NL8702063A - NON-AQUEOUS LIQUID, NON-IONIC LAUNDRY DETERGENT COMPOSITION, CONTAINING A PERZOUT BLEACH AND CALCIUM CYANAMIDE AS A BLEACH ACTIVATOR AND METHOD FOR USING THE COMPOSITION. - Google Patents

Description

<* VO 9292

Non-aqueous liquid nonionic laundry detergent composition containing a persalt bleach and calcium cyanamide as a bleach activator, as well as a method of using the composition.

The invention relates to non-aqueous liquid compositions for the treatment of fabrics, in particular to liquid non-ionic laundry detergent compositions containing an inorganic persalt bleaching compound and calcium cyanamide as bleach activator. The compositions are stable against phase separation and gel formation and are easy to pour. The compositions are used for cleaning dirty tissues.

Liquid non-aqueous laundry detergent compositions are well known. Compositions of this type may contain a liquid nonionic surfactant material in which particles of a builder material are dispersed, as described, for example, in U.S. Patents 4,316,812, 3,630,929, and 4,264,466 and British Patents 1,205,711 , 1,270,040 and 1,600,981.

Related pending U.S. Patent Applications 15 are No. 717,726, filed March 29, 1985, relating to a liquid nonionic laundry detergent composition containing a perborate bleach, a bleach activator and hydroxylamine sulfate as a bleach stabilizer and specifically as a catalase inhibitor; No. 597,793, filed April 6, 1984, relating to a non-aqueous liquid nonionic surfactant detergent composition comprising a suspension of a builder salt and containing a nonionic surfactant with terminal acid group (eg, the reaction product of a non- ionic surfactant and succinic anhydride) to improve dispersibility of the composition in an automatic washing machine; No. 687,815, filed December 3, 1984, relating to a non-aqueous liquid nonionic surfactant detergent composition comprising a suspension of builder salt and containing an alkylene glycol monoalkyