BE899324A - ANTI-SOIL LIQUID DETERGENT AND PROCESS FOR THE PRODUCTION THEREOF. - Google Patents

Abstract

Storage-stable liquid anti-fouling detergent, comprising a non-ionic synthetic organic detergent, optionally in admixture with an anionic synthetic organic detergent, and a specific type of anti-fouling copolymer of ethylene terephthalate and ethylene oxide in a aqueous medium with a maximum content of ionizable salts of 2%, with a pH of 6 to 9, as well as possibly enzymes which hydrolyze the soiling and a stabilizer therefor and / or a softener of the ammonium salt type quaternary for tissue.

Description

       

  The present invention relates to liquid detergent compositions. More particularly, it relates to such compositions which contain an anti-fouling polymer which is deposited on the polyesters and the polyester blends during the washing and facilitates the removal of the lipophilic soils subsequently applied to

  
these matters. Preferably, the liquid detergent may include an enzyme to promote cleaning, with a stabilizer for the enzyme, and it may also include a fabric softener, for example a quaternary ammonium salt. It is surprising to note that the compositions of the present invention are physically and functionally stable in storage, even when they contain one or more enzymes and one or more fabric softeners.

  
Liquid detergents have been used to wash linens in washing machines and have often been applied to soiled areas of laundry, such as shirt collars, before washing. The use of copolymers of polyethylene terephthalate and polyoxyethylene terephthalate in detergent compositions, as anti-fouling agents, has been described in various patents, some of which relate to liquid preparations.

   However, the liquid detergents described are not of the type of the present invention since those of the patents in question contain triethanolamine and / or water-soluble ionizable salts (other than anionic detergents) which tend to cause separation of the liquid detergent and to destabilize the anti-fouling polymer during storage so that it subsequently loses its anti-fouling effectiveness.

  
In liquid detergents, enzymes tend to lose their activity in storage unless they are stabilized, for example by salts such as sodium formate, glycols, for example propylene glycol, or other materials of this guy. However, the salts mentioned tend to destabilize fabric softeners of the quaternary ammonium halide type and anti-fouling copolymers which are desirable components of the liquid detergents of the invention, and this destabilization of the anti-fouling agent is particularly pronounced in the presence of lower alkanolamines or their salts, for example triethanolamine
(TEA), the present of which should be avoided.

   Consequently, it is surprising that the liquid detergents of the invention can be obtained in a clear and stable form which does not separate, the various functional components of which are effective after storage at elevated temperatures.

  
According to the present invention, a liquid anti-fouling detergent comprises a proportion with detersive action, of a nonionic detergent or of a mixture of nonionic and anionic detergents, a proportion favoring the elimination of soiling, of a polymer anti-fouling

  
polyethylene terephthalate and polyoxyethylene terephthalate and an aqueous medium, the pH of which is in the range of 6 to 9 and which contains not more than 2% of

  
ionizable water-soluble salt, non-anionic surfactant. The invention also relates to a process for manufacturing the compositions described.

  
Preferred liquid compositions of this type also contain enzymes and enzyme stabilizers, as well as, preferably, a fabric softener. Thus, a stable liquid detergent containing enzymes comprises a proportion with detergent action, of a nonionic detergent, a proportion, reinforcing the action of the detergent and increasing the substantivity of the fluorescent brightening agent, of a detergent of the higher fatty alcohol polyethoxylate sulfate type, a proportion favoring the elimination of the soiling of an anti-fouling polymer of polyethylene terephthalate and of polyoxyethylene terephthalate, a proportion of enzyme sufficient for hydrolysing enzymatically protein and / or starchy smears on the fabrics during their washing with an aqueous solution for washing the liquid detergent,

   a proportion with stabilizing effect of a stabilizer for the enzyme (s), and an aqueous medium, in which the pH is between approximately 6 and 9 and which contains not more than 2% of water-soluble ionizable material other than the detergent of the type higher fatty alcohol polyethoxylate sulfate. Similarly, a stable liquid detergent containing enzymes, dirt repellants and fabric softeners includes a proportion

  
detergent effect of a nonionic detergent, a proportion favoring the elimination of the soiling of an anti-fouling polymer of polyethylene terephthalate and polyoxyethylene terephthalate, a proportion with softening effect of a fabric softener for salt type of quaternary ammonium, a proportion of enzyme sufficient to enzymatically hydrolyze the protein and / or starchy soils of the tissues during their washing with an aqueous washing solution of the liquid detergent, a proportion with stabilizing effect of an enzyme stabilizer, and an aqueous medium, in which the pH is between approximately 6 and 9 and which does not contain more than 2% of water-soluble ionizable material, for example salts and / or triethanolamine.

  
Although various synthetic organic nonionic detergents with satisfactory physical characteristics can be used, including the condensation products of ethylene oxide and propylene oxide with each other and with hydroxyl bases, for example nonylphenol and oxo type alcohols, for best results, it is preferable that the nonionic detergent is a condensation product of ethylene oxide and higher fatty alcohol. In these products, the higher fatty alcohol contains 10 to 20 carbon atoms, preferably 12 to 15 or 16 carbon atoms, and the nonionic detergent contains 2 or 3 to 20 or 30 ethylene oxide groups per mole, of preferably 6 to 11

  
or 12. More preferably, the nonionic detergent is a detergent in which the higher fatty alcohol has about 12 to 15 or 12 to 14 carbon atoms and which contains

  
6 or 7 to 11 moles of ethylene oxide, for example 7. Among

  
  <EMI ID = 1.1>

  
Conoco Division of E.I. DuPont de Nemours, Inc., and "Neodols &#65533;
23-6.5 and 25-7, available from Shell Chemical Company. Among their particularly interesting properties, in addition to good detergency with regard to oily and greasy dirt deposits on the articles to be washed, and excellent compatibility with

  
the polymeric anti-fouling agents of the invention, there is compatibility with anionic-soluble detergents of the types of (alkyl sup b -benzene sulfonate with linear alkyl groups and sulfate of higher fatty alcohol polyethoxylate, the enzymes , enzyme stabilizers, fabric softeners and other components of the compositions of the invention, and long-term stability of

  
viscosity in aqueous and aqueous alcoholic solutions.

  
The anionic detergent that can be used

  
in liquid detergents according to more extensive aspects of the invention is preferably a (higher alkyl) benzene sulfonate with a linear alkyl group or a sulfate

  
higher fatty alcohol polyethoxylate. Normally, the water-soluble salts of these materials are preferred, for example the alkali metal salts and, among them, the sodium salts are generally preferred to the potassium salts. When the anionic detergent is a sodium (higher alkyl) -benzene sulfonate, the higher alkyl group normally contains from 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, and better still 12 or 13 carbon atoms, in particular 12. When this nonionic detergent is a higher fatty alcohol polyethoxylate sulfate, as is the case with liquids containing enzymes, in which the detergent increases the detergent power and promotes an increase in the subs

  
  <EMI ID = 2.1>

  
cool higher fat has 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, and better yet
12 or 12 to 15 carbon atoms, and the polyethoxylate has 1, 2 or 3 to 20 ethoxy groups, preferably 3

  
to 10, and better still 3 to 6 or 7, for example 3, 6.5 or

  
7. Although not preferable, mixtures of such anionic detergents can be used in the enzyme-free compositions, generally at ratios of

  
  <EMI ID = 3.1>

  
nics and surfactants are normally omitted from liquid detergents for fabric softening.

  
The polymer promoting the anti-fouling effect

  
which is an essential component of the compositions of the present invention is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate which is soluble (which is preferred) or dispersible in water and can be deposited from washing water containing the detergent (s) on synthetic organic polymeric fiber materials, in particular polyesters and polyester mixtures, so as to give them

  
anti-soiling properties while retaining the comfort for the user of such garments made from these materials and by not preventing or notably inhibiting the transmission of vapor through these garments. These polyesters have also been shown to have anti-redeposition properties and often promote the elimination of stains on substrates. They tend to keep soiling, especially oily or greasy soiling, in dispersion in the wash water during washing and rinsing, so that it is not redeposited on the laundry. Useful products from

  
this type are copolymers of ethylene glycol or another suitable source of ethylene oxide units, of polyoxyethylene glycol and of terephthalic acid or an appropriate source of terephthalic fragment. Copolymers can also be considered to be the condensation products of polyethylene terephthalate, which can sometimes be referred to as a polymer of ethylene terephthalate, and polyoxyethylene terephthalate. Although the terephthalic unit is preferred as the sole diacid unit in the polymer, the invention contemplates using relatively small proportions of isophthalic acid and / or orthophthalic acid (and sometimes other di-acids as well) for modify the properties of the polymer.

   However, the proportions of these acids or sources of such additional units introduced into a reaction mixture, and the corresponding proportions in the

  
  <EMI ID = 4.1>

  
none of all the phthalic units present, and preferably will be less than 5% of this total.

  
The molecular weight of the polymer will be in the range of about 15,000 to 50,000, preferably about 19,000 to 43,000, more preferably between 19,000 and 25,000, for example about 22,000. These molecular weights are weight average molecular weights, as distinguished from number average molecular weights which, in the case of the present polymers, are often less. In the polymers used, the polyoxyethylene will have a molecular weight in the range of about 1,000 to 10,000, preferably about 2,500 to 5,000, more preferably 3,000 to

  
4,000, for example approximately 3,400. In these polymers, the molar ratio of the polyethylene terephthalate units to the polyoxyethylene terephthalate units (considering

  

  <EMI ID = 5.1>


  
as such patterns) will be in the range of 2: 1 to 6: 1 in particular from 5: 2 to 5: 1, and more preferably from 3: 1 to 4: 1, for example about 3: 1. The proportion of ethylene oxide units to phthalic units in the polymer will be at least 10: 1 and often 20: 1 or better still 20: 1 to
30: 1 and more particularly about 22: 1. Thus, it can be seen that the polymer can be considered to be essentially a modified ethylene oxide polymer, the phthalic unit being only a minor component, whether the calculation is carried out on a molar basis or on a weight basis. It is considered surprising that with such a small proportion of ethylene terephthalate or terephthalate

  
polyethylene in the polymer, it is sufficiently analogous to the polymer of the polyester fiber substrate (or other polymers to which it adheres, for example polyamides) to be retained there - during - lifting, rinsing and drying . However, as shown by the comparative tests and various washing tests in which the soil release effect is measured, the polymer described in the detergent compositions of the invention is effective in depositing on the washed synthetic materials, in particular polyesters, so

  
to make them more easily able to be freed from washing oily soiling with a nonionic liquid detergent composition or another detergent product. It is considered that the greater hydrophilic nature of the polymer attributable to the high proportion of hydrophilic ethylene oxide units which it contains may be responsible for the excellent anti-fouling properties (for the elimination of lipophilic soiling) which it confers. to the material on which it is deposited, and this can also help the polymer to cooperate with the components of the liquid nonionic detergent.

  
Various articles, texts and patents in the literature describe processes for manufacturing polymers

  
  <EMI ID = 6.1>

  
Polymer Science "Vol. 3, pages 609-630 (1948) and Vol. 8 pages 1-22 (1951). Although these documents describe suitable methods of making the polymers of the invention, it is believed that none none of them describes the particular polymers which are used in the present invention (but which are commercially available) and none describes the detergent compositions of the invention. These polymers can be considered to have a statistical structure formed of units polyethylene terephthalate and polyoxyethylene terephthalate, such as those obtainable by reacting polyethylene terephthalate (for example of quality for spinning) and polyoxyethylene terephthalate, or by reacting ethylene glycol, polyoxyethylene glycol and their acid precursors (or methyl ester).

   However, the invention also envisages using more ordered copolymers, such as those obtained by reacting components having chain lengths or predetermined or known molecular weights, so as to obtain what could be called copolymers block or non-random copolymers. The grafted polymers can also be used.

  
The materials described are available from a variety of sources, the products of one of which are now described in more detail. Copolymers useful for the manufacture of the detergent compositions of the present invention are marketed by Alkaril Chemicals, Inc., and commercial products of this Company which have been successfully used to produce satisfactory detergent compositions promoting the elimination effect of soiling is that sold by the said Company under the trademarks "Alkaril QCJ" and "Alka-

  
  <EMI ID = 7.1>

  
products offered by this Company in limited quantities, designated by 2056-34B and 2056-41 have also been shown to be acceptable. The QCJ product, normally supplied in the form of an aqueous dispersion with a concentration of approximately 14 or
15% in water and preferably used to manufacture the liquid detergents of the invention, is also available in the form of an essentially anhydrous solid material (QCF). In these two types of products, the molar ratio of the ethylene oxide units to the phthalic unit is approximately 22: 1. In a dispersion at 16% in water, in the form of QCJ, the viscosity at 100 [deg.] C, is about

  
  <EMI ID = 8.1>

  
resembles a light brown hard wax and the ratio of its hydrophilic: hydrophobic motifs is approximately 16 to 1, the viscosity being approximately 265.10-6 m <2> / s (265 centistokes). Polymer 2056-34B resembles a brown hard wax having a hydrophilic: hydrophobic ratio of approximately 10.9: 1 and its viscosity, under the same conditions as previously mentioned, is approximately 255.10-6 m <2> / s (255 centistokes). The higher the molecular weight of the polymer, the lower the hydrophilic: hydrophobic molar ratio and the detergent compositions of the invention still provide a satisfactory effect reinforcing the anti-fouling action. QCJ and QCF polymers have melting points (by differential thermal analysis) of around 50

  
at 60 [deg.] C, an analysis of the content of carboxyl groups of

  
5 to 20 or 30 equivalents / 106 grams and a pH of 6 to 8 in distilled water at a concentration of 5%. The molecular weights (weight average) are from 20,000 to 25,000 and the molar ratio of the ethylene terephthalate units to the polyoxyethylene terephthalate units is approximately
74:26. All the products represented by the aforementioned trademarks are water-soluble or substantially water-soluble in lukewarm or hot water (40-70 [deg.] C) or at least easily dispersible, and they can be characterized by a high, higher molecular weight. to 15,000, generally between 19,000 and 43,000, or better
20,000 to 25,000, for example about 22,000.

  
The enzymes used in certain compositions of the invention include proteolytic and amylolytic enzymes, for example alkaline proteases (subtilysine) and alpha-amylase. Among the preferred enzyme preparations which are useful there may be mentioned Alcalase 2.5L (2.5 Anson units per gram) and Termamyl 120L, both manufactured by Novo Industri, A / S. However, other suitable proteolytic and amylolytic enzyme preparations can also be used. The compositions mentioned are in liquid form and contain 5% of active enzyme in combination with 65% of propylene glycol and 30% of water. In the present specification, the proportions to which we refer are those of the enzymes active in the preparations.

  
The stabilizer or a mixture of stabilizers for the enzyme is preferably sodium formate or

  
  <EMI ID = 9.1>

  
for example potassium formate, can also be used and acetates can also be useful, as well as other equivalent salts or mixtures of such salts and alkali metal formate.

  
The fabric softener of the quaternary ammonium salt type which is used in certain liquid detergent compositions of the invention may be any suitable material of this type which is stable in

  
  <EMI ID = 10.1>

  
read the known imidazolinium halides with satisfactory stability in place of the conventional quaternary ammonium halides. However, quaternary ammonium halides are preferred. These compounds are preferably chlorides, although bromides and iodides may be useful. Among the four substituents attached to the quaternary nitrogen, at least one, and preferably two, is a long chain substituent such as a linear or higher fatty group, and preferably two of these substituents are a higher fatty group .

   The chain length is generally from 10 to 20 carbon atoms, preferably from 12 to 18 carbon atoms, chain lengths from 12 to 14 carbon atoms or their mixtures, for example coconut alkyl (derived from oil coconut or equivalent material) being particularly preferred. The other substituents on the nitrogen are lower alkyl groups, usually having 1

  
with 3 carbon atoms, and among them, the methyl group is particularly preferred. Thus, although other quaternary ammonium halides may also be useful, at least when they are only part of the quaternary fabric softener, the one which is preferred and which is most stable in the liquid detergents of l The invention is di-coco-dimethyl ammonium chloride. This product is available in the form of a liquid comprising 75% of active ingredient, 14% of isopropanol and 11% of water.

  
The aqueous medium used comprises water and preferably also a lower alkanol. The water is advantageously deionized water, but it is possible to use city water with a hardness reaching approximately 300 ppm, in the form of calcium carbonate (the hardness is generally due to the mixed ions magnesium and calcium) well that it is preferable that the hardness be less than 100 ppm, in order to avoid destabilization of the liquid detergent or separation of its constituents. A little water can come from the starting materials, for example aqueous anti-fouling agents, enzyme preparations, softeners, alkanols and colorants. The lower alkanol can be ethanol, isopropanol or n-propanol, but ethanol is much preferred.

   When ethanol is used, it is normally in the form of a denatured alcohol, for example 3A, which contains a small proportion of water plus a denaturing agent. The aqueous medium may also contain small amounts of compatible dissolved salts, but these are normally avoided as far as possible.

  
Another liquid which can advantageously be used in some of the liquid detergents of the invention, for example those containing enzymes and fabric softeners, is a lower glycol such as a glycol having 3 to 6 carbon atoms in the alkyl group. . Although hexylene glycol can be used in some formulations, it can, in some others, promote instability, so that propylene glycol is preferred.

  
Various suitable adjuvants can be present in the liquid detergents of the invention, for example

  
fluorescent dyes, simple dyes (dyes and pigments dispersible in water such as ultramarine blue), bactericides, fungicides and perfumes. The concentrations of these components are generally kept low, often less than 1% and preferably less than 0.7%. Thus, the perfume concentration is generally less than 1%, preferably from 0.2 to 0.6%, for example 0.4%. Fluorescent brighteners or optical brighteners can be present in the liquid detergent in a proportion of 0.02 to 2%, preferably 0.1 to 1%, more preferably 0.2 to 0.5 %. The percentages indicated apply to materials sold commercially.

   Such brightening agents are known as cotton brightening agents, brightening agents soluble in the bleaching agent, polyamide brightening agents and polyester brightening agents and, in general, their blends are used so that the detergent can be used for brightening a wide variety of washed materials, including cotton and

  
synthetic materials. Examples of such suitable brightening agents are those identified by: TA, DM, DMEA, DDEA, DMDDEA, BS, NTS, BBI, AC, DP, BBO, BOS and NTAS

  
  <EMI ID = 11.1>

  
Bleaches in the Soaps and Detergents "by FG Villaume, appearing in" The Journal of the American Oil Chemists' Society "(October 1958), Vol. 35, n [deg.] 10, pages 558-566. Useful fluorescent lights are sold under the trademarks: "Calcofluor White ALF" (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 brightening agents are normally present in the form of their water-soluble salts, but they can also be used in the corresponding acid forms.

   Most of these materials are useful for brightening cotton and are of the stilbene-sulfonic or aminostilbene acid (or salt) type, which is designated herein by stilbene-type brightening agents and an this type of brightening which we prefer is "Tinopal 5BM Extra Conc." from CIBA-Geigy. For fabric softening detergent, the pre-

  
  <EMI ID = 12.1>

  
preferably between 0.05 and 0.15%, for example 0.1%. The possible proportion of dyes, for example the polar bright blue "Polar Brilliant Blue" represents 0.001

  
  <EMI ID = 13.1>

  
quide, for example 0.0025% or 0.01%. The various adjuvants are chosen taking into account their compatibility with the other components of the formulation and the non-separation characteristics. Because the water-soluble ionizable salts, whether mineral or organic, are generally compatible with anti-fouling agents, their presence is generally to be avoided. Among these salts which should advantageously be avoided, mention may be made of sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, ammonium chloride and ammonium sulfate, but these are only examples of these salts.

   Although sodium formate is also to be removed from many liquid detergents, it has been surprisingly found that a limited proportion of it is compatible with the other components of the formulation of the invention, in combination. The presence of ionizable species, such as triethanolamine (TEA), diethanolamine, ethanolamine, diisopropanolamine, n-propanolamine and mono-, di-

  
and lower tri-alkanolamines and mixed lower alkanolamines of 2 to 4 carbon atoms per alkanol unit is to be avoided because, like the salts mentioned, it destabilizes the anti-fouling polymer and / or the liquid detergent. Among them, TEA seems to be the most destabilizing by causing serious separations of the polymer. In the present specification, these ionizable species which can form salts, must be considered to be part of the admissible proportions of all salts of

  
this type may be present. In general, it is advantageous to avoid the presence of adjuvants other than dyes, perfumes, fluorescent brighteners, antioxidants, and any neutralizing agents which can be used to adjust the pH of the liquid detergent in the stable range. It is preferable that any neutralizing agent which can be used, generally to increase the pH of the liquid detergent mixture, is an alkali metal hydroxide, such as sodium hydroxide, in aqueous solution at a concentration of 5 to 40 %, for example from 15 to 25%. The triethanolamine salts and the free triethanolamine are to be avoided in particular.

  
The liquid detergent produced has a desirable viscosity, often in the range of 50 to 500 mPa.s, preferably 100 to 200 mPa.s, and the viscosity can be adjusted by varying the proportion of lower alkanol in the range indicated. Liquid detergent should be poured easily but should have a desired consistency. Its pH should be 6 to 9, preferably 6.1 to 7.9, and more preferably 6.5 to 7.5.

  
In the liquid anti-fouling detergents of the invention which have better storage stability so that the anti-fouling polymer and the enzyme (s) do not undergo degradation and do not separate from the rest of the composition, the proportions of the various

  
  <EMI ID = 14.1>

  
meres, although mentioned in the singular, also include mixtures. The proportions of the components which follow apply in the broad sense of the invention, to the product containing enzymes and to the product containing enzymes and a softener, respectively.

  
The nonionic detergent (which comprises mixtures of such detergents) or a mixture of nonionic and anionic detergents (both of the synthetic organic type) represents 25 to 50% of the product, preferably
20 to 40% for the nonionic detergent and 3 to 15% for the anionic detergent. Preferably, the proportions of these detergents are 25 to 35% and 5 to 10%, respectively, for example about 32% and about 7%, respectively. The polymer promoting the elimination of soiling represents approximately 0.5 to 10%, preferably 1 to

  
6%, and better still 1 to 3%, for example around 2%. The lower alkanol content is from 3 to 15%, preferably from 5 to 12% and better still from 6 to 10%, for example about 8%, and the water content, in the presence of lower alkanol , is around 30 to 60% ,. preferably 45 to
55%, and in the absence of lower alkanol, this range is increased to replace the lower alkanol with water.

  
The content of ionizable water-soluble salts, whether organic or mineral, must be kept at a low value, generally not more than 1% of the liquid detergent, preferably less than 0.5%, and better still less than 0.3 %, and the content of triethanolamine is similarly limited, in order to avoid separation of the anti-fouling polymer, the desired limits being 0.5, preferably 0.2%, and better still 0%. In certain cases, the salt content is kept within limits lower than the accepted content of alkanolamine because certain salts can be even more harmful for the stability of the product than the alkanolamines.

   Naturally, the content of anionic detergent present, which can be considered as an ionizable salt, is not included in the limited proportions of such a salt present since it seems not to have the same type of destabilizing effect on the compositions of the invention. Although the liquid detergent may contain suitable adjuvants, such as a dye, a perfume and a fluorescent brightening agent, previously mentioned, the proportion of these adjuvants is normally minimized, and is generally less than 2%, &#65533; e preference less than

  
1%, and better still less than 0.8%, but the dye and the brightening agent are not destabilizing.

  
For the product containing enzymes (without softener), the content of synthetic organic nonionic detergent is normally between 25 and 40% of the product, preferably 28 to 36%, and better still

  
30 to 34%, for example 32%. The fatty alcohol alkoxylate sulfate content is generally from 1 to 8%, preferably from 2 to 7%, and better still from 2 to 6%, for example from 3% or 5%. The content of fluorescent brightening agent is from 0.02 to 2%, and preferably from 0.1 to 1%,

  
for example 0.2% or 0.4%. The percentage of active ingredient in the brightening agent can often be from 0.01 to

  
1%, for example from 0.01 to 0.1%. The content of anti-fouling polymer is approximately 0.5 to 5%, preferably 0.8 to 3%, and better still 0.8 to 2.5%, for example approximately 1% or 2 % (based on the active ingredient). The total enzyme content is between 0.0005 and 0.15%, preferably between 0.025 and 0.1%, the protease content of which is 0.005 to 0.1% and the amylase content which may be present is 0.005 at 0.05%. Preferred levels of enzymes are 0.01 to 0.1% and 0.01 to 0.03%, respectively. The percentage of protease is preferably from 0.02 to 0.05%. The particular formulation percentages are about 0.03 and 0.02%, respectively.

   The enzyme stabilizer, generally an alkali metal salt of an aliphatic acid lower than 1 to 3 carbon atoms, for example sodium formate, generally represents 0.2 to 2%, preferably 0.5 to 1.5 %, and better still 0.7 to 1.3%, for example 1%. The lower alkanol content is from 3 to 12%, preferably from 4 to 9%, and better still from 5 to 8%, for example from 5.5 to 7.5%. The water content is about 40 to 65%, preferably 46 to 62%, more preferably 50 to 60%, for example about

  
54 or 55%.

  
The content of ionizable water-soluble salts, whether organic or mineral, must be kept at a low value, less than 2%, and generally not more than 1% of the liquid detergent, preferably less than 0.5%, and better still less than 0.3%, and the triethanolamine content is also limited to avoid separation of the anti-fouling polymer, the desired limits being 0.5%, preferably 0.2%, and better still 0% . In some cases, the salt content is kept at lower limits than the accepted alkanolamine content because certain salts may even be more detrimental to the stability of the product than the alkanolamine.

   However, in the compositions of the invention, the content of water-soluble alkali metal lower carboxylate such as sodium formate, can reach 2%, because these components stabilize the enzymes, and at such concentrations, in particular at about 1% or less, they are compatible with the detergent and the anti-fouling polymer, so that separation of the polymer does not occur.

  
For liquid enzymatic detergents and fabric softeners, the content of synthetic organic nonionic detergent (which includes mixtures of such detergents) is between 10 and 35% of the product, preferably between 15 and 30%, and better still between 20 and 25%, for example 22%. The anti-fouling polymer content is approximately 0.5 to 5%, preferably 0.7 to 2%, and more preferably 0.8 to 1.5%, for example approximately 1%
(based on the active ingredient). The content of quaternary compound is from 1 to 10%, preferably from 3 to 8%, and better still from 3 to 6%, for example 4.5%. The enzyme content can range from 0.005 to 0.15%, preferably from 0.025 to 0.05%, the protease content of which is from 0.005 to 0.1% and the amylase content which may be present is from 0.005 to 0, 05%.

   The preferred levels of enzymes are 0.01 to 0.05% and 0.01 to 0.025% respectively. Preferably, the protease content is from 0.015 to 0.04%. The particular formulation percentages are about 0.023-0.015%, respectively. The enzyme stabilizer, a lower aliphatic acid salt such as sodium formate, generally constitutes 0.2 to 2%, preferably 0.5 to 1.5%, and more preferably 0.7 to 1.3% , for example 1%. The lower alkanol content is 1 to
10%, preferably 1.5 to 3%, and more preferably 2 to 2.5%, for example 2 or 2.2%. The lower glycol content is 2 to 10%, preferably 3 to 8%, more preferably 4 to 7%, for example 6%. The water content is about 40 to 80%, preferably 50 to 70%, more preferably 60 to 65%, for example about 63%.

  
The content of ionizable water-soluble salts, whether organic or mineral, must be kept at a low value, generally not more than 1%

  
  <EMI ID = 15.1>

  
and preferably less than 0.3%, and the triethanolamine content is also limited to avoid separation of the anti-fouling polymer, the desired limits being 0.5%, preferably 0.2%, and better still

  
0%. In some cases, the. salt content is maintained at lower limits than the accepted alkanolamine content, since certain salts can be even more harmful for the stability of the product than is the alkanolamine. However, in the compositions of the invention, the content of lower carboxylates of water-soluble alkali metals, for example sodium formate, can reach 2%, because these components stabilize the enzymes.

  
and, at such concentrations, particularly around

  
1% or less, they are compatible with the detergent product.

  
The liquid detergents of the invention can be manufactured by mixing their various components with the aqueous medium, preferably containing at least part of the lower alkanol, until they dissolve therein (or disperse therein). suitably) or the individual components may be selectively dissolved in portions of water and / or lower alkanol and / or lower glycol, and / or the anti-fouling polymer preparation, and / or liquid enzyme preparation, then the various liquid fractions can be mixed together. It is often better to adjust

  
the pH of the liquid in the range of 6.1 to 7.9, preferably 6.5 to 7.5, by adding an appropriate neutralizing agent (which is not triethanolamine) which has not destabilizing effect on the anti-fouling polymer, the enzyme (s), the softening agent or the liquid product containing them, so that it does not degrade and does not separate from the liquid detergent during storage, in particular at high temperature. The preferred neutralizing agent is an aqueous solution of sodium hydroxide, which normally comprises 10 to 40% sodium hydroxide, preferably 15 to 25%, although more dilute concentrations may sometimes be desirable. The viscosity of the product can then be adjusted by adding alkanol and / or water.

  
The liquid detergent composition of the invention can be used for washing (and treating) laundry containing synthetic fibers such as polyester fibers, for example "Dacron". in the normal way that is used for washing with other liquid detergents.

  
However, a lesser amount of the product of the invention can be used due to its soiling action and, in many cases, the cleaning and softening effects are greater. Different concentrations of the liquid detergent can be used, normally between about 0.02 or 0.04 and 0.3 or 0.6%, preferably between 0.05 or 0.1 and 0.15 or 0.3% , the concentration generally being about 1/2 cup per wash in a top-loading machine for the product containing a fabric softener, and about 1/4 cup for washing with the other two types of products. In general, it is best to use about 1/4 or 1/2 cup (about 60 or 120 ml) of liquid detergent per normal wash load (about

  
64 liters for a top-loading washing machine), which represents a concentration of about 0.1 or 0.2% of the liquid detergent in the washing water. About the same concentration can be used when washing in a front loading machine, although less water is used
(thus less detergent composition is used). We normally put about 3 in the washing machine

  
3.5 kg of laundry. The temperature of the washing water is preferably at least 49 [deg.] C, but suitable washing and treatment results can be obtained with the anti-fouling polymer, the enzymes and the softener in the liquid detergent at temperatures between about 40 and 80 [deg.] C, preferably between 45 and 70 [deg.] C. The dry weight of the materials to be washed and treated is generally about 5 to 15 or 20 of the weight of the aqueous washing medium, preferably about 5 to 10% of this weight.

  
Washing is carried out with stirring over a period of about five minutes to half an hour or an hour, often between 10 and 20 minutes. Then the washed materials are rinsed, usually several times, and they are dried, for example in an automatic clothes dryer. Preferably, the first washing of the material to be treated is carried out when this material is not very dirty, so that the anti-fouling polymer is deposited on a surface as clean as possible. However, this is not necessary, and there is an improvement in the cleaning of materials and batches subsequently soiled when the first washing is not carried out on a cleaner substrate. Several washes with the liquid detergent of the present invention increase the anti-fouling properties of

  
the material treated, and this effect sometimes persists until

  
3 or 5 treatments.

  
When polyester and polyester / cotton blend fabrics are washed as described with the compositions of the present invention, and are then soiled or stained with dirty engine oil and washed with a detergent of the present invention or another commercial detergent (often of the type comprising a detergency aid), there is a significant elimination

  
lipophilic soiling, compared to similar treatments in which the liquid detergent initially used does not contain an anti-fouling polymer. In other comparisons, when large proportions of water-soluble ionizable salt, for example 5% sodium sulfate, or more than 1% triethanolamine

  
or one of its salts, are present in the liquid detergent, we find that after a storage at high temperature (43 [deg.] C) for two weeks, simulating a longer storage at room temperature, the phases

  
separate from the liquid detergent body and the anti-fouling properties of the polymer it contains are reduced, as well as the enzymatic and softening activity, when these materials are present in the formulation. When the enzyme stabilizer is omitted, the enzymatic action is significantly reduced during storage. Thus, the compositions of the present invention are important because they are stable and give more effective products for the desired applications, improving the removal of soiling, the cleaning effects and the softening of the washed fabrics, as well than a more attractive liquid detergent composition that does not separate during storage.

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

EXAMPLE 1

  

  <EMI ID = 16.1>
 

  
The liquid detergent in the formulation is made by mixing part of the water together with the nonionic and anionic detergents, then adding the anti-fouling polymer, ethanol, fluorescent brightener, dye and l remaining water. Then you can use an acid or a base (NaOH is preferred), if you

  
desired, to adjust the pH to the desired range. In the example above, the pH is 7.8 (undiluted). However, when the pH is below the desired range, an aqueous solution of sodium hydroxide (20%) is used to raise it to the desired value, for example 7.5, and the proportion used is low, for example about

  
0.2% NaOH or less. Then we add the proportion

  
fragrance of the formulation. The product obtained is tested by storage at 43.3 [deg.] C for two weeks, after which it is noted that it comprises only one phase, essentially analogous to the product initially produced.

  
Shortly after its manufacture, the liquid detergent is used to wash a test load of clean fabrics comprising partly polyester and partly a mixture

  
65% polyester and 35% cotton. The washing concentration is 0.1% by weight of the liquid detergent, based on the weight of the washing water, and the batches washed are about 5% of the weight of the washing water. After washing in a normal test washing machine, using

  
under the conventional conditions previously described, the batches are rinsed and dried. Then each test batch is stained with about three drops of dirty engine oil of a conventional type used for such a test and it is washed in the same type of machine, using a detergent.

  
Trade. As controls, batches which have not been previously treated with the liquid detergent of the invention are used. The temperatures of the treatment and subsequent washing are the same in all cases, namely 49 ° C., which is considered to be an optimal temperature for the treatment. In certain tests, the subsequent washing is carried out with the liquid detergent composition of the invention. In all the tests, the treated batches are clearly whiter to the eye and by reflectometer test than the control batches, which shows that the anti-fouling component

  
of the liquid detergent composition effectively promotes the removal of applied dirt from the batches during subsequent washes. Also, it is noted that the redeposition on the non-soiled parts of the fabrics of the dirty engine oil removed (from the application of stains) is reduced when the anti-fouling polymer is applied to the fabric before it is dirty for the 'test. Thus, the liquid detergent containing the anti-fouling polymer, in addition to promoting the elimination of soiling, also helps to keep it in suspension, by preventing a deposit of this loose soiling on the other parts of the test material.

  
When the liquid detergent of the formulation indicated above contains 2% or 3% of triethanolamine to replace part of the water, after two weeks of storage at 43.3 [deg.] C, it is found that the detergent has separated . Separation also occurs in the absence of triethanolamine and in the presence of 5% sodium sulfate in the formulation. Also, in the presence of triethanolamine, the anti-fouling action of the liquid detergent is significantly reduced, compared

  
to the experimental formulation of the present invention after two weeks of aging at elevated temperature at 43.3 [deg.] C, followed by a test as previously described. In addition, storage at room temperature also results in such a decrease in the anti-fouling action of the formulation containing triethanolamine, compared to the experimental formulation.

  
When the amount of anti-fouling polymer

  
is reduced to 1% or increased to 3%, the same results are obtained as those indicated above, with the difference that the formation of anti-fouling polymer at 3% is more effective than the formulation at 2% for promoting removal of soiling according to the tests described, and that the 1% formulation is slightly less effective, although at the two concentrations of 1% to 3%, good and excellent results are obtained respectively.

  
When conducting similar tests using other lipophilic soils, such as corn oil
(red), butter, shoe polish, lipstick, mayonnaise sauce and barbecue sauce, similar results are obtained, the greatest improvements in the case of the experimental agent compared to the control being obtained for corn oil, lipstick and dirty engine oil. Elimination is 100% for corn oil, butter, "French dressing" sauce and barbecue sauce and it is almost 100% for lipstick. Similar results are obtained when the fabrics tested are Dacron &#65533; knitted, simple, in Dacron &#65533; double knitted and in Dacron / cotton blends and also with processing temperatures above 32 [deg.] C.

   These results can also be obtained

  
using a commercial or household washing machine of the top or side loading type in place of the laboratory test washing machine.

EXAMPLE 2

  
In the first formulation of Example 1, the linear sodium dodecylbenzene sulfonate is replaced by the corresponding tridecylbenzene sulfonate in the first case and by Neodol 25-3-S, which is the sodium salt of a sulfated condensation product about 3 moles of ethylene oxide and a higher fatty alcohol having on average 12 to 15 carbon atoms per mole in another case, and the nonionic detergent is replaced by Neodol 25-7 in both cases . When the resulting compositions are tested for high temperature stability and storage stability, as described in Example 1, equally good results are obtained.

   Similarly, when the compositions contain more than 0.5% triethanolamine in place of an equal proportion of water and / or in the presence of 2% sodium sulfate or other water-soluble ionizable salt, separation occurs. components of the liquid detergent. When the liquid detergents of this example are used to wash polyester fabrics of the types mentioned in Example 1, after which the fabrics are soiled and then washed, better removal of lipophilic soils is achieved compared to controls which do not contain no anti-fouling polymer of the type used in the formulations of this example.

   Also, when each of the formulations contains more than 0.5% of triethanolamine and / or 2% of water-soluble ionizable salt such as sodium sulfate, after aging at high temperature or at room temperature for periods of two weeks and three months , respectively, if the separate composition is shaken to disperse its various components and then used in the manner previously described, its anti-fouling effect is still considerably reduced, compared to the experimental formulations containing neither triethanolamine nor salt.

  
EXAMPLE 3

  
The first formulation of the invention given in Example 1 is modified by replacing its anionic detergent with Neodol 25-7, so that the product contains

  
39% non-ionic detergent and replacing ethanol with deionized water. The product does not undergo separation during storage and has dirt removal characteristics similar to those of the products of the invention of Examples 1 and 2. Also, the experimental product is stable during accelerated aging at elevated temperature and during longer storage periods at room temperature, while a comparison product containing 1% triethanolamine and / or 2% sodium sulfate undergoes separation. Similarly, these comparison products do not facilitate the removal of deposited lipophilic soiling, to the same degree as that obtained with the experimental products of this example.

  
EXAMPLE 4

  
When varying the various experimental formulations of the present invention, shown in Examples 1 to 3, t 10% and &#65533; 25%, while maintaining the proportions of the various materials within the ranges indicated in the description and when, in these formulations, instead of using the anti-fouling polymer QCF (aqueous solution), 2% of QCF is substituted for it
(Alkaril Chemicals CAS 9016-88-0) and 12.3% water, by first dissolving QCF in water, a good anti-fouling effect is obtained, analogous to those described in Examples 1-3 , and the products are stable and do not separate during shopping. This is also the case when the fluorescent dye, the simple dye and the perfume are removed from the formulations of this example.

   Similarly, when these formulations contain triethanolamine or an ionizable salt outside the limits indicated, the product becomes less stable and less effective in promoting the elimination of soiling during washing.

  
According to other variants of this example, the nonionic detergent is a mixture of equal parts of Neodol 25-7 and Neodol 91-6 and the anionic detergent is Neodol 45-2.25-S. Results identical to those previously indicated in Examples 1-3 are obtained both in experimental washing machines and in actual laundering, using a commercial or domestic washing machine with top or side loading.

  
This is also the case when the pH adjustments are made with potassium hydroxide and when these adjustments, made with sodium hydroxide or potassium hydroxide, give pH values of

  
7.0, 6.6 and 7.4. Normally, these pH adjustments use less than 1% of sodium hydroxide solution, preferably less than 0.5% of such a solution, and more preferably less than 0.2%. In some cases, sodium hydroxide can be added as a constituent of the formulation in said proportion as is known to obtain the desired pH (based on past experience with the formulation), but it is still preferable to l 'add before perfume, although this is not necessary. Similarly, although a concentration of 20% sodium hydroxide solution may often be preferred, other concentrations may also be used.

  
EXAMPLE 5

  

  <EMI ID = 17.1>


  
1. Condensation product of about 7 moles of ethylene oxide and a higher fatty alcohol having on average 12 to 15 carbon atoms per mole.

  
2. Sodium salt of the sulfuric acid ester of

  
nonionic condensation product of higher fatty alcohol having on average 14 to 15 carbon atoms with 2.25 moles of ethylene oxide.

  
3. Proteolytic enzyme, sold by Novo Industri,

  
A / S (5% active ingredient of the enzyme type,

  
65% propylene glycol and 30% water)

  
4. Amylolytic enzyme sold by Novo Industri,

  
A / S (5% enzyme as active ingredient, 65% propylene glycol and 30% water)

  
5. Fluorescent brightening agent of the stilbene type

  
sold by CIBA-Geigy

  
The liquid detergent of the formulation is prepared in the same manner as in Example 1, by mixing together part of the water with the anionic and nonionic detergents, then adding the anti-fouling polymer, ethanol, l fluorescent brightener (sometimes dissolved in ethanol or ethanol-water solutions), enzymes, sodium formate (dissolved in a little water), the dye, and the rest of the water. Then, it is possible, if desired, to use an acid or a base (NaOH is preferred) to adjust the pH in the desired range, for example to 7. When

  
the pH is lower than the desired value, an aqueous solution of sodium hydroxide (20%) is used to raise it to the desired value. The proportion of NaOH used

  
is low, for example about 0.2% or less. Then the proportion of fragrance of the formulation is added. The product obtained is tested by storage at 43.3 [deg.] C for one week, after which it is found that it is a clear light blue liquid in a single stable phase, essentially analogous to that which the we had obtained during the preparation. Protease activity is better than that of a control liquid detergent containing 7% sodium dodecylbenzene sulfonate, 2.8% triethanolamine (TEA) and no alcohol ether sulfate, and much better than other compositions analogous to the control but not containing sodium formate in one case and - no TEA in the other. When we remove both formate and TEA from

  
the control formulation (in all cases, the differences are compensated for by water), the protease and amylase activities are considerably reduced. The control and the first two variants are unstable during storage, the polymer separating.

  
Shortly after its manufacture, the liquid detergent is used to wash a test load of clean fabrics, comprising, for one part, polyesters and, for the other, a material of 65% polyester and 35% cotton. The washing conditions are the same as in Example 1, and the results are very similar, except for the additional enzymatic cleaning action. These advantageous activities are obtained despite the presence in

  
the liquid of sodium formate and all other salts.

  
When the liquid detergent in the formulation

  
  <EMI ID = 18.1>

  
TEA salt, replacing part of its water, after storage for a week at 43.3 [deg.] C, we see that the detergent has separated. Separation also appears in the absence of triethanolamine and in the presence of. 5% sodium sulfate in the formulation. Shopping

  
at room temperature also results in a separation and a corresponding decrease in the anti-fouling activity of the formulations containing the indicated proportions of triethanolamine and / or sodium sulfate, compared to the experimental formulation.

