-promoting polymer, with the desirable limits being 0.5%, preferably 0.2% and most preferably 0%. In some 15 cases, the salt content will be kept at limits lower than the permissible alkanolamine content, because some salts may be even more detrimental to product stability than the alkanolamine. However, in the present detergents, the contents of water-soluble alkali metal lower carboxylate, such as sodium formate, can be up to 2% because such components stabilize the enzymes, and at such concentrations, especially at ca. 1% or less, they are compatible with the detergent product and the dirt solution promoting polymer so that polymer separation does not occur.

For the enzymatic and emollient liquid detergents, the content of synthetic organic nonionic detergent (including mixtures thereof) will range from 20 to 35% of the product, preferably 20 to 30% and more preferably 20 to 25%, f. eg. 22% of the product. The content of dirt release promoting polymer will be 1 to 5%, preferably 1-2% and more preferably 1 to 1.5%, e.g. ca. 1% (calculated as active ingredient). The content of quaternary compound will be from 1 to 10%, preferably 3 to 8% and more preferably 3 to 6%, e.g. 4.5%. The enzyme content can be from 0.005 to 16

DK 161716 B

0.15%, preferably 0.025 - 0.05%, of which the protease content is from 0.005 to 0.1% and the amylase content if amylase is present from 0.005 to 0.05%. Preferred contents of the enzymes are 0.01 - 0.05% and 0.01 - 0.025% respectively.

More preferably, the content of protease will be from 0.015 to 0.04%. Specific prescription percentages are approx. 0.023 and 0.015%. The stabilizer for the enzymes, a lower aliphatic acid salt such as sodium formate, will usually range from 0.2 to 2%, preferably 0.5 to 1.5% and more preferably from 0.7 to 1.3%, f. eg. 1%. The lower alkanol content will be from 1 to 10%, preferably 1.5 to 3% and more preferably 2 to 2.5%, e.g. 2 or 2.2%. The lower glycol content is from 2 to 10%, preferably 3 to 8% and more preferably 4-7%, e.g. 6%. The water content will be from 15 approx. 40 to 80%, preferably 50 to 70% and more preferably 60 to 65%, e.g. ca. 63%.

The contents 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 more preferably less than 0. , And the content of triethanolamine will similarly be limited to avoid separation of the dirt solution-promoting polymer, with the desirable limits being 0.5%, preferably 0.2% and most preferably 0%. In some cases, the salt content will be kept at lower limits than the permissible alkanolamine content. because some salts can be even more detrimental to product stability than the alkanolamine. However, in the disclosed agents, the contents of water-soluble alkali metal lower carboxylate, such as sodium formate, can be up to 2%, because such components stabilize the enzymes, and at such concentrations, especially at ca. 1% or less, they are compatible with the detergent product.

DK 161716B

17

The present liquid detergents can be prepared by mixing their various components with the aqueous medium / preferably containing at least some of the lower alkanol until dissolved (or dispersed satisfactorily) therein, or the various components can be selectively dissolved in portions of the water and / or the lower alkanol and / or the lower glycol and / or the liquid dirt solution enhancing polymer composition and / or the liquid enzyme preparation, and the various liquid fractions 10 can then be mixed together. It will often be preferable to adjust the pH of the liquid to range from 6.1 to 7.9, more preferably from 6.5 to 7.5, by the addition of a suitable neutralizing agent (not triethanolamine) which does not will have a destabilizing effect on the dirt solution-promoting polymer, enzyme or enzymes, softening the clean or liquid product containing them so that they will not decompose and will not separate from the liquid detergent upon storage, especially at elevated temperature.

