BE1001835A4 - LIQUID DETERGENT COMPOSITIONS NOT AQUEUESES NONIONIC persalt AS CONTAINING BLEACH AND METHODS OF USE FOR CLEANING TISSUE SALIS. - Google Patents

Abstract

Detergent composition for cleaning soiled fabrics whose whitening action is improved. The composition contains a mineral persalt, in particular a perborate, as a bleaching agent, and calcium cyanamide as an activator for the bleaching agent. The preferred compositions are nonaqueous liquids based on liquid nonionic surfactant and comprise a detergency builder salt suspended in the liquid nonionic surfactant. The bleaching action of these compositions is improved at low temperatures without the activator having an adverse effect on the detergency.

Description

       

    <Desc / Clms Page number 1>
 



    NON-IONIC AND NON-AQUEOUS LIQUID DETERGENT COMPOSITIONS CONTAINING PERSON AS A WHITENING AGENT AND METHODS OF USING SAME FOR CLEANING
SALIS FABRICS
The present invention relates to non-aqueous liquid compositions for the treatment of fabrics: The invention relates more particularly to non-ionic liquid detergent compositions for washing clothes, which contain, as a bleaching agent, a mineral persalt and, as an activator of the bleaching agent, calcium cyanamide, i.e. calcium cyanamide. The compositions are stable against phase separation and gelation and are capable of being easily poured. The compositions are used for cleaning soiled fabrics.



   Non-aqueous liquid detergent compositions for heavy laundry work are well known in the art. For example, compositions of this type can comprise a liquid nonionic surfactant in which are dispersed particles of a detergency builder, as is known for example from the patents of the United States of America NOs 4 316 812.3 630 929 and 4,264,466 and British patents NOs 1,205,711, 1,270,040 and 1,600,981.



   The Applicant's related French patent applications are as follows:

  <Desc / Clms Page number 2>

 
86 044 68 deposited on March 27, 1986, describes a non-ionic liquid detergent composition for washing clothes, containing a perborate as a bleaching agent, a bleaching agent activator and hydroxylamine sulfate as a bleaching agent stabilizer and, in particular as a catalase inhibitor,
85 048 31 deposited on March 29, 1985, describes a non-aqueous liquid detergent composition based on nonionic surfactant, comprising a suspension of a detergency builder salt and containing a nonionic acid-terminated surfactant (for example the reaction product of '' a nonionic surfactant and succinic anhydride)

   to improve the dispersibility of the composition in an automatic washing machine.



   85 19 510 deposited on December 31, 1985, described, a non-aqueous liquid detergent composition based on nonionic surfactant, comprising a suspension of an adjuvant detergency salt and containing a monoalkyl ether of alkylene-g1yco1 as a viscosity control agent and anti-gelation, in order to improve the dispersibility of the composition in an automatic washing machine.



   85 05 319 filed April 9, 1985, describes a nonaqueous liquid detergent composition based on nonionic surfactant, comprising a suspension of a detergency builder salt of polyphosphate type and containing an alkanolic ester of phosphoric acid to improve the stability of suspension against sedimentation during storage.



   These applications relate to non-aqueous non-ionic liquid detergent compositions for washing clothes.



   Liquid detergents are often considered more convenient to use than dry products

  <Desc / Clms Page number 3>

 in powder or particles and consumers have therefore given them great preference. They are easy to dose; dissolve quickly in washing water and can be easily applied in concentrated solutions or dispersions on soiled areas of clothing to be washed, and they do not generate dust and usually take up less storage space:

   In addition, it is possible to incorporate into the formulation of liquid detergents materials which cannot withstand drying operations without degradation, materials which it would often be desirable to use in the manufacture of particulate detergent products. Although they have many advantages over solid products in particulate or discrete units, liquid detergents are also often affected by certain inherent disadvantages which must be overcome in order to obtain commercially acceptable detergents. Thus, some of these products separate on storage and others separate on cooling and are not easy to redisperse.

   In some cases, the viscosity of the product changes and it becomes either too thick to be poured, or fluid enough to resemble water.



  Some clear products cloud and others gel on standing.



   The Applicant has been interested in studying the behavior of nonionic liquid surfactant systems containing a particulate matter in suspension. Particular attention was paid to non-aqueous liquid detergent compositions for washing clothes containing a detergency builder and to the problem of sedimentation of the detergency builder and other laundry washing additives in suspension, as well as gelation problem which

  <Desc / Clms Page number 4>

 is associated with non-ionic surfactants. These considerations have an impact, for example, on the stability and dispersibility of the products and their suitability for pouring.



   It is known that one of the major problems encountered with liquid detergents for washing laundry containing detergency builders is that of their physical stability. This problem arises from the fact that the density of the solid particles dispersed in the nonionic liquid surfactant is greater than the density of the liquid surfactant.



   Consequently. dispersed particles tend to settle. Two basic solutions exist to solve the sedimentation problem: increase the viscosity of the nonionic liquid surfactant and reduce the size of the dispersed solid particles.



   It is known that suspensions can be stabilized against sedimentation by the addition of thickeners or mineral or organic dispersants.
 EMI4.1
 ques, such as for example mineral materials ä. very large specific surface, such as finely divided silica, clays, etc., organic thickeners such as cellulose ethers, acrylic polymers and acrylamide polymers, polydlectrolytes, etc. However, such increases in viscosity of the suspensions are naturally limited by the need for the liquid suspension to be easy to pour and to flow easily, even at low temperatures. In addition, these additives do not contribute to the cleaning action of the composition.



   Grinding to reduce the particle size offers the following advantages:
1. The specific surface of dispersed particles increases and, consequently, the wetting of

  <Desc / Clms Page number 5>

 particles by the nonaqueous vehicle (liquid nonionic surfactant) is proportionally improved.



   2. The average distance between dispersed particles is reduced with a proportional increase in the interaction between particles. Each of these effects contributes to increasing the resistance to gelling at rest and the flow limit of the suspension while, at the same time, grinding significantly reduces the plastic viscosity.



   The flow limit is defined as the minimum stress necessary to induce plastic deformation (collapse) of the suspension.



  Thus, by representing the suspension as a loose network of dispersed particles, if the applied stress is lower than the flow limit, the suspension behaves like an elastic gel and no plastic flow occurs. As soon as the flow limit is exceeded, the network breaks at certain points and the sample begins to flow, but with a very high apparent viscosity. If the shear stress is sufficiently greater than the limit of the flow, the particles are partially deflected by shear and the apparent viscosity decreases.

   Finally, if the shear stress is very much higher than the flow limit, the dispersed particles are totally deflocculated by shearing and the apparent viscosity is very low as if there were no interaction between the particles.



   Consequently, the higher the flow limit of the suspension, the higher the viscosity apparent at a low shear rate and the better the physical stability against sedimentation of the product.



   Besides the problems posed by sedimentation

  <Desc / Clms Page number 6>

 or phase separation, non-aqueous liquid detergents for laundry based on liquid non-ionic surfactants have the disadvantage that. Nonionic surfactants tend to gel when added to cold water. This is a problem which is of particularly great importance in the current use of automatic household washing machines of European type where the user places the detergent composition for washing clothes in a dispensing device (for example a dispensing drawer). the machine.