  
The tests on the liquid detergent to determine the cleaning power by the enzymatic route are satisfactory, which shows that the proteolytic and amylolytic enzymes are functionally effective in the stable liquid detergent. This is so despite the fact that enzymes are often unstable in liquid detergent systems, especially at high temperatures.

  
EXAMPLE 6

  
In a variant of the formulation of Example 5, when the proportion of Neodol 45-2.25S is increased to 5%, the proportion of ethanol is increased to 7.5%, which is used 0 , 01% of brilliant polar blue dye instead of 0.0025%, and that the brightening agent is replaced by 0.24%: of Tinopal 5BM and 0.1% of Phorwite BHC, we obtain a detergent stable liquid having dirt removal properties, enzymatic efficiency and detergent power similar to those of the composition of Example 5, or even better. The detergent is a clear blue and, in the absence of dye, it can be light in color, so that it can advantageously also be dyed using other dyes.

   Instead of the above-mentioned brightening agent system, equivalent proportions of Tinopal RBS-200, Tinopal 4226 (CIBA-Geigy) or Phorwite RKH (Mobay Chemical Company) and their mixtures can be substituted. In all cases the substantivity of the fluorescent brightening agent is improved due to the presence of higher fatty alcohol ethoxylate sulfate, and unlike other anionic detergents, for example linear sodium dodecylbenzene sulfonate, the fatty alcohol ethoxylate sulfate does not destabilize the anti-fouling polymer agent in the presence of an enzyme and an enzyme stabilizer.

  
EXAMPLE 7

  
The formulation of Example 5 is varied so that it contains 5% of Neodol 25-3S instead of the 3% of Neodol 45-2.25S. The product obtained is stable

  
and clear after storage at high temperature, and the stability of Alcalase and Termamyl are equal to that of the first control mentioned in Example 5. However, when the formulation also contains 2.8% TEA, the product is unstable, the polymer anti-fouling QCJ separating by flocculation after storage at 43 [deg.] C for

  
one week.

  
EXAMPLE 8

  
The contents of the various experimental formulations of the present invention are varied from Examples

  
  <EMI ID = 19.1>

  
of various materials in the ranges indicated in the description. In these formulations, in place of the anti-fouling polymer QCJ (aqueous solution), 2% of QCF (Alkaril Chemicals CAS 9016-88-0) and 11.4% of water are used, the QCF being first of all dissolved in water. Other enzymes, stabilizers, alcohols and dyes can also be used, as described in the description, in the given ranges of proportions. The resulting detergents are clear, stable and do not separate, and they have good anti-fouling, cleaning and brightening properties, such as those described in Examples 5-7. This is also the case when removing the fluorescent dye, the single dye and the scent from the formulations of this example.

   Similarly, when these formulations contain triethanolamine or an ionizable salt beyond the limits indicated and other anionic detergents such as sodium (upper alkyl) benzenesulfonates are substituted for the alcohol ethoxylate sulfate,

  
the product becomes less stable and is less effective in removing dirt during washing, and when sodium formate is removed, 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 is Neodol 23-6.5 or a mixture of equal parts of Neodol 23-6.5 and Neodol 25-7, the total proportions used being the same and an effective stable product is obtained. . Also, the alcohol ethoxylate sulfate can be a mixture of equal parts of Neodol 25-3S and 45-2.25S, and the results obtained are satisfactory. With these modifications, results analogous to those previously given in Examples 5-7 can be obtained in test washing machines and domestic and commercial washing machines, which are top-loading or side-loading. This is also the case when pH adjustments are made with potassium hydroxide and when these adjustments are made.

  
with sodium hydroxide or potassium hydroxide, give pH values of 6.6, 7.4, 7.9 and 8.6. Normally, these pH adjustments use less than 1% sodium hydroxide solution, preferably less than 0.5%,

  
and better still less than 0.2%. In some cases, sodium hydroxide may be added as a component of the formulation in said proportion, as is known, to obtain the desired pH (based on past experience with the formulation), but it it is still preferable that it be added before the fragrance, although this is not

  
not necessary. Similarly, although a concentration of the 20% sodium hydroxide solution may often be preferable, other concentrations may also be used.

  
From Examples 5-8 and the foregoing description, it can be seen that the present invention provides a stable and attractive liquid detergent which contains various components which could be expected to disturb the stability of the final product. However, and this is surprising, a stable product can be obtained with the invention. This product has advantageous anti-soiling properties,

  
decomposition of soiling, fluorescent brightening (in the presence of brightening agent) and detergency. Several of the components of the compositions of the invention have a double effect. For example, alcohol ethoxylate sulfate promotes detergency and helps make substrates (fibers of the laundry) more substantive so that fluorescent brighteners are more effective. Sodium formate, which is an enzyme stabilizer, does not destabilize the anti-fouling agent, as might be expected. The various components of these liquid detergents work together to produce a surprisingly stable, attractive and effective detergent composition.

   Thus, it can be seen that the compositions of the invention represent an unexpected advance in the technique of manufacturing stable products which are preferably of attractive clarity (transparent or translucent), although in some cases opalescent products can be produced. and semi-transparent or voluntarily creamy.

  
EXAMPLE 9

  

  <EMI ID = 20.1>


  
  <EMI ID = 21.1>

  
by Sherex Industries (contains 75% active ingredient, 14% isopropanol and 11% water)

  
The liquid detergent of the formulation is prepared in a manner essentially analogous to that used for Examples 5-8, but comprising the fabric softener and removing the anionic detergent. The product obtained is tested by storage at 43.3 [deg.] C for one week, after which it is noted that it is a clear light blue liquid in a single stable phase, essentially similar to that which had prepared. The protease activity is 70% of that existing at the time of the preparation of the liquid detergent and the amylase activity is 85% of this initial value.

  
Shortly after the manufacture of the liquid detergent, it is used to wash a test load consisting of clean fabrics, part of which is made of polyesters and others made of 65% polyester and 35% cotton material. The washing concentration and other washing conditions are as in Example 5 and the results are essentially the same as well, except that better softening of the fabrics is achieved in this example. Similarly, when the liquid detergent of the formulation indicated above contains 2% or 3% of triethanolamine or TEA salt, replacing part of its water, after two weeks of storage at 43.3 [deg. ]VS,

  
we see that the detergent has separated. A separation also appears under these conditions when the formulation does not contain triethanolamine but contains 5% sodium sulfate. Also, in the presence of triethanol amine, the anti-fouling action of the liquid detergent is markedly reduced. Storage at room temperature also results in such a reduction in the anti-fouling activity of the formulations containing the indicated proportions of triethanolamine and / or sodium sulfate, compared to the experimental formulation. When the amount of anti-fouling polymer is lowered to 0.8% or increased to 2%, the same types of results are obtained as indicated above.

  
Tests on the liquid detergent to determine the fabric softening properties and the enzymatic cleaning power are satisfactory, which shows that the quaternary ammonium halide and the proteolytic and amylolytic enzymes are functionally effective in the liquid detergent stable. he

  
This is so despite the fact that enzymes and quaternary ammonium halides are often unstable in liquid detergent systems, particularly at elevated temperatures. However, by replacing propylene glycol with higher glycols, for example those having 8 to 12 carbon atoms, we notice a separation of the product in two phases. In the particular formulation indicated, the complete replacement of propylene glycol with hexylene glycol also causes phase separation, although hexylene glycol and amylene glycol are considered to be useful glycol components herein type of liquid detergent, if used in smaller amounts and in conjunction with lower glycols such as propylene glycol. Likewise,

  
if di-coco-dimethyl ammonium chloride is replaced by di- (hydrogenated tallow) dimethyl ammonium chloride,

  
the liquid detergent also separates into two phases,

  
in particular in the presence of hexylene glycol (replacing propylene glycol). However, here again, in some cases, di- (hydrogenated tallow) -dimethylammonium chloride can be used in a stable product, reducing the proportion present and mixing it with di-coco-dimethyl ammonium chloride or others. quaternary di- (higher alkyl) - di- (lower alkyl) -ammonium halides of which the higher alkyl groups have 12

  
with 14 carbon atoms and the lower alkyl groups have 1 or 2 carbon atoms. Alternatively, a more hydrophilic quaternary ammonium halide such as di-tallow-dimethylammonium chloride, which has a higher degree of unsaturation, can be successfully used

  
and is therefore more insensitive to electrolytes.

EXAMPLE 10

  
When, in the first formulation of Example 9, the non-ionic detergent is replaced by Neodol
23-6.5, that 0.01% of polar bright blue dye is used instead of 0.0025% and that there is a fluorescent brightening agent of the stilbene type, for example Tinopal RBS-200 , Tinopal 5BM or Tinopal 4226 (all sold by CIBA-Geigy), or Phorwite RKH or Phorwite BBP (sold by Mobay Chemical Co.) in the proportion of 0.1%, a stable and effective product is obtained which acts like that of Example 9, but has less bleaching power due to the presence of the brightening agent, which is stable in the product. The product in this example also has an attractive transparent appearance and is stable during shopping.