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

The present liquid detergent can be used for washing (and treating) laundry containing synthetic fibers, such as polyester fibers, e.g. "Dacron" ®, in the normal way used for washing with other liquid detergents. However, less of the present product can be used because its dirt-promoting effect and in many cases the cleaning and softening effects obtained will be superior. Different concentrations of the liquid detergent can be used, usually from 0.02 or 0.04 to 0.3 or 0.6%, preferably from 0.05 or 0.1% to 0.15 or 0.3%, with the concentration

DK 161716B

18 is approx. 1/2 cup per wash to a machine with top filling for the product containing the softener and approx. 1/4 cup per wash for the other two product types. In general, it would be advisable to use approx. 1/4 or 1/2 cup (about 60 or 5 120 ml) of the liquid detergent per standard washing refill (approx. 650 liters for a washing machine with top filling), which corresponds to a concentration of approx. 0.1 or 0.2% of the liquid detergent in the wash water. Ca. the same concentration can be used when washing is done in a front-loading machine 10, even though the amount of water used is smaller (so that less detergent is used). Normally, approx. 3 - 3.5 kg of laundry will be loaded on the washing machine. The temperature of the washing water will preferably be at least 49 ° C, but good washing and treatment by means of the dirt-releasing polymer, the enzymes and plasticizer in the detergent can be obtained at temperatures of 40-80 ° C, preferably 45-70 ° C. The dry weight of the material being washed and treated will usually be from about 1 5 to 15 or 20% by weight of the aqueous washing medium, preferably about 20%. 5 - 10% thereof. The washing will be performed with agitation over a period of approx. 5 minutes to 1/2 or 1 hour, often from 10 to 20 minutes. Then the washed materials are rinsed, usually with multiple rinses, and dried, e.g. in an automatic laundry dryer. Preferably, the first washing of the material to be treated will be carried out when the material is not too dirty, so that the dirt solution-increasing polymer will be applied to as clean a surface as possible. However, this is not necessary and improvements in the cleaning of 30 subsequent contaminated materials and fabric samples will be observed when no particular effort is exerted to allow the first washing to be done with a cleaner material backing. Up to a certain limit, sometimes approx. 3 or 5 treatments, more washings with the liquid detergent of the invention increase the dirt of the treated material 19

DK 161716 B

solution-enhancing properties.

When polyester and polyester / cotton textile blends are washed in the manner described with the detergents of the invention and then contaminated or stained with dirty engine oil and washed with the detergent of the invention or other commercial detergent (often of the compound type), significant removal of the detergent is observed. lipophilic dirt as compared to similar treatments in which the liquid detergent used initially did not contain any dirt solution-promoting polymer. In other comparisons, when substantial amounts of water-soluble ionizable salt, such as 5% sodium sulfate or more than 1% triethanolamine or a salt thereof, are present in the liquid detergent, it is found that after storage at elevated temp. Temperature (43 ° C) for 2 hours, mimicking a longer storage at room temperature, separating phases from the liquid detergent mass, and degrading the polymer's soot-promoting properties, as is the case for the enzymatic and plasticizing properties, when such materials are found in composition. When the enzyme stabilizer is omitted, the enzymatic action is significantly impaired upon storage. Thus, the detergents of the invention are important because they are stable, result in more effective products for the intended purposes, dirt solution enhancement, cleaning effects and softening of the washed textiles, and furthermore result in a more attractive liquid detergent which does not separate upon storage. .

The following examples further illustrate the invention.

Unless otherwise stated, all parts are parts by weight and all temperatures are listed in ° C.

20

DK 161716 B

EXAMPLE 1.

Component Percent "Neodol" 23-6.5 (condensation product of approx.

6.5 moles of ethylene oxide and a 5 higher fatty alcohol with an average of 12 - 13 carbon atoms per mol) 32.0%

Sodium linear dodecylbenzenesulfonate (LDBS) 7.0%

Sodium sulphate (accompanying LDBS) 0.2% 10 Dirt solution-promoting polymer (a copolymer of polyethylene terephthalate and polyoxyethylene terephthalate having a molecular weight of about 22,000, wherein the polyoxyethylene has a molecular weight of about 3,400, the molar ratio of polyethylene terephthalate units to polyethylene terephthalate units is about 3: 1 and the ratio of the ethylene oxide molecule 20 to the phthalic acid molecule in the polymer is about 22: 1, which polymer is sold by Alkaril Chemicals, Inc. as "Alkaril" QCJ in the form of a 14% solution in 25 water) %