   During the operation of the machine, the detergent contained in the dispenser is subjected to a stream of cold water to be transferred into the main body of the washing solution. It occurs especially during. month
 EMI6.1
 in winter, when the detergent composition and the water supplying the dispenser are particularly cold, the viscosity of the detergent increases sharply and a build-up takes place. As a result, part of the composition does not is not expelled from the dispenser during operation of the machine, and that a deposit of composition accumulates during repeated washing cycles, which ultimately forces the user to sweep the dispenser with hot water.



   The gelation phenomenon can also be a problem every time you want to wash using cold water, as may be recommended for certain synthetic and delicate fabrics or for certain fabrics which may shrink in warm water or hot.



   . The tendency of concentrated detergent compositions to gel in storage is compounded by storage of the compositions in unheated storage rooms, or by

  <Desc / Clms Page number 7>

 transport of the compositions during the winter months in unheated transport vehicles.



   Partial solutions to the problem of gelation of aqueous compositions substantially
 EMI7.1
 free of detergent additives have been proposed, and consist for example of a dilution of the nonionic surfactant liquid with certain solvents regulating the viscosity and certain agents inhibiting the gelification, such as lower alkanols, for example ethyl alcohol (see US Patent 3,953,380), alkali metal formates and adipates
 EMI7.2
 lin (see US Patent No. 4,368,147), hexylene glycol, polyethylene glycol, etc., and modification and optimization of the structure of the nonionic surfactant.

   As an example of modification of the nonionic surfactant, a particularly happy result was obtained by acidifying the terminal group of the hydroxy fragment of the nonionic mold. The benefits of introducing a carboxylic acid to the end of the nonionic molecule include inhibiting freezing at dilution, lowering the dropping point of the nonionic surfactant and forming an anionic surfactant by neutralization in the washing liquor. Optimization of the nonionic structure related to the chain length of the hydrophobic-lipophilic fragment and to the number and the constitution of the alkylene oxide units (for example ethylene oxide) of the hydrophilic fragment.

   For example, it has been found that a fatty alcohol Cl3 ethoxylated with 8 moles of ethylene oxide shows only a tendency
 EMI7.3
 limited to gel formation.



  It is desirable to improve the bleaching properties and the stability and inhibition of gelation of non-aqueous liquid compositions

  <Desc / Clms Page number 8>

 for treating laundry containing a bleaching agent and a bleaching agent activator.



   According to the present invention, a non-aqueous, stable and highly concentrated liquid detergent composition is prepared for washing clothes, containing a persalt as a bleaching agent and calcium cyanamide calcium cyanamide as a bleaching agent activator. A preferred parsley as a bleaching agent is sodium perborate monohydrate.



   Calcium cyanamide, which is the bleach activator, is used to replace commonly used organic bleach activators such as tetraacethyl ethylene diamine (TAED), which release an acid detrimental to detergent action.



  Calcium cyanamide acts as an activator against the bleaching parsley, it increases the alkalinity of the aqueous washing liquor and it improves the detergency.



   The system of bleaching parsley and calcium cyanamide (bleach activator) of the present invention can be used in compositions containing phosphate-type detergency builder salts with a low phosphate content.



   In order to improve the viscosity characteristics of the composition, an acid-terminated nonionic surfactant can be added. To further improve the viscosity characteristics of the composition and its storage properties during storage, it is possible to add to the composition viscosity-enhancing and anti-freezing agents such as monoalkylene glycol ethers and an anti-sedimentation agent such as an alkanolic ester of phosphoric acid.

   In a preferred form of rea-

  <Desc / Clms Page number 9>

 
 EMI9.1
 In accordance with the invention, the detergent composition contains sodium perborate monohydrate as a bleaching agent, calcium cyanamide. as a bleach activator, an acid-terminated nonionic surfactant, a monoalkyl ether
 EMI9.2
 alkylene glycol and an alkanolic ester of phosphoric acid as an anti-freezing stabilizing agent.



   The peroxygen bleaching compounds commonly used, for example perborate, percarbonate, perphosphate and sodium persulfate, can be used as a bleaching agent.



   In one embodiment of the invention, the detergency builder components of the composition can be ground to a particle size of less than 100 micrometers, for example less than 40 micrometers and preferably less than 10 micrometers to improve still the stability of the suspension of the detergency builder components in the liquid nonionic detergent surfactant.



   In addition, other ingredients can be added to the composition, such as anti-fouling agents, sequestering agents, anti-foaming agents, optical brighteners, enzymes, anti-deposition agents, perfume and colorants.



   Therefore, in one of its aspects, the present invention provides a liquid composition for heavy laundry work, consisting of a suspension of a peroxy bleaching compound.
 EMI9.3
 gene and a detergency builder salt, for example a phosphate-type detergency builder, in a liquid nonionic surfactant, the composition containing as bleach activator an effective amount of calcium cyanamide.



   In another aspect, the invention provides a

  <Desc / Clms Page number 10>

 concentrated liquid detergent composition for heavy laundry work, which has good bleaching properties at low temperature, which is stable, does not settle during storage and does not gel
 EMI10.1
 not for storage and use. The liquid compositions of the present invention are easy to pour, easy to dose and easy to put in the washing machine, and are easily dispersed in water.



   In another aspect, the invention provides a method for dispensing a non-ionic liquid laundry detergent composition, into and / or with cold water without gelation occurring. In particular; a method is provided for filling a container with a non-aqueous liquid detergent composition for washing laundry in the
 EMI10.2
 which detergent is composed, at least predominantly, of a liquid nonionic surfactant, and for dispensing the composition by passing it from the container into an aqueous washing bath, process in which the dispensing is carried out by directing a stream of unheated water on the composition such that the composition is entrained by the stream of water into the washing bath.



   The use of calcium cyanamide as. bleach activator in the composition in place of the commonly used organic bleach activators, such as TAED, provides good bleaching properties at low temperatures while increasing the alkalinity of the aqueous wash liquor, and increases the detergent power. composition.



   The concentrated non-aqueous liquid detergent compositions based on non-ionic surfactant for washing clothes according to the present invention have the advantages of being stable, of not being

  <Desc / Clms Page number 11>

 get sedimented during storage and not gel during storage. The liquid compositions are easy to pour, easy to dose and easy to introduce into washing machines and are easily dispersed in water.



   An object of the present invention is to provide a stable non-aqueous liquid nonionic detergent composition for heavy work, containing a persalt as a bleaching agent and calcium cyanamide as a bleaching agent activator, at least one regulating agent for the viscosity and antifreezing, an anti-sedimentation stabilizing agent and an anionic detergency builder salt of the phosphate type suspended in a nonionic surfactant.



   Another object of the invention is to provide liquid compositions for treating fabrics, which have good detergent properties at low temperature, better detergent power, and which are suspensions of mineral particles insoluble in a nonaqueous liquid and are stable during storage, easy to pour and disperse in cold water,
 EMI11.1
 warm or hot.



  Another object of the invention is to formulate non-aqueous liquid detergent compositions based on non-ionic surfactant with a high content of detergency builders for heavy laundry work, which can be poured at any temperature and which can be dispersed at repeatedly from the dispenser device of automatic washing machines of the European type without clogging or obstructing the dispenser even during the winter months.



   A particular object of the present invention is to provide non-aqueous nonionic liquid detergent compositions containing a detergent builder

  <Desc / Clms Page number 12>

 Tergence for large laundry washing work in the form of stable and non-gelling suspensions which contain parsley as a bleaching agent and an effective amount of calcium cyanamide as a bleaching agent activator.