  
EXAMPLE 11

  
The proportions of the formulations are varied

  
  <EMI ID = 22.1>

  
while maintaining the proportions of the various materials within the ranges specified in the description. In these formulations, instead of using the anti-fouling polymer QCJ (aqueous solution), it is replaced by 1% of QCF
(Alkaril Chemicals CAS 9016-88-0) and 5.7% water, the QCF being first dissolved in water. It is also possible to use other enzymes, stabilizers, fabric softeners, glycols, alcohols and dyes, as described in the description, in the ranges of proportions indicated. The resulting detergents are clear, stable, do not separate and have good anti-fouling, softening, cleaning and brightening properties, similar to those described in Examples 9 and 10. This is also the case when the fluorescent dye , the simple colorant and the perfume are omitted in the formulations of this example.

   Similarly, when these for-

  
  <EMI ID = 23.1>

  
nisable beyond the limits indicated, the product becomes less stable and less effective in removing dirt during washing, and when the sodium formate and glycol are removed, the effects of the enzyme are lost after only a few days of storage at the elevated temperature of the test.

  
In other variants of this example, the nonionic detergent is a mixture of equal parts of Neodol 23-6.5 and Neodol 25-7, the total proportion being the same. Results analogous to those previously given in Examples 9 and 10 can be obtained in test washing machines and domestic and commercial washing machines, which are top-loading or side-loading. This is also the case when pH adjustments are made with potassium hydroxide and when these adjustments are made with hydroxide.

  
sodium or potassium hydroxide, give pH values of 6.6, 7.4, 7.9 and 8.6.

  
From Examples 9-11 and the preceding examples, as well as the description, it can be seen that the present invention resides in a stable and attractive liquid detergent despite the fact that it contains various components which might be expected. 'They disturb the stability of the final product. However, and this is surprising, a stable product is obtained, which has anti-soiling, softening of fabrics, decomposition of soils and advantageous detergents. Several of the components of the compositions of the invention have a double effect. For example, propylene glycol helps solubilize lipophilic materials in the formulation while at the same time promoting the stabilization of enzymes. Sodium formate, which is an enzyme stabilizer, does not destabilize the anti-fouling agent, as might be expected.

   Although certain quaternary ammonium halides and certain glycols can destabilize liquid detergent formulations such as those of the present invention, this is not the case with the materials of the invention. This is surprising in that the hydrophobic quaternary ammonium halides which normally separate from the solution by flocculation under the effect of the electrolytes are stable in the liquid detergents of the invention. Thus, it can be seen that the compositions of the present invention represent an unexpected advance in the art of making stable liquid detergents.

CLAIMS

  
1.-Liquid detergent for the elimination of soiling, characterized in that it comprises a proportion with detergent action of nonionic detergent or of a mixture of nonionic and anionic detergents, a proportion

  
with soil removal action of an anti-fouling polymer of polyethylene terephthalate and polyoxyethylene terephthalate and an aqueous medium, in which

  
the pH is between 6 and 9, and not containing "more than

  
2% of water-soluble ionizable salt which is not a water-soluble anionic surfactant salt.


    

Claims (1)