Denatured ethanol (3A) 8.0%

Fluorescent Detergent ("Tinopal" 5BM, Extra Wife) 0.24%

Dye (Polar Brilliant Blue) 0.01% 30 Perfume 0.4%

Deionized water until 100% ~ - 100.0% 21

DK 161716 B

The liquid detergent according to the recipe is prepared by mixing a portion of the water with the nonionic and anionic detergents, followed by the addition of the dirt-soluble polymer, the ethanol, the fluorescent brightening agent, the dye and the residual water amount. Then, if desired, an acid or base (NaOH preferred) can be used to adjust the pH to the desired range. In the above example, the pH is 7.8 (undiluted). However, if the pH is 10 lower than desired, an aqueous solution of sodium hydroxide (20%) is used to increase it to the desired level, e.g. 7.5, and the amount used is small, e.g. ca.

0.2% NaOH or less. Then add the prescription amount of perfume. The prepared product is tested at storage 15 at 43.3 ° C for 2 weeks, after which it is seen to be in a single phase, essentially as it was first produced.

Shortly after preparation of the liquid detergent, this is used to wash a sample filling of clean fabrics including some of polyester material and others 20 of 65% polyester and 35% cotton. The wash concentration is 0.1% by weight of the liquid detergent calculated in relation to the weight of the wash water, and the washed textile samples constitute 5% by weight of the wash water weight. After completion of washing in a washing machine for standard experiments using 25 of the previously described standard conditions, the textile samples are rinsed and dried. Then, each fabric sample is stained with approx. 3 drops of a standard type of dirty engine oil used for such testing and is washed in the same kind of machine using a commercial detergent. Textile pieces which have not previously been treated with the present liquid detergent are used as a control test. The temperatures of the wash and subsequent wash are the same in all cases, being 49 ° C, 22

DK 161716 B

which is considered to be an optimal treatment temperature. In some experiments, the subsequent washing is carried out with the liquid detergent according to the invention. In all experiments, the treated textile pieces are significantly whiter for the eye to look at and according to the reflectometer test than the trap is for the control textile samples, which shows that the dirt solution enhancing component of the liquid detergent effectively contributed to the removal of such applied dirt from the textile pieces during the subsequent washes. It is also noted that the re-deposition on uncontaminated portions of the fabrics of the removed dirty motor oil (from the stain application) is diminished when the dirt-releasing polymer is applied to the fabric prior to the experimental contamination thereof.

Thus, without contributing to the removal of the dirt, the liquid detergent containing the dirt solution promoting polymer also helps to keep the dirt suspended as it inhibits re-deposition of such removed dirt on other parts of the test material.

When 2 or 3% triethanolamine is present in the liquid detergent with the above composition instead of part of the water content, the detergent appears to be separated at 43.3 ° C after 2 weeks of storage. Separation also occurs under such conditions where the triethanolamine is omitted and 5% sodium sulfate is present in the composition. Furthermore, when the triethanolamine is present, the liquid detergent-promoting effect of the liquid detergent is significantly diminished compared to the dirt-removing effect of the test composition of the invention after 2 weeks at increased aging temperature 30 of 43.3 ° C, followed by testing as previously described. Furthermore, storage at room temperature also results in such a deterioration of the dirt solution-promoting effect of the triethanolamine-containing composition as compared to the experimental composition.

DK 161716B

23 When the amount of the dirt solution-promoting polymer is reduced to 1% or increased to 3%, the same results as those stated above are obtained with the changes that the composition containing 3% solution polymer is more effective than the composition containing the 2% solution polymer in promoting The solution containing 1% is slightly less effective, although at both 1% and 3% concentrations good and excellent results are obtained, respectively.

10 When similar tests are performed using other lipo-file contaminants such as corn oil (red), butter, shoe ink, lipstick, French dressing and barbecue sauce, similar results are obtained, with the best improvements of the test compared to the control sample obtained with corn oil. , 15 lipstick and dirty engine oil. The loose ice cream is 100% for stains of corn oil, butter, French dressing and barbecue sauce and it is almost 100% for lipstick. Similar results are obtained when the test fabrics are single-knit 'Dacron' ®, double-knit 'Dacron' ® and 'Dacron' ® / cotton blends, and they are also obtained at treatment temperatures above 32 ° C. Such results are also obtained when a commercial washing machine or a top-level household or side-type washing machine is used in place of the laboratory testing washer.