   These and other objects of the invention will emerge better from the following detailed description of its preferred embodiments and are generally achieved by preparing a detergent composition comprising a non-aqueous liquid nonionic surfactant, a persalt such as bleaching agent and a calcium cyanamide as bleaching agent activator, said composition comprising mineral or organic tissue treatment additives, for example viscosity improving agents and one or more antifreeze agents, anti-fouling agents, regulation agents pH, agents
 EMI12.1
 defoamer, optical brighteners, enzymes, anti-deposition agents, perfume and colorants.



  , Bleaching Persels The nonaqueous liquid nonionic detergent compositions for washing clothes of the present invention contain, as essential ingredients of the composition, a persalt as a bleaching agent and calcium cyanamide as an activating agent whitening.



   Whitening persalts are well known in the art; they are dispersed as solids in the nonionic surfactant and they are easily soluble at the time of the addition of the detergent composition to the aqueous washing bath. Persalts, or oxygenated bleaches, are per-compounds that release hydrogen peroxide in aqueous solution. Preferred examples include perborates, percarbonates, sodium and potassium perphosphates,

  <Desc / Clms Page number 13>

 and potassium monopersulfate. Perborates, especially sodium perborate monohydrate, are particularly preferred.



   Hydrogen peroxide and its precursors which release hydrogen peroxide are good oxidizing agents for the removal of stains from clothing, in particular stains from wine, tea, coffee, cocoa, fruit, etc. It has generally been observed that hydrogen peroxide and its precursors exert a
 EMI13.1
 rapid and more effective whitening action at a relatively high temperature, for example around 800 to 100 ° C.



   In order to take advantage of effective low temperature detergents and low temperature wash cycles which are now commonly used for temperature sensitive fabrics, parsley or peroxygen bleach is used in admixture with an activator whitening.



   Until now, organic bleach activators have been used, such as tetraacethyl ethylene diamine (TAED). The use of such organic bleach activators increases the acidity of the aqueous wash liquor and therefore adversely affects the detergent action of the composition.



   Cyanamide-calcium is used as an activator for bleaching persalts. The calcium cyanamide reacts in the aqueous washing liquor with the hydrogen peroxide generated by the bleaching persalt, producing a fragment with bleaching activity at low temperature.



   . The calcium of the calcium cyanamide contained in the aqueous washing liquor increases the alkalinity of the washing liquor and improves the detergent power of the detergent composition. The addition of cyan

  <Desc / Clms Page number 14>

 Amide calcium as a bleach activator to the detergent composition can lower the effective action temperature of bleaching peroxides to values as low as about 60 C.



  In detergent compositions for which lower working temperatures are desired, small amounts of commonly used bleach activators such as TAED can be added. In the preferred embodiment of the invention, calcium cyanamide is the only activator of bleaching agent "or the major constituent, that is to say that it represents more than 50%, of the activator d 'ëg: nt of total chemistry used in the detergent composition.



   Only small amounts of calcium cyanamide are needed as a bleach activator to activate the peroxygen bleach compound. For example, based on the total weight of the nonionic liquid surfactant composition, suitable proportions of calcium cyanamide are in the range of about 1 to about 15%, preferably about 1 to about 8%, and better
 EMI14.1
 still about 2 to 6%.



   The bleach activator usually interacts with the peroxygen compound to form a bleaching peroxyacid in the wash water. It is preferable to incorporate a sequestering agent of high complexing power to inhibit any undesirable reaction between this peroxyacid and hydrogen peroxide in the washing solution in the presence of metal ions.



   Suitable sequestering agents for this purpose include sodium salts of nitrilotriaceous acid.
 EMI14.2
 tick (NTA), ethylenediantinetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid

  <Desc / Clms Page number 15>

 (DEPTA), diethylenetriaminepentamethylenephosphonic acid (DTPMP) sold under the trademark Dequest 2066, and ethylenediaminetetramethyrenephosphonic acid (EDITEMPA). The sequestering agents can be used alone or as a mixture.



   In order to avoid loss of the bleaching perxide, for example sodium perborate, as a result of an enzymatic decomposition, for example under the effect of a catalase type enzyme, the compositions may additionally contain an enzyme inhibitor compound, that is, a compound capable of inhibiting the enzymatic decomposition of bleaching peroxide. Appropriate inhibitors are described in U.S. Patent No. 3,606,990.



   As specially integrated inhibitor compounds
 EMI15.1
 In particular, 011 may mention hydroxylamine sulfate and other water-soluble hydroxylamine salts.



  In the preferred nonaqueous compositions of the present invention, suitable proportions of inhibitory hydroxylamine salts may be as low as about 0.01-0.47. In general, however, suitable proportions of enzyme inhibitors are up to about 15%, for example from 0.1 to 10%, based on the weight of the composition.



   It is also possible to add stabilizers to the composition, such as for example an organic phosphorus acid compound comprising an acid group -POH, such as a partial ester of phosphorous acid and an alkanol.



   Non-ionic detergent surfactants can be reinforced with detergent build-up salts — fully polyphosphate type or low polyphosphate content.



   SurfactantNonIonicDetergent
Non-synthetic organic detergents

  <Desc / Clms Page number 16>

 Ionic used in the practice of the invention can be any of a wide variety of known compounds.



   As is well known, non-ionic synthetic organic detergents are characterized by the presence of a hydrophobic organic group and a hydrophilic organic group and they are typically produced by the condensation of an aliphatic or alkyl-aromatic hydrophobic organic compound with ethylene oxide (hydrophilic in nature). Almost any hydrophobic compound carrying a carboxy, hydroxy, amido or amino group with a labile hydrogen atom attached to nitrogen can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to form a nonionic detergent. The length of the polyoxyethylene hydrophilic chain can be easily adjusted to achieve the desired ratio between the hydrophobic and hydrophilic groups.

   Typical suitable nonionic surfactants are those described in the U.S. Patents? 4,316,812 and 3,630,929.



   Generally, nonionic detergents are lipohilic compounds polyalkoxylated by lower alkoxy groups, in which the hydrophilic ratio
 EMI16.1
 the desired lipophilic is obtained by adding a hydrophilic poly (lower alkoxy) group to a lipophilic moiety. A preferred class of the nonionic detergent used is that of the higher alkanols polyalkoxylated by lower alkoxy groups or the alkanol has from 9 to 18 carbon atoms and where the name—
 EMI16.2
 number of moles of lower alkyl oxide (with 2 or 3 carbon atoms) is 3 to 12.

   Among these materials, it is preferable to use those of which higher alkanol is a fatty alcohol higher than 9 to 11 or 12 to 15 carbon atoms and which contain 5 to 8

  <Desc / Clms Page number 17>

 or 5 to 9 lower alkoxy groups per mole. Preferably, the lower alkoxy group is the ethoxy group but, in certain cases, it can be advantageously mixed with the propoxy group which, if it is present, often only constitutes a minor proportion (less than 50%).



   Representative examples of such compounds are those in which the alkanol has from 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per molecule, for example Neodol 25-7 and Neodol 23-6. 5 which are products manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide , and the second is a corresponding mixture where the number of carbon atoms in the higher fatty alcohol is 12 to 13 and the number of methylene oxide groups present is on average about 6.5. The higher alcohols are primary alkanols.