2. Liquid detergent according to claim 1, characterized in that the proportion of nonionic detergent or mixture of nonionic and anionic detergents is in the range of 25 to 50%, the proportion of anti-fouling polymer is between 0.5 and 10%, and the anti-fouling polymer is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate having a molecular weight of between approximately 15,000 and 50,000, the polyoxyethylene of polyoxyethylene terephthalate having a molecular weight of between approximately 1,000 and 10,000, the molar ratio of the ethylene terephthalate units with polyoxyethylene terephthalate units in the range of 2: 1 to 6: 1 3.- liquid detergent according to claim 2, characterized in that it comprises 20 to 40% of detergent non-ionic, which is a condensation product of a fatty alcohol higher than 10 to 20 carbon atoms and 3 to 20 moles of ethylene oxide per mole of higher fatty alcohol, 3 to 15% of anionic detergent chosen from a linear (higher alkyl) -benzene-sulfonate in <EMI ID = 24.1> and a pol yethoxyl ate sulfate of higher sodium fatty alcohol in which the higher fatty alcohol contains 10 to 20 carbon atoms and the polyethoxy group contains 3 to 20 ethoxy groups, and 3 to 15% of a lower alkanol of 1 at 3 carbon atoms. 4. Liquid detergent according to claim 3, characterized in that the nonionic detergent is a condensation product of a fatty alcohol greater than 12 to 15 carbon atoms and 6 to 11 moles of ethylene oxide per mole of higher fatty alcohol, the anionic detergent is a linear (higher alkyl) -benzene-sulfonate in which the higher alkyl group contains 12 or 13 carbon atoms, the anti-fouling polymer has a molecular weight of 19,000 to 25,000, the polyoxyethylene of polyoxyethylene terephthalate has a molecular weight of between 3,000 and 4,000, the molar ratio of the ethylene terephthalate units to the polyoxyethylene terephthalate units of the polymer is included between 3: 1 and 4: 1 and the molar ratio of the ethylene oxide units to the phthalic units is between 20: 1 and 30: 1, the lower alkanol is ethanol, the content of water-soluble ionizable salt other that the water-soluble anionic surfactant salt is less than 0.5%, the liquid detergent contains less than 0.2% of triethanolamine and the proportions of nonionic detergent, anionic detergent, anti-fouling polymer, alcohol and water are respectively in the ranges of 25 to 35%, 5 to 10%, 1 to 6%, 5 to 12% and 30 to 60%. 5. A liquid detergent according to claim 4, characterized in that it essentially consists of approximately 32% of nonionic detergent which is a condensation product of a fatty alcohol higher than 12 to 15 carbon atoms and of approximately 7 moles of ethylene oxide per mole of higher fatty alcohol, approximately 7% of sodium dodecylbenzenesulfonate, approximately 2% of anti-fouling polymer having a weight average molecular weight of approximately 22,000, in which the polyoxyethylene of polyoxyethylene terephthalate has a molecular weight of about 3,400, the molar ratio of the ethylene terephthalate units to the polyoxyethylene terephthalate units of the polymer is about 3: 1 and the molar ratio of the ethylene oxide units with phthalic units is approximately 22: 1, approximately 0.2% fluorescent brightening agent, approximately 8% ethanol and approximately 51% water, the pH being about 7.8, this liquid detergent does not contain triethanolamine and the content of water-soluble ionizable salt other than the water-soluble anionic surfactant salt which may be present is less than 0.3%. 6.- A method of manufacturing a liquid detergent for removing dirt, characterized in that it consists in mixing together a proportion with detergent action of a nonionic detergent or of a mixture of nonionic and anionic detergents and an amount of soil removal effect of an anti-fouling polymer of polyethylene terephthalate and polyoxyethylene terephthalate in an aqueous medium and by mixing with this mixture an aqueous neutralizing agent to adjust the pH of the detergent in the range from 6.1 to 7.9, which detergent, after neutralization, does not contain more than 1% of water-soluble ionizable salt other than the water-soluble anionic surfactant salt. 7.- Method according to claim 6, characterized in that the liquid detergent comprises 25 to 35% of a nonionic detergent, which is a condensation product of a fatty alcohol higher than 12 to 15 carbon atoms and 6 to 11 moles of ethylene oxide per mole of higher fatty alcohol, 5 to 10% of anionic detergent which is a linear (higher alkyl) -benzene-sulfonate in which the alkyl group contains 12 or 13 carbon atoms , 1 to 6% of an anti-fouling polymer which has a molecular weight of between 19,000 and 25,000 and in which the polyoxyethylene of polyoxyethylene terephthalate has a molecular weight of between 3,000 and 4,000, the molar ratio of ethylene terephthalate units to the polyoxyethylene terephthalate units of the polymer are between 3: 1 and 4: 1 and the molar ratio of the ethylene oxide units to the phthalic units is between 20: 1 and 30: 1, 5 to 12% of ethanol, 0.1 to 0.5% of fluorescent brightening agent and 30 to 60% of water, the content of water-soluble ionizable salt other than a water-soluble anionic surfactant salt being less than 0.5% and the content of triethanolamine being less than 0.2%, neutralization being carried out with an aqueous solution of sodium hydroxide. 8.- liquid detergent for the removal of dirt, stable, containing enzymes, according to claim 1, characterized in that it comprises a proportion with detergent action of a nonionic detergent, a proportion reinforcing the detergent and increasing the substantivity of the fluorescent brightening agent of a detergent of the higher fatty alcohol polyethoxylate sulfate type, a proportion of soil removal action of a polyethylene terephthalate anti-fouling polymer and polyoxyethylene terephthalate, a proportion of enzyme sufficient to enzymatically hydrolyze protein and / or starchy soils on fabrics during their washing with an aqueous washing solution liquid detergent, a stabilizing proportion of a stabilizer for enzymes, and an aqueous medium, in which the pH is between approximately 6 and 9 and containing not more than 2% of water-soluble ionizable material other than polyethoxylate sulfate higher fatty alcohol detergent. 9. A liquid detergent according to claim 8, characterized in that the proportion of nonionic detergent is between 25 and 40%, the polyethoxylate sulfate of higher fatty alcohol is in the form of a sodium salt and is present at 1 to 8%, the anti-fouling polymer is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate having a molecular weight of about 15,000 to 50,000, in which polyoxyethylene terephthalate polyoxyethylene has a molecular weight of between approximately 1,000 and 10,000, the molar ratio of the ethylene terephthalate units to the polyoxyethylene terephthalate units being between 2: 1 and 6: 1, a proportion of 0.5 to 5% of that -when being present, the enzyme comprises a proteolytic enzyme, and is present in an amount of 0.005 to 0.1%, with the presence from 0.2 to 2% of enzyme stabilizer. 10.- liquid detergent according to claim 9, characterized in that it comprises 28 to 36% of nonionic detergent, which is a condensation product of a fatty alcohol higher than 10 to 20 carbon atoms and -3 to 20 moles of ethylene oxide per mole of higher fatty alcohol, 2 to 7% of polyethoxylate sulfate of higher sodium fatty alcohol in which the higher fatty alcohol has 10 to 20 carbon atoms and the polyethoxylate has 1 to 20 ethoxy groups per mole, 0.02 to 2% of one or more fluorescent brightening agents, 0.01 to 0.1% of proteolytic enzyme, 0.005 to 0.05% of amylolytic enzyme, 0, 5 to 1.5% of enzyme stabilizer and 3 to 12% of a lower alkanol. 11. A liquid detergent according to claim 10 characterized in that the nonionic detergent is a condensation product of a fatty alcohol greater than 12 to 15 carbon atoms and 6 to 11 moles of ethylene oxide per mole of higher fatty alcohol, polyethoxylate of higher fatty alcohol is a compound of the type in which the alcohol contains 10 to 15 carbon atoms and contains 1 to 5 ethoxy groups per mole, the fluorescent brightening agent is a brightening agent of the stilbene type, the anti-fouling polymer has a molecular weight of between 19,000 and 25,000, the polyoxyethylene of polyoxyethylene terephthalate has a molecular weight between 3,000 and 4000, the molar ratio of the ethylene terephthalate units to the polyoxyethylene terephthalate units of the polymer is between 3: 1 and 4: 1 and the molar ratio of the ethylene oxide units to the phthalic units is from 20: 1 to 30: 1, the enzyme stabilizer is sodium formate, the lower alkanol is ethanol, and the proportions of nonionic detergent, higher fatty alcohol polyethoxylate sulfate, fluorescent brightening agent, anti-fouling polymer, proteolytic enzyme, amylolytic enzyme, sodium formate, ethanol and water are in the respective ranges of 30 to 34%, 2 to 6% , 0.1 to 1%, 0.8 to 3%, 0.02 to 0.05%, 0.01 to 0.03%, 0.7 to 1.3%, 4 to 9% and 46 to 62 %. 12.- liquid detergent according to claim 11, characterized in that it is clear and consists essentially- -only in about 32% of a nonionic detergent which is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and about 7 moles of ethylene oxide per mole of higher fatty alcohol, approximately 5% of sodium fatty alcohol polyethoxylate sulfate in which the higher fatty alcohol has 12 to 15 carbon atoms, and the ethoxylate has about 3 moles of ethylene oxide per mole of higher fatty alcohol, about 0.3% of fluorescent brightening agent like stilbene, about 2% anti-fouling polymer with a weight average molecular weight of about 22,000, in which the polyoxyethylene of polyoxyethylene terephthalate has a molecular weight of about 3,400, the molar ratio of the ethylene terephthalate units to polyoxyethylene terephthalate units of the polymer is approximately 3: 1 and the molar ratio of the ethylene oxide units to the phthalic units is approximately 22: 1, approximately 0.03% of proteolytic enzyme, approximately 0, 02% amylolytic enzyme, approximately 1% sodium formate, approximately 5.5% ethanol, approximately 0.4% perfume and approximately 54% deionized water. 13.- Liquid detergent containing enzymes, stable, softening the tissues, with the effect of removing dirt, according to claim 1, characterized in that it comprises a proportion of detergent action of a nonionic detergent, a proportion of action for removing dirt from an anti-fouling polymer of polyethylene terephthalate and polyoxyethylene terephthalate, a proportion of fabric softening effect of a fabric softener for quaternary ammonium halide type, a proportion of enzyme sufficient to enzymatically hydrolyze protein and / or starchy soils on fabrics during their washing with an aqueous washing solution of liquid detergent, a stabilizing proportion of an enzyme stabilizer,  and an aqueous medium in which the pH is between approximately 6 and 9 and containing not more than 2% of water-soluble ionizable material. 14.- liquid detergent according to claim 13, characterized in that the proportion of nonionic detergent is between 10 and 35%, the anti-fouling polymer is a polymer of polyethylene terephthalate and polyoxyethylene terephthalate having a molecular weight of between approximately 15,000 and 50,000, wherein the polyoxyethylene of polyoxyethylene terephthalate has a molecular weight of about 1,000 to 10,000, the molar ratio of the ethylene terephthalate units to the polyoxyethylene terephthalate units being between 2: 1 and 6: 1, and is present in a proportion of 0.5 to 5%, the quaternary ammonium halide is a di (higher alkyl) -dimethylammonium halide and is present in a proportion of 1 to 10%, the enzyme comprises a proteolytic enzyme, and is present in a proportion of 0.005 to 0.1%, with the presence of 0.2 to 2% of the stabilizer for the enzyme. 15.- liquid detergent according to claim 14, characterized in that it comprises 15 to 30% of nonionic detergent, which is a condensation product of a fatty alcohol higher than 10 to 20 carbon atoms and 3 to 20 moles of ethylene oxide per mole of higher fatty alcohol, 3 to 8% of quaternary ammonium halide, which is a chloride, and in which the higher alkyl groups have 12 to 18 carbon atoms, 0.005 to 0.05% of proteolytic enzyme, 0.005 to 0.05% of amylolytic enzyme, 0.5 to 1.5% of a stabilizer for enzymes and 1 to 10% of a lower alkanol. 16.- liquid detergent according to claim 15, characterized in that the nonionic detergent is a condensation product of higher fatty alcohol with 12 to 15 carbon atoms and 6 to 11 moles of ethylene oxide per mole d higher fatty alcohol, the anti-fouling polymer has a molecular weight of between 19,000 and 25,000, the polyoxyethylene of polyoxyethylene terephthalate has a molecular weight between 3,000 and 4,000, the molar ratio of the ethylene terephthalate units to the polyoxyethylene terephthalate units of the polymer is between 3: 1 and 4: 1 and the molar ratio of the oxide oxide units ethylene with phthalic units is 20: 1 to 30: 1, the quaternary ammonium halide is di-coco-dimethyl ammonium chloride, the enzyme stabilizer is sodium formate, the lower alkanol is ethanol, with the presence of 2 to 8% of propylene glycol, and the proportions of non-ionic detergent, anti-fouling polymer, fabric softener, proteolytic enzyme, amylolytic enzyme, sodium formate, ethanol, propylene glycol and water being respectively between 20 and 25%, 0.8 and 1.5%, 3 and 6%, 0.015 and 0.03%, 0.01 and 0.025%, 0.7 and 1.3%, 1.5 and 3%, 3 and 8% and 50 and 70%. 17. A liquid detergent according to claim 16, characterized in that it is clear and essentially consists of approximately 22% of a nonionic detergent which is a condensation product of a fatty alcohol higher than 12 to 15 carbon atoms and about 7 moles of ethylene oxide per mole of higher fatty alcohol, about 1% of anti-fouling polymer having a weight average molecular weight of about 22,000, wherein the polyoxyethylene terephthalate has a molecular weight of about 3,400, the molar ratio of the ethylene terephthalate units to the polyoxyethylene terephthalate units of the polymer is approximately 3: 1 and the molar ratio of the ethylene oxide units to the phthalic units is about 22: 1, approximately 4.5% di-cocodimethyl ammonium chloride, approximately 0.023% proteolytic enzyme, approximately 0.015% amylolytic enzyme, approximately 1% sodium formate, approximately 2% ethanol, approximately 6% of propylene glycol, about 0.4% of perfume and about 63% of deionized water.