EXAMPLE 2.

In the primary composition of Example 1, the linear sodium dodecylbenzenesulfonate is replaced with the corresponding tridecylbenzenesulfonate in one case and with "Neodol" 25-3-S, which is the sodium salt of a sulfated condensation product 30 3 moles of ethylene oxide and a higher fatty alcohol with a gene average between 12 and 15 carbon atoms per mole, in another case, and the nonionic detergent is replaced by "Neodol" 24

DK 161716 B

25-7 in both cases. When the resulting agents are tested for stability at elevated temperature as well as for storage stability as described in Example 1 #, similar good results are obtained. Similarly, when more than 0.5% triethanol-5 amine is present in the agents instead of a corresponding amount of water and / or when 2% sodium sulfate or another water-soluble ionizable salt is present, separation of the liquid takes place detergent components location. When the liquid detergents of this example are used to wash polyester textiles of the types mentioned in Example 1, after which the fabrics are contaminated and then washed, improved removal of lipophilic dirt is achieved compared to control samples containing no dirt solution promoting polymer of the type used in the compositions of this example. Also, when more than 0.5% triethanolamine and / or 2% water-soluble ionizable salt, such as sodium sulfate, is present in each of the compositions, it is found that after aging at elevated temperature or room temperature, respectively, for a period of for 2 weeks and 3 months, respectively, if the separated agent is shaken to disperse its various components and then used in the same manner as described above, its dirt-releasing effect is still significantly diminished compared to the effect of the test compositions containing neither triethanolamine nor such salt.

EXAMPLE 3.

The first composition of the invention set forth in Example 1 is modified by replacing the content of the anionic detergent with "Neodol" 25-7 so that the product contains 30% of non-ionic detergent and by replacing the ethanol with deionized water. The product is non-separating upon storage and has dirt removing properties similar to the properties 25

DK 161716 B

In addition, the test product is stable under accelerated aging at elevated temperature storage and for longer periods at room temperature storage, while a comparison product containing 1% triethanolamine and / or 2% sodium sulfate separates. Similarly, such comparison products do not help to loosen deposited lipo-felt dirt to the extent obtainable with the test products of this example.

EXAMPLE 4.

When the contents of the various test compositions of the invention set forth in Examples 1-3 are varied - 10% and -25% while retaining the amounts of the various materials in the ranges disclosed in the specification, compositions instead of using the dirt-releasing polymer QCJ (aqueous solution) use 2% QCF (Alkaril Chemicals, CAS 9016-88-0) and 12.3% water, first dissolving the QCF in the water to obtain good dirt-solubilization properties, such as those described in Examples 1-3, 20, and the products produced are stable and non-separable upon storage. This is also the case when the fluorescent dye, colorant and perfume are omitted by the compositions of this example. Similarly, when triethanolamine or ionizable salt is present in such compositions beyond the stated limits, the product becomes less stable and less effective in promoting dirt release during washing.

By other changes in this example, the nonionic detergent is a mixture of equal parts "Neodol" 25-7 and "Neodol" 30 91-6, and the anionic detergent is "Neodol" 45-2.25-S. Results like the ones mentioned in Examples 1-3 can

DK 161716B

26 is obtained in both test washing machines and in practical washing, where commercial washing machines with top filling or side filling or household washing machines are used. This is also the case when pH adjustments are made with potassium hydroxide and when such adjustments are made with sodium hydroxide or potassium hydroxide at pH values of 7.0, 6.6 and 7.4. Typically, such pH adjustments will use less than 1% sodium hydroxide solution, preferably less than 0.5% thereof and more preferably less than 0.2% thereof. In some cases, the sodium hydroxide may be added as a prescription ingredient in said amount, as it is known to lead to the desired pH control (based on previous experience with the composition), but it will still be preferable to add it before the perfume, although not 15 is necessary. Similarly, although a solution concentration of 20% Na triium hydroxide may be preferable, similarly other concentrations thereof may also be used.