   Other examples of such detergents include Tergitol 15-S-7 and Tergitol-15-S-9 which are both secondary linear alcohol ethoxylates manufactured by Union Carbide Corp. The first is the mixed ethoxylation product of a secondary linear alkanol of 11 to 15 carbon atoms with seven moles of ethylene oxide and the second is a similar product but where nine moles of ethylene oxide reacted .



   Higher molecular weight nonionic surfactants are also useful in the present invention as a component of a nonionic detergent, such as Neodol 45-11, which are similar products of condensation of ethylene oxide on higher fatty alcohols. higher fatty alcohol with 14 to 15 carbon atoms and the number of groups

  <Desc / Clms Page number 18>

 ethylene oxide being approximately 11 per molecule.



  These products are also manufactured by Shell Chemical Company.



   Other useful nonionic surfactants are represented by the class of commercially known nonionic surfactants which are sold under the trademark Plurafac. Plurafac series surfactants are the reaction products of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, finished by a hydroxyl group. Examples are the products (A) a C13-C15 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide, (B) a C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, (C) a fatty alcohol in C - e condenses with 5 moles of propylene oxide and 10 moles of ethylene oxide, and.

   (D) an equal mixture of products (B) and (C).



   Another class of liquid nonionic surfactants is commercially available from Shell Chemical Company, Inc. under the trademark Dobanol: Dobanol 91-5 is a fatty alcohol
 EMI18.1
 in C9 - Cl I ethoxylG with an average of 5 moles of ethylene oxide and Dobanol 25-7 is a fatty alcohol in C-, - This ethoxyl with an average of 7 moles of ethylene oxide, per mole of 'fatty alcohol' ..



   In preferred alkanols polyalkoxylated with preferred lower alkoxy groups, to obtain the best ratio between hydrophilic and lipophilic moieties, the number of lower alkoxy groups is usually 40% to 100% of the number of carbon atoms present in the alcohol higher, preferably 40 to 60% of this number, and the nonionic detergent preferably contains at least 50% of this al-

  <Desc / Clms Page number 19>

 preferred polyalkoxylated upper canol. Higher molecular weight alkanols and various other normally solid detergents and surfactants may contribute to the gelation of the liquid detergent and, therefore,

   they are preferably omitted or incorporated in limited quantities in the present compositions, although minor proportions can be used for their cleaning properties, etc. With respect to both preferred and less preferred nonionic detergents, the alkyl groups present therein are generally linear although a low degree of tree structure can be tolerated, for example at the carbon atom level contiguous with the terminal carbon atom, or distant from two positions of the terminal carbon atom,
 EMI19.1
 of the straight chain and opposite of the ethoxy chain, provided that the length of this alkyl branch does not exceed three carbon atoms.

   Normally, the proportion of carbon atoms in such a branched configuration should be minor and rarely exceed 20% of the total number of carbon atoms in the alkyl group. Likewise, although the linear alkyl groups which are joined by the terminal carbon atom to the ethylene oxide chains are greatly preferred and are considered to give the best combination of detergency, biodegradability and non-gelling characteristics , it can appear in the chain a median junction or se-
 EMI19.2
 conditional on ethylene oxide. There is normally only a minor proportion of such alkyl groups, generally less than 20%, but this proportion can be greater, as is the case with the mentioned Tergitols.

   In addition, when the propylene oxide is present in the lower alkylene oxide chain, it generally constitutes less than 20% and preferably less than 10%.

  <Desc / Clms Page number 20>

 



   If larger proportions than alkanols whose alkoxylation is not terminal are used, as mentioned above, of alkanols polyalkoxylated by lower alkoxy groups containing propylene oxide and nonionic detergent at lower cost hydrophilic-lipophilic, and if other non-ionic detergents are used in place of the super
 EMI20.1
 preferred nonionic materials listed here, the resulting product may not have as good detergency, stability, viscosity and gel-forming properties as the preferred compositions, but the use of viscosity regulating and anti-gelation compounds. the invention can also improve the properties of detergent products based on such nonionic surfactants.

   In some cases, for example when a higher molecular weight polyalkoxylated higher alkanol is used, often for its detergency, its proportion can be adjusted or limited according to the results of routine tests to obtain the desired detergency while the product still remains non-gelling and of desired viscosity. It has moreover been found that it is only rarely necessary to make use of non-ionic surfactants of higher molecular weight for their detergent properties since the preferred nonionic surfactants described here are excellent detergents and also allow to achieve the desired viscosity of the liquid detergent product without freezing at low temperatures.



   Another class of non-ionic surfactants is the series of "Surfactant T" products available from the company British Petroleum. The non-ionic surfactants Surfactant T are obtained by ethoxylation of secondary fatty alcohols in Cl3 with a narrow distribution of ethylene oxide contents.

  <Desc / Clms Page number 21>

 lene. Surfactant T5 contains on average 5 moles of ethylene oxide; Surfactant T7 contains on average 7 moles of ethylene oxide; Surfactant T9 contains an average of 9 moles of ethylene oxide and Surfactant T12 contains an average of 12 moles of ethylene oxide per mole of C-o secondary fatty alcohol.



   In the compositions of the present invention, the preferred conventional nonionic surfactants include
 EMI21.1
 take the secondary C'Ce fatty alcohols with relatively narrow ethylene oxide contents, in the range of about 7 to 9 moles, and the C9 - C11 fatty alcohols ethoxylated with about 5 to 6 moles of oxide ethylene.



   Mixtures of two or more of the liquid nonionic surfactants can be used and in some cases benefits can be derived from the use of such mixtures.



   Non-lonic Surfactant with Acid Termination
 EMI21.2
 The viscosity and gelation properties of liquid detergent compositions can be improved by incorporating into the composition an effective amount of an acid-terminated liquid nonionic surfactant. Acid-terminated nonionic surfactants consist of a nonionic surfactant which has been modified to transform a free hydroxyl group of this surfactant into a moiety having a free carboxyl group, for example an ester or partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.



   As described in patent application FR-85 05.319 filed April 9, 1985, the nonionic surfactants modified by a free carboxyl group, which can roughly be characterized as polyether-carboxylic acids, act by lowering

  <Desc / Clms Page number 22>

 the temperature at which the liquid nonionic surfactant forms a gel with water.



   The addition of acid-terminated nonionic surfactants to the favored liquid nonionic surfactant
 EMI22.1
 increases the ability of the composition to be dispensed, that is to say its ability to be poured, and lowers the temperature at which the liquid nonionic surfactants form a gel in water without reducing their stability against sedimentation, Acid-terminated nonionic surfactant reacts in washing machine water with the alkalinity of the dispersed detergency builder salt phase of the detergent composition and acts as an effective anionic surfactant.



   Particular examples include the hemi-esters of the nonionic surfactant (A) with succinic anhydride, the ester or hemi-ester of Dobanol 25-7 with the succinic anhydride, and the ester or hemi-ester of Dobanol 91-5 with succinic anhydride. Instead of succinic anhydride, other anhydrides or polycarboxylic acids can be used. for example maleic acid, maleic acid anhydride, glutaric acid, malonic acid, phthalic acid, phthalic anhydride, citric acid, etc.



   Acid-terminated nonionic surfactants can be prepared as follows:
Acid-terminated product (A): 400 g of non-ionic surfactant (A), which is a C1-C3 alkanol having been alkoxylated, are mixed so as to introduce therein 6 ethylene oxide units and 3 propylene oxide units per unit d alkanol, with 32 g of succinic anhydride, and the whole is heated for 7 hours at 100 C. The mixture is cooled and filtered to remove the unreacted succinic material.

  <Desc / Clms Page number 23>

 



  Infrared analysis shows that almost half of the nonionic surfactant has been transformed into its acid hemi-ester.



   Acid-terminated Dobanol 25-7: 522 g of Dobanol 25-7, a non-ionic surfactant which is the ethoxylation product of a C12-Cl 2 alkanol and contains about 7 ethylene oxide units per molecule, are mixed. alkanol, with 100 g of succinic anhydride and 0.1 g of pyridine (which acts as an esterification catalyst) and the whole is heated to 2600C for two hours, cooled and filtered to remove the unreacted succinic material . Infrared analysis shows that virtually all of the free hydroxyl groups in the surfactant have reacted.



   Acid-terminated Dobanol 91-5: 1000 g of Dobanol 91-5, a nonionic surfactant which is the ethoxylation product of a C9 to Cll alkanol and contains about 5 ethylene oxide units per molecule d, are mixed. alkanol, with 265 g of succinic anhydride and 0.1 g of pyridine as catalyst, and the whole is heated at 260 ° C. for 2 hours, cooled and filtered to remove the unreacted succinic material. Infrared analysis shows that virtually all of the free hydroxyl groups in the surfactant have reacted.



   Other esterification catalysts, such as an alkali metal alcoholate (eg sodium methylate), can be used in place of, or in admixture with, pyridine.



   The acidic polyether, ie the acid-terminated nonionic surfactant, is preferably added in the dissolved state to the nonionic surfactant.



   Adjuvant Detergent Salts
The non ionigoe liguidenon aqueous surfactant used

  <Desc / Clms Page number 24>

 in the compositions of the present invention contains, in the dispersed and suspended state, fine particles of organic and / or mineral detergency builder salts.



   The detergent compositions of the invention include adjuvant detergent salts soluble in water and / or insoluble in water. Alkaline mineral water-soluble detergency builder salts that can be used alone with the detergent compound or in admixture with other detergency builders are carbonates, bicarbonates, borates, phosphates, polyphosphates, and alkali metal silicates ( it is also possible to use ammonium or substituted ammonium salts).

   Particular examples of these salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate. um, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono- and di-orthophosphates and potassium bicarbonate.



  Sodium tripolyphsophate (TPP) is particularly preferred.



   Since the compositions of the present invention are generally very concentrated and therefore can be used in relatively low doses, it is desirable to supplement any detergency builder of the phosphate type (such as sodium tripolyphosphate ) by an auxiliary detergency builder such as a lower polycarboxylic acid or a polymeric carboxylic acid having a high calcium binding capacity in order to inhibit incrustation which could otherwise be caused by the formation of a phosphate insoluble calcium.

  <Desc / Clms Page number 25>

 



   Suitable lower polycarboxylic acids include the alkali metal salts of lower polycarboxylic acids, preferably the sodium and potassium salts. Suitable interior polycarboxylic acids have two to four carboxylic acid groups. The preferred sodium and potassium salts of lower polycarboxylic acids are the citric and tartaric acid salts.



  The sodium salts of citric acid are the most suitable, in particular trisodium citrate. You can also use monosodium and disodium citrates.



  It is also possible to use the monosodium and disodium salts of tartaric acid. The alkali metal salts of lower polycarboxylic acids are particularly good detergency builder salts; thanks to their strong capacity for fixing calcium and magnesium, they inhibit incrustation which could, without them, be caused by the formation of insoluble salts of calcium and magnesium.



   In order to obtain a phosphate-free detergent composition, the whole polyphosphates can be replaced by one or more of the auxiliary detergency builder salts.



   Other organic detergency builders are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their alkali metal salts. More particularly, these detergency builder salts may consist of a copolymer which is the product of the reaction, of an approximately equal number of moles of methacrylic acid and anhydride. m, älgique, having been completely neutralized to form its sodium salt. This detergency builder is commercially available under the trademark Sokalan CP5. This detergency builder is used, even when used in small amounts, to

  <Desc / Clms Page number 26>

 hiber inlay.



   Examples of sequestering alkaline organic detergent builder salts which may be used with the detergency builder salts or in admixture with other organic and inorganic detergent builders are aminopolycarboxylates of alkali metals, ammonium and substituted ammonium, for example sodium and potassium echylenediaminetetraacetate (EDTA), sodium and potassium nitriloacetates (NTA) and triethanolamine N- (2-hydroxyethyl) nitril-odiacetates. Mixtures of these aminopolycarboxylates are also suitable.



   Other detergency builders or suitable auxiliary detergency builders of the organic type include carboxymethylsuccinates, tartronates and glycolates. Polyacetal-carboxylates are particularly interesting. Polyacetalcarboxylates and their use in detergent compositions are described in the patent application of the Applicant FR 86 11 852 filed on August 19, 1985, and in the patents of the United States? 4,144,226.4 315,092 and 4,146,495.



   The alkali metal silicates are useful adjuvant detergency salts which also act by adjusting or regulating the pH and making the composition anticorrosive to the parts of the washing machine. Sodium silicates with Na20 / SiO2 ratios ranging from 1.6/1 to 1/3, 2, especially from about 1/2 to 1/2, 8, are preferred. Potassium silicates with the same ratios can also
 EMI26.1
 be used.



   Other typical suitable detergency builders include, for example, those described in U.S. patents? 4,316,812.4 264,466 and 3,630,929. Alkaline detergency builder salts

  <Desc / Clms Page number 27>

 minerals can be used with the non-ionic surfactant detergent or mixed with other organic or mineral detergency builder salts.



   It is also possible to use crystalline and amorphous aluminosilicates insoluble in water of the zeolite type. Zeolites correspond to the general formula: -
 EMI27.1
 (mao) x. (Al) y. (SiO) 'wHO in which x is l, y ranges from 0.8 to 1.2 and is preferably 1, z ranges from 1.5 to 3.5 or more and: preferably from 2 to 3, w ranges from 0 to 9 and preferably from 2.5 to 6, and M is preferably sodium.

   A typical zeolite is a zeolite of type A or of similar structure, type 4A being particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of approximately 200 milliequivalents per gram or more, for example 400 meq / g. .



   Various crystalline zeolites (i.e. aluminosilicates) which can be used are described in British Patent No. 1,504,168, United States Patent No. 4,409,136 and Canadian Patents No. 1,072,835 and 1,087,477. An example of the amorphous zeolites useful here can be found in Belgian patent NO 835 351.



   Other materials such as clays, particularly water-insoluble types, may be useful auxiliaries in the compositions of the present invention. Bentonite is particularly useful. This material consists mainly of montmorillonite which is a hydrated aluminum silicate of which about one sixth of the aluminum atoms can be replaced by magnesium atoms and with which various quantities of hydrogen, sodium, potassium, calcium, etc. may be weak-

  <Desc / Clms Page number 28>

 combined.

   Bentonite, in its purest form (i.e. free of any sand, abrasive particles, etc.) suitable for detergents, contains at least 50% of montmorillonite and therefore its capacity to The replacement of cations is at least about 50 to 75 meq per 100 g of bentonite. Particularly preferred bentonites are bentonites from the western United States of America or Wyoming which have been sold under the designations Thixo-jels 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textiles such as described in British patents Nos. 401,413 and 462,221.



   Viscosity and Antifreeze Adjusters
The storage properties of the detergent composition during storage can be significantly improved by incorporating into the composition an effective amount of low molecular weight amphiphilic compounds which act as viscosity regulating agents and inhibit freezing towards the surfactant. non-ionic. Viscosity adjusting and gelling inhibiting agents work
 EMI28.1
 so as to lower the temperature at which the nonionic surfactant forms a gel when added to water.

   These viscosity adjusting and gelling inhibiting agents may be, for example, amphipruue compounds of the lower monoalkyl ether type of low molecular weight allene oxide.



  Amphiphilic compounds can be considered analogous by their chemical structure to liquid nonionic surfactants of the ethoxylated fatty alcohol type.
 EMI28.2
 and / or propoxyl, but they have relatively short hydrocarbon chains (C2 to Ca) and a relatively low content of ethylene oxide (about 2 to 6 ethylene oxide groups per molecule).

  <Desc / Clms Page number 29>

 



   Suitable amphiphilic compounds can be represented by the following general formula:
 EMI29.1
   in which Rest a C2 - C8 alkyl group, R2 is hydrogen or a methyl group and n is a number with a value of 1 to 6 on average.



   In particular, these compounds are lower monoalkyl ethers (C2 to Ce) of alkylene glycol in
 EMI29.2
 lower (C2 z C ..).



  More particularly, these compounds are lower monoalkyl ethers (Ci to C) of mono-, di- or trialkylene-lower glycol (C2 to C3).



   Particular examples of suitable amphiphilic compounds include the following: ethylene glycol monoethyl ether (C2H5-0-CH2CHOH) diethylene glycol monobytyl ether
 EMI29.3
 tetraethylene glycol monobutyl ether
 EMI29.4
 and
 EMI29.5
 dipropylene glycol methyl ether
 EMI29.6
 
 EMI29.7
 Especially preferred is monobutyl ether of diethylene glycol.



   The incorporation into the composition of the lower molecular weight lower alkylene glycol monoalkyl ether reduces the viscosity of the composition, so that it is easier to pour, improves the stability against sedimentation and improves the dispersibility of the composition. when she is

  <Desc / Clms Page number 30>

 added to warm or cold water.



   The compositions of the present invention have improved viscosity and stability characteristics and remain stable and suitable for pouring at temperatures as low as about 5 "C or less.



   In one embodiment of the present invention, a stabilizing agent which is an alkanolic ester of phosphoric acid may be added to the formulation. Improvements in the stability of the composition can be brought about by the incorporation of a small effective amount of an acidic organic phosphorus compound bearing an acid group - POH, for example a partial ester of phosphorous acid and an alkanol . As described in the patent application FR-85. 053 19 deposited on April 9, 1985, the acidic organic compound of phosphorus carrying an acid group -POH can increase the stability of the suspension of detergency adjuvants in the non-aqueous nonionic liquid surfactant.

   The acidic organic phosphorus compound can be, for example, a partial ester of phosphoric acid and an alcohol such as an alkanol having a lipophilic nature because it has, for example, more than 5 carbon atoms, for example 8 to 20 carbon atoms.



   A particular example is a partial ester of phosphoric acid and a C16 to C18 alkanol (Empiphos 5632 from Marchon); this product consists of approximately 35% monoester and 65% diester.



   The incorporation of very small amounts, for example 0.3% by weight of the organic phosphorus acid compound makes the suspension more stable against sedimentation at rest while leaving it suitable for pouring, however only at low concentrations of stabilizing agent. , for example less than about 1%, its

  <Desc / Clms Page number 31>

 plastic viscosity generally decreases.



   Other useful bleach activators can be added to the composition: among them, bleach activators can be mentioned
 EMI31.1
 chiment such as tetraacetyl-ethylene-diamine (TAED) and pentaacetyl-glucose, derivatives of acetylsalicylic acid, ethyliden benzoate-acetate and its salts, an ethyliden carboxylate-acetate and its salts, a carboxylate- ethylidene acetate and its
 EMI31.2
 salts, an alky1- or alkenyl-succinic anhydride, tetraacetylglycouri1e (TAGU), and derivatives of these activators. Other useful classes of activators are described, for example, in U.S. Patents NO 4,111,826.4 422,950 and 3,661,789.



   The second bleach activator or auxiliary bleach activator can be. added to supplement the calcium bleach activating cyanamide and to further lower the temperature, for example below about 60 C, at which the peroxygen bleaching compound becomes effective.



   In addition to detergency builders, various other additives or builders may be present in the detergent product to give it additional desired properties, whether functional or aesthetic in nature. Thus, one can include in the formulation of minor amounts of antiredeposition agents or of suspension of soiling, for example a polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose. A preferred antiredeposition agent is a carboxy-methyl-cellulose sodium having a CM / CMC ratio of 2: 1, which is sold under the trade name Relatin DM 4050.



   It is also possible to incorporate small quantities of Duet 787, which is a perfume, into the composition.

  <Desc / Clms Page number 32>

 and which is provided by International Flavors and Fragrances, Inc., Union Beach, New Jersey 07735 U. S. A.



  Duet 787 can be added in proportions, for example from 0.3 to 1.0 percent, preferably from 0.2 to 2.0 percent, especially from 0.5 to 2 percent, such as from 0.3 1.0% of the weight of the composition.



   Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include stilbene, triazole and benzidine-sulfone compositions, especially sulfonated triazinyl-stilbene, sulfonated naphtotriazole-stilbene, benzidine-sulfone, etc., the most preferred being combinations of stilbene and triazole. A preferred brightener is Stiibene Brightener N4 which is a polysulfonate of
 EMI32.1
 dimorpholino-dianilino-stilbene.



   Enzymes may be added, preferably proteolytic enzymes, such as subtilisin, bromelain, papain, trypsin and pepsin, as well as amylase-like enzymes, lipase-like enzymes and mixtures thereof. Preferred enzymes include a protease suspension, an esperase suspension and an amylase. A preferred enzyme is Esperase SL8 which is a proteolytic enzyme. Antifoaming agents, for example silicon compounds such as Silicane L 7604, can also be added in small effective amounts.



   It is also possible to use bactericides, for example tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (dispersible in water), preservatives, ultraviolet absorbers, anti-yellowing agents such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color preservatives,

  <Desc / Clms Page number 33>

 perfume, coloring agents and whitening agents such as ultramarine blue.



   In one embodiment of the invention, the stability of the detergency builder salts in the composition during storage and
 EMI33.1
 Persistence of the composition in water is improved by grinding and reducing the particle size of solid detergency builders to less than 100 microns, preferably to less than 40 microns and more preferably to less than 10 microns. Solid detergency builders, for example sodium tripolyphosphate (TPP) are generally supplied in particle sizes of about 100,200, or 400 microns. The liquid non-ionic surfactant phase can be mixed with the solid detergency builders before or after the grinding operation is carried out.



   In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to the action of an attrition type mill in which the particle sizes of the solid ingredients are reduced unless about 10 micrometers, per edlemple to an average particle size of 2 to 10 micrometers or even less (for example 1 micrometer) Preferably less than about 10Z, and especially less than about 5% of all particles suspension have dimensions greater than 10 micrometres. Compositions with dispersed particles of such small dimensions exhibit better stability against separation or sedimentation during storage.