EXAMPLE 5.

Component Percent 20 "Neodol" 25-7 1) 32.0% "Neodol" 45-2.25S 2) 3.0% "Alkaril" QCJ Dirt Solution Promoting Polymer (15%) 13.4%

Denatured ethanol (3A) 5.5%

Sodium formate 1.0% "Alcalase" 2.5L 3) 0.6% "Thermamyl" 120L 4) 0.4% "Tinopal" 5BM 5) 0.27%

Dye (Polar Brilliant Blue) 0.0025%

Perfume 0.4% 30 Deionized water to 100%; 100.0%

DK 161716B

27 1) Condensation product of approx. 7 moles of ethylene oxide and a higher fatty alcohol with an average of 12 - 15 carbon atoms per moth.

2) Sodium salt of the sulfonic acid ester of the nonionic condensation product of a higher fatty alcohol having a gene average of 14-15 carbon atoms with 2.25 moles of ethylene oxide.

3) Proteolytic enzyme sold by Novo Industri A / S (5% active enzyme component, 65% propylene glycol and 30% 10 water).

4) Amylolytic enzyme sold by Novo Industri A / S (5% active enzyme component, 65% propylene glycol and 30% water).

5) Fluorescent detergent of stilbene type.

The liquid detergent thus formed is prepared in a manner similar to that of Example 1 by mixing a portion of the water and the anionic and nonionic detergents, followed by the addition of the dirt solution-promoting polymer, the ethanol, the fluorescent clarifier. agent (sometimes dissolved in ethanol or ethanol-aqueous solutions), enzymes, sodium formate (dissolved in some water), dye and the remaining amount of water. If desired, an acid or base (NaOH preferred) can then be used to adjust the pH to be in the desired range, e.g. to 7. When the pH is lower than desired, an aqueous solution of sodium hydroxide (20%) is used to raise it to the desired level. The amount used is small, e.g. 0.2% NaOH or less. Then add the prescribed amount of perfume. The prepared product is tested by storage at 43.3 ° C for one week, after which it is seen that 28

DK 161716 B

be a clear, light blue liquid in a stable single phase, essentially like when it was manufactured. The protease activity is better than the protease activity of a liquid control detergent containing 7% sodium dodecyl benzene sulfonate, 2.8% triethanolamine (TEA) and no alcohol ether sulfate, and it is much better than other agents similar to the control agent but not containing sodium formate in one case and no TEA in the other. When both the formate and TEA are omitted from Composition 10 of the control agent (in all cases the differences are replaced by water), both protease and amylase activity are drastically diminished. The control agent and the first two variants are unstable upon storage as the polymer precipitates.

Shortly after preparation of the liquid detergent 15, this is used to wash a sample load of clean fabrics including some of polyester materials and others of 65% polyester and 35% cotton material. The washing conditions are the same as in Example 1, and the results are very similar, with the exception of the additional enzymatic cleaning effect obtained. Such desirable effects are achieved despite the presence of the sodium formate and optionally one or more other salts in the liquid.

When 2.8% triethanolamine or TEA salt is present in the liquid detergent of the above composition 25 to replace part of its water content, the detergent is found to be separated after storage for a week at 43.3 ° C. . Separation also occurs under such conditions when the triethanolamine is omitted and 5% sodium sulfate is present in the composition. Storage at room temperature 30 also results in such separation and correspondingly to diminish the soot-promoting effect of compositions containing the indicated amounts of triethanolamine and / or sodium sulfate as compared to the test composition.

DK 161716B

29

Liquid detergent testing for enzymatic cleaning strength is satisfactory, showing that the proteolytic and amylolytic enzymes are functionally effective in the stable liquid detergent. This is the case despite the fact that enzymes are often unstable in liquid detergent systems, especially at elevated temperatures.

EXAMPLE 6.

By changing the composition of Example 5, where the amount of "Neodol" 45-2.25S is increased to 5%, the ethanol amount is increased to 7.5%, 0.01% Polar Brilliant Blue dye is used instead of 0.0025%, and the clarifier is replaced by 0.24% "Tinopal" 5BM and 0.1% "Phorwite" BHC, a stable liquid detergent having dirt-solubility, enzymatic efficiency and purity similar to that of Example 5 is obtained. or even better properties. The liquid detergent is clear blue, and in the absence of dye it may have a light color so that it may also be dyed in the desired manner using other dyes. Instead, said detergent system equivalents of "Tinopal" RBS-200, "Tinopal" 4226 or "Phorwite" RKH and mixtures thereof may be used. In all such cases, the substantivity of the fluorescent brightening agent is enhanced by the presence of the higher fatty alcohol ethoxylate sulfate, and unlike other anionic detergents such as linear sodium dodecylbenzenesulfonate, the fatty alcohol ethoxylate sulfate does not destabilize the polymeric dirt-reducing enzyme-promoting enzyme and

DK 161716B

EXAMPLE 7.

The composition of Example 5 is changed such that 5% "Neodol" 25-3S is present instead of the 3% "Neodol" 45-2.25S. The product obtained is stable and clear after storage at elevated temperature and the stability of "Alkalase" and "Thermamyl" corresponds to the stability of the primary control agent mentioned in Example 5. However, when 2.8% TEA is also present in the composition, the product is unstable as the dirt-releasing QCJ polymer flocculates after storage at 43 ° C for one week.

EXAMPLE 8.

The contents of the various test compositions of the invention disclosed in Examples 5-7 are changed + + - 10% and - 25%, with the amounts of the various materials being kept within the ranges mentioned in the specification.

Instead of using the dirt-releasing polymer QCJ (aqueous solution) in such compositions, 2% QCF is used.

and 11.4% water, with QCF

• First dissolves in the water. Also other enzymes, stabilizers, alcohols and coloring agents described in the specification can be used within the indicated range of quantities. The resultant detergents are clear, stable and non-separable and have good dirt solution-promoting, cleaning and clarifying properties, as is the case for those described in Examples 5-25. This is also the case when the fluorescent dye, colorant and perfume are omitted from the compositions of this example. Similarly, when triethanolamine or an ionizable salt is present in such compositions beyond the indicated limits and when other anionic detergents such as sodium higher alkylbenzenesulfonates are used in place of the alcohol ethoxylate sulfate, the product similarly becomes less stable and less effective with to

DK 161716B

31 vision to promote dirt release during washing, and when the sodium formate is omitted, the effects of the enzyme are lost after only a few days of storage at the elevated test temperature.

In other variants of this example, the nonionic detergent "Neodol" is 23-6.5 or a mixture of equal parts "Neodol" 23-6.5 and "Neodol" 25-7, using the same total amount and obtaining a stable, efficient product. The alcohol ethoxylate sulfate can also be a straight mixture of 10 "Neodol" 25-3S and "Neodol" 45-2.25S and good results are obtained. With such changes, results such as those mentioned in Examples 5-7 can be obtained in both test washing machines and household washing machines as well as commercial washing machines having either top filling or side filling. This is also the case when pH adjustments are made with potassium hydroxide and when such adjustments made with sodium hydroxide or potassium hydroxide occur at pH values of 6.6, 7.4, 7.9 and 8.6. Typically, such pH settings will use less than 1% sodium hydroxide solution, preferably less than 0.5% thereof, and more preferably less than 0.2% thereof. In some cases, the sodium hydroxide may be added as a prescribed component in said amount, since it is known to lead to the desired pH control (based on previous experience with the composition), but it would still be preferable to add it before the perfume, although it is not necessary. While a 20% sodium hydroxide solution concentration may often be preferable, other concentrations thereof may also be used.