   The addition of the acid-terminated nonionic surfactant can decrease the flow limit of these dispersions and improve their dispersibility without causing

  <Desc / Clms Page number 34>

 correlation duction and blastability of dispersions against sedimentation.



   In the grinding operation, it is preferable that the proportion of solid ingredients is high enough (for example at least about 40%, as well as about 50%) so that the solid particles are in contact between them and are not substantially isolated from each other by the liquid nonionic surfactant. After the grinding stage. any remaining liquid nonionic surfactant can be added to the ground composition. Grinders which use grinding balls (ball mills) or similar movable grinding elements have given very good results. Thus, one can use a laboratory mill-attritor working in portions containing grinding balls in steatite. 8 mm in diameter.

   For an operation on a larger scale, one can use a mill operating in continuous mode in which there are grinding balls of 1 mm or 1, 5 mm in diameter working in a very small interval formed between a stator and a rotor rotating a relatively high speed (for example a CoBall crusher);

   when using such a mill, it is advantageous to first pass the mixture of nonionic surfactant and solid ingredients through a mill which does not perform such a fine milling (eg a colloid mill) in order to reduce the particle size to less than 100 micrometers (for example to about 40 micrometers) before the grinding step to a diameter. average particle size of less than about 10 micrometers which takes place in the ball mill operating in continuous mode.



   In the liquid detergent compositions for heavy laundry washing work according to the invention

  <Desc / Clms Page number 35>

 tion, typical proportions (in percent based on the total weight of the composition, unless otherwise indicated) of the ingredients are as follows:
Liquid nonionic surfactant detergent: in the range of about 10 to 60 percent, such as from 20 to 50 percent, for example about 30 to 40 percent.



   Acid-terminated nonionic surfactant as a viscosity improver: in the range of about 0 to 20 percent, such as from 3 to 15 percent, for example about 4 to 10 percent.



   Detergency builder, eg sodium tripolyphosphate (TPP): in the range of about 10 to 60 percent, such as from 15 to 50 percent, for example about 25 to 35 percent.



   Copolymer of metal salt of polyacrylic acid and polymaleic anhydride, for example Sokalan CP5, as anti-scaling agent: in the range of about 0 to 10 percent, as from 2 to 8 percent, for example about 3 at 5 percent.



   Monoalkyl ether of alkylene glycol as anti-gelling agent: in the range of about 30 to one hundred, such as from 5 to 20 percent, for example about 5 to 15 percent.



   Alkanolic ester of phosphoric acid as a stabilizing agent: in the range of 0 to 2.0 percent or from 0.1 to 1.0 percent, as from 0.2 to 0.5 percent.



   Bleach: in the range of about 5 to 30 percent, such as 2 to 20 percent, for example about 5 to 15 percent.



   Cyanamide calcium as a bleach activator: in the range of about 1 to 15 percent, like 1 to 8 percent, for example about 2 to 6 percent.

  <Desc / Clms Page number 36>

 



   Sequestering agent for the bleaching agent, for example Dequest 2066: in the range of about 0 to 3.0 percent, preferably 0.5 to 2.0 percent, for example about 0.75 to 1 , 25 percent.



   Anti-redeposition agent, for example Relatin DM 4050: in the range of about 0 to 4.0 percent, preferably 0.5 to 3.0 percent, for example 0.5 to 1.5 percent .



   Optical brightener: in the range of about 0 to 2.0, preferably from 0.05 to 1.0 percent, for example 0.15 to 0.75 percent.



   Enzymes: in the range of about 0 to 3.0 percent, preferably 0.5 to 2.0 percent, for example 0.75 to 1.25 percent.



   Perfume: in the range of about 0 to 3.0 percent, preferably 0.10 to 1.25 percent, for example 0.25 to 1.0 percent.



   Various additives among those previously mentioned can be added optionally to obtain the desired function of these added materials.



   The calcium bleach activator calcium cyanamide is preferably used with at least one of the viscosity control and antifreeze agents that are the alkylene glycol monoethers and the acid-terminated nonionic surfactants.



  In some cases, benefits can be derived from the simultaneous use of the alkylene glycol monoethers and acid-terminated nonionic surfactants.



   With regard to the choice of additives, these must be chosen so as to be compatible with the main constituents of the detergent composition. In the present specification, as mentioned above, all the proportions and all the percentages are expressed by weight relative to the weight of the total composition or formulation, unless otherwise indicated.

  <Desc / Clms Page number 37>

 opposite.



   The concentrated nonaqueous liquid nonionic detergent composition of the present invention is easy to dispense into the water of the washing machine.



   In one embodiment of the invention, a detergent composition of typical formulation is prepared using the ingredients designated below:
 EMI37.1
 2 by weight Non-ionic surfactant detergent 30 - 40 Acid-terminated surfactant, viscosity improving agent 0-20 Phosphate, detergency builder salt 10 - 60 Anti-scaling agent 0-10
 EMI37.2
 Alkylene glycol monoalkyl ether, antifreeze agent 5-15 Alkanolic ester of phosphoric acid, stabilizing agent 0-2, 0 Anti-redeposition agent 0-4, 0 Alkali metal perborate, bleaching persalt 5 - 15 Calcium cyanamide, bleach activator 1, 0-8, 0 Sequestering agent for bleach 0 - 3, 0 Duet 787 0 - 3.0 Optical brightener 0, 15-0,

   75
 EMI37.3
 Enzymes 0.75-1.25 Perfume O-3.0 The following examples further illustrate the. present invention.



  EXAMPLE 1
A concentrated nonaqueous liquid detergent composition based on nonionic surfactant is prepared from the following ingredients.

  <Desc / Clms Page number 38>

 specified conditions.



   % by weight Non-ionic surfactant 38.8 Acid-terminated reaction product of Dobanol 91-5 with succi-5, 0 anic acid Sodium tripolyphosphate (TPP) 29, 6 Diethylene glycol monobutyl ether, anti-gelling agent 10 Ester alkanolic phosphoric acid (Emphiphos 5632) 0, 3 Sodium perborate monohydrate, bleach 9, 0 Calcium cyanamide, bleach activator 4, 5 Anti-redeposition agent (DM 4050 relationship) (1) 1.0 Optical aviator 0, 2
 EMI38.1
 Perfume (Duet 787) 0.6 Enzyme (Esperase) 1.0
100, 0 (1) mixture CMC / MC = 2: 1 of sodium carboxymethylcellulose and hydroxymethylcellulose.



   The composition is ground for about 1.0 hour to reduce the particle size of the detergency builder salts in suspension to less than 40 microns. It is found that the detergent composition prepared is stable and non-gelling during storage, that it disperses easily in water and that it has good whitening properties and better detergent power.



  EXAMPLE 2
A concentrated nonaqueous liquid detergent composition based on nonionic surfactant is prepared from the following ingredients in the specified proportions.