From Examples 5 to 8 and the foregoing description, it will be seen that the present invention relates to a stable and tract liquid detergent containing various components which could be expected to generate stability of the final product. Yet, surprisingly, a stable product of the invention can be obtained. Such a product has desirable 32

DK 161716 B

dirt-promoting, dirt-breaking, fluorescent-clearing (when the detergent is present), and detergent-active properties. Several of the components of the present invention exert dual effects therein. For example, the alcohol ethoxylate sulfate contributes to purity and helps to make the substrates (laundry fibers) more adhesive friendly, so that the fluorescent detergents will be more effective. The sodium formate, which is a stabilizer for enzymes, does not de-stabilize the dirt-releasing agent, as one would expect. The various components of these liquid detergents work together to produce a surprisingly attractive, stable and effective detergent. Thus, it is seen that the agents in question represent an unpredictable advance in the manufacture of stable products, which are preferably attractively clear (transparent or translucent), although in some cases opalescent and semi-clear or intended cream-like products can be produced.

EXAMPLE 9.

20 Component Percent

"Neodol" 25-7 22.0 p

"Alkaril" QCJ Dirt Solution Promoting Polymer (15%) 6.7% "Adogen" 462 6) 6.0%

Propylene Glycol 5.0% Denatured Ethanol (3A) 2.2%

Sodium formate 1.0% "Alcalase" 2.5L 0.45% "Thermamyl" 120L 0.3%

Dye (Polar Brilliant Blue) 0.0025% 30 Perfume 0.4%

Deionized water until 100% _ 100.0% 33

DK 161716 B

6) Dichocosimethyl ammonium chloride, (contains 75% active ingredient, 14% isopropanol and 11% water).

The liquid detergent thus composed is prepared in a manner substantially similar to those used in Compound 5 of Examples 5-8, but it contains the fabric softener and omits an anionic detergent. The product obtained is tested by storage at 43.3 ° C for one week, after which it turns out to be a clear, light blue liquid in a stable single phase, essentially as when it was made. The protease activity is 70% of the activity when the liquid detergent was produced and the amylase activity is 85% of the value to begin with.

Shortly after the preparation of the liquid detergent, it is used to wash a sample filling of clean fabrics 15 comprising some of polyester material and others of 65% polyester and 35% cotton material. The wash concentration and other washing conditions are the same as discussed in Example 5, and the results are also essentially the same, except that improved fabric softening is achieved in this example. When 2% or 3% triethanolamine or TEA salt is present in the liquid detergent with the above composition instead of part of its water content, the detergent is similarly shown after 2 weeks storage at 43.3 ° C. to be separated. Separation also occurs under such conditions when the triethanolamine is omitted and 5% sodium sulfate is present in the composition. Furthermore, when the triethanolamine is present, the liquid detergent-promoting effect of the liquid detergent is significantly diminished. Storage at room temperature also results in such a decrease in the dirt solution-promoting effect of compositions containing the indicated amounts of triethanolamine and / or sodium sulfate in comparison with the test composition. When the amount of dirt solution promotion- 34

DK 161716 B

if the polymer is increased to 2%, the same type of results as above are obtained.

Liquid detergent tests for textile softening and enzymatic cleaning strength are satisfactory, demonstrating that the quaternary ammonium halide and proteolytic and amylolytic enzymes are functionally effective in the stable liquid detergent. This is the case despite the fact that enzymes and quaternary ammonium halides are often unstable in liquid detergent systems, especially at elevated temperatures. However, replacement of propylene glycol with higher glycols, such as glycols of 8-12 carbon atoms, will result in two-phase separation of the product. In that particular composition, a complete replacement of propylene glycol with hexylene glycol will also cause phase separation, although hexylene glycol and amylene glycol are considered useful glycol components in the liquid type detergent type if used in smaller quantities and if used in combination with lower glycols such as propylene glycol. If dichocosymethyl dimonium chloride 20 is replaced with dihydrogenated tallow dimethyl ammonium chloride, the liquid detergent similarly separates into two phases, especially in the presence of the hexylene glycol (as a substitute for propylene glycol). Here too, however, the dihydrogenated tallow dimethylammonium chloride can, under certain circumstances, be used in a stable product by reducing the amount thereof and mixing it with dicocosimethylammonium chloride or other di-higher alkyl-di-lower alkyl quaternary ammonium halides where the higher alkyl groups have 12-14 carbon atoms and the lower alkyl groups have 1 or 30 carbon atoms. As an alternative, a more hydrophilic quaternary ammonium halide, such as ditalg-dimethylammonium chloride, which has a greater degree of unsaturation and thus better tolerates electrolytes, can be successfully used.

35

DK 161716 B

EXAMPLE 10.

When the nonionic detergent in the primary composition of Example 9 is replaced by "Neodol" 23-6.5, 0.01%

Polar Brilliant Blue dye is used instead of 0.0025% 5 thereof, and a fluorescent styling type binder is present, e.g. "Tinopal" RBS-200, "Tinopal" 5BM or "Tinopal" 4226 or "Phorwite" RKH or "Phorwite" BBP, in an amount of 0.1%, yields a stable and effective product that functions just like the product of Example 9, but it has a greater whiteness producing strength due to the presence of the detergent which is stable in the product. The product of this example also has an attractive clear appearance and is stable upon storage.

EXAMPLE 11.

The contents of the test compositions according to Examples 9 + +

and 10 are varied - 10% and - 25%, keeping the amounts of the various materials within the ranges mentioned in the specification. In such compositions, 1% QCF is used instead of the dirt-releasing polymer QCJ (aqueous solution).

and 5.7% water, with QCF

first dissolves in the water. Also other enzymes, stabilizers, textile softeners, glycols, alcohols and dyes described in the specification can be used in the indicated amount of 25 intervals. The resulting detergents are clear, stable and non-separating, and have good dirt-release, softening, cleansing and clarifying properties just like those described in Examples 9 and 10. This is also the case when the fluorescent dye, colorant and perfume 50 are omitted by the compositions of this example. Similarly, when triethanolamine or ionizable salt is at 36

DK 161716 B

present in such compositions beyond the stated limits, the product becomes less stable and less effective in promoting dirt release during washing, and when the sodium formate and glycol are omitted, the effects of the enzyme are lost. 5 only a few days storage at the elevated test temperature.

In other variants, the nonionic detergent in this example is a mixture of equal parts "Neodol" 23-6.5 and "Neodol" 25-7, using the same total amount. Results similar to those set forth in Examples 9 and 10 above can be obtained in both test washing machines and household washing machines as well as commercial washing machines using either top filling or side filling. This is also the case when pH adjustments are made with potassium hydroxide and when such adjustments made with sodium hydroxide or potassium hydroxide occur at pHs of 6.6, 7.4, 7.9 and 8.6.

From Examples 9-11 and the foregoing Examples as well as from the specification, it will be seen that the present invention relates to a stable and attractive liquid detergent, regardless of the fact that it contains various components which might be expected to generate stability of the final product. Nevertheless, surprisingly, a stable product is obtained which has desirable dirt release-promoting, textile softening, dirt-degrading and cleansing properties. Several of the components of the coping agents exert dual effects therein. For example, the propylene glycol can help solubilize lipophilic materials in the composition while also helping to stabilize the enzymes. The sodium formate, which is a stabilizer for enzymes, does not destabilize the dirt-releasing agent as would be expected. Although some quaternary ammonium halides and some glycols may destabilize liquid detergent compositions like the detergents of the present invention, the materials of the present invention do not. This is surprising because hydrophobic

Claims (3)

1. Dirt solution-promoting, stable, aqueous liquid detergent containing 20-50% by weight of a non-ionic detergent or mixture of non-ionic and anionic detergents, 1-5% by weight of a polyethylene terephthalate and polyoxyethylene terephthalate-promoting polymer having a total molecular weight of 15,000-50,000, the molar ratio of polyethylene terephthalate units to polyoxyethylene terephthalate units ranging from 2: 1 to 6: 1, and polyoxyethylene terephthalate having a molecular weight in the range of 1000-10,000, and an aqueous medium in which pH The value is 6-9, characterized in that it contains at most 2% water-soluble ionizable salt, which is not an anionic, surfactant water-soluble salt. Detergent according to claim 1, characterized in that it contains not more than 0.3% by weight of water-soluble ionizable salt which is not an anionic surfactant water-soluble salt. Detergent according to claim 1 or 2, characterized in that the water-soluble ionizable salt, which is not an anionic surfactant-water-soluble salt, is sodium. 35