  <Desc / Clms Page number 39>

 



   X by weight Non-ionic surfactant, Product D 13, 5 Surfactant T7 10 Surfactant T9 10 Acid-terminated reaction product of Dobanol 91-5 with succinic anhydride 5 Sodium tripolyphosphate (TPP) 29, 6 Anti-encrustation agent (Sokalan CP5 ) 4, 0
 EMI39.1
 Diethylene glycol monobutyl ether, anti-grading agent 10 Alkanolic phosphoric acid ester (Emphiphos 5632) 0, 3 Sodium perborate monohydrate, bleaching agent 9 Calcium cyanamide, bleaching agent activator 4, 5 Sequestering agent for agent bleaching agent (Dequest 2066) 1, 0 Anti-redeposition agent (Relatin DM 405. 01) 1, 0 '
 EMI39.2
 Optical brighteners (Sti1bène) 0, 5 Enzyme (suspension of Esperase) 1, 0 Duet 787 (2) 0, 6
100, 0 (1) CMC / MC mixture = 2:

     l sodium carboxymethylcellulose and hydroxymethylcellulose.



   (2) Duet 787 which is a fragrance from IFF, Inc.



   The composition is ground for about 1 hour to reduce the particle size of the detergency builder salts in suspension to less than 40 microns. It is found that the detergent composition prepared is stable and non-gelling during storage and that it disperses easily in water. The bleach is active at 60 C on the immediate dark.



  The 4.5Z concentration of calcium cyanamide gives an Rd value = 5.3 compared to a value

  <Desc / Clms Page number 40>

   A, Rd from 0, 8 without activator. The pH of the aqueous washing liquor without bleach activator is 9,6, it is 9,9 with 4,5% of calcium cyanamide activator, and it is 9,0 with 4,5 % of
TAED as activator.



   The compositions of Examples 1 and 2 can be prepared without grinding detergency builder salts and suspended solid particles to a small particle size, but the best results are obtained by grinding the composition to reduce the particle size. suspended solid particles.



   The detergency builder salts can be used as supplied, or the detergency builder salts and suspended solid particles can be ground or partially ground before being mixed with the nonionic surfactant. The . grinding can be carried out in part before the mixing operation and can be completed after the mixing operation, or else the entire grinding operation can be carried out after mixing with the liquid surfactant. Compositions which contain a detergency builder and suspended solid particles with a particle size of less than 40
 EMI40.1
 micrometres are preferred.



   The persal bleaching system and calcium cyanamide bleach activator of the present invention can also be used in detergent compositions based on nonionic surfactant for dishwashing, cream scouring products, and other compositions in which bleaching is necessary as dry powder and granular detergent compositions.


    

Claims (19)

 CLAIMS 1. A detergent composition for treating tissues, comprising a liquid nonionic detergent surfactant, a peroxygenated mineral compound as a bleaching agent and calcium cyanamide as a bleaching agent activator.  2. Detergent composition according to claim 1, characterized in that it comprises an agent for adjusting the viscosity and anti-gelling.  3. Detergent composition according to claim 1, characterized in that it comprises at least one agent for adjusting the viscosity and anti-gelation chosen from a monoalkyl ether of alkylene glycol and a nonionic surfactant with acid termination.  4. Detergent composition according to claim 1, characterized in that it comprises a suspension of insoluble mineral salts detergency adjuvants.  5. Detergent composition according to claim 4, characterized in that the detergency builder salt comprises an alkali metal polyphosphate.  EMI41.1   6. A detergent composition according to claim 4, characterized in that the insoluble mineral detergency builder comprises 10 to 60 percent of a detergency builder polyphosphate.  7. Detergent composition according to claim 1, characterized in that it comprises one or more detergent additives chosen from an anti-encrustation agent, a sequestering agent, an anti-redeposition agent, an optical brightener, enzymes and a perfume.  8. Detergent composition according to claim 1, characterized in that it comprises 10 to 60 percent of nonionic liquid detergent surfactant.  <Desc / Clms Page number 42>    9. Detergent composition according to claim 3, characterized in that it comprises 5 ä. 30 percent of an alkylene glycol monoalkyl ether.  10. Detergent composition according to claim 4, characterized in that the adjuvant salt of mineral detergent has a particle size less than 40 micrometers.  11. A detergent composition according to claim 1, characterized in that it contains about 0.1 to about 0.5 percent by weight, based on the weight of the total composition, of an alkanolic ester of phosphoric acid as an agent anti-food stabilizer.  12. A non-aqueous liquid detergent composition containing a detergency builder for heavy laundry work, which can be poured at low and high temperatures and does not gel when mixed with cold water, comprising at least one non-surfactant ionic liquid in a proportion of about 10 to 60 percent by weight; at least one sei mineral detergency builder suspended in the nonionic surfactant in a proportion of about 10 to about 60 percent by weight; a peroxygen mineral bleach in an amount of about 5 to 15 percent by weight; calcium cyanamide as a bleach activator, in a proportion of about 1 to 8 percent by weight, an acid-terminated nonionic surfactant as a gelling inhibitor additive, in a proportion of  EMI42.1  from 0 to 20 percent by weight;  and a compound of-  EMI42.2  mule-: 1, 2 R'-O (CHCHO) H,  EMI42.3  or R- is a ü-Cn alkyl group, R esc L hydrogen or a methyl group and n is a number having a  <Desc / Clms Page number 43>  average value of about 1 to 6, as a gelling inhibiting additive, in an amount up to about 5 to 30 percent by weight.  13. Detergent composition according to claim 12, characterized in that it contains one or more detergent additives chosen from an anti-encrustation agent, a sequestering agent, an anti-redeposition agent, an optical brightener, an enzyme and a perfume.  14. Detergent composition according to claim 12, characterized in that it comprises: approximately 20 to 50% by weight of nonionic surfactant, approximately 3 to 15% by weight of nonionic surfactant with acid termination as viscosity improving agent, approximately . 15-50 X by weight of tripolyphosphate  EMI43.1  sodium, about 2-8 X by weight <. ssldeaociiur: deocpolyt'ece of polyacrylic acid and polymaleic anhydride, about 5 - 20% by weight of monoalkyl ether of diethylene glycol, about 0, 1 - 1, 0% by weight of alkanolic ester of phosphoric acid , approximately 2 - 20% by weight of sodium perborate monohydrate as a bleaching agent, and approximately 1 - 8 X by weight of calcium cyanamide.  15. Detergent composition according to claim 12, characterized in that it comprises: approx.  EMI43.2  ron 30 - 40% by weight of nonionic surfactant, about 3 - 15% by weight of acid-terminated nonionic surfactant as viscosity enhancing agent, about 25-35 X by weight of sodium tripolyphosphate, about 3-5 X in weight of sodium salt of copolymer of polyacrylic acid and polymaleic anhydride, approximately 5-15% by weight of diethylene glycol monobutyl ether, approximately 0.2 - 0.5% by weight of alkanolic ester phosphoric acid, about 5 - 15% by weight of sodium perborate mono-  <Desc / Clms Page number 44>  hydrate as bleaching agent, approximately 2 - 6.0 Z by weight of calcium cyanamide,  about 0.75-1.25% by weight of sequestering agent for the bleaching agent, and about 0.5-1.5% by weight of anti-deposition agent.  16. Method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the detergent composition of claim 1.  17. A method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the detergent composition for washing the laundry of claim 12.  18. Method for cleaning soiled fabrics according to claim 17, characterized in. that it consists in bringing the soiled fabrics into contact with the detergent composition for washing the laundry of claim 14.  19. Method for cleaning soiled fabrics according to claim 17, characterized in that it consists in bringing the soiled fabrics in contact with the detergent composition for washing clothes of claim 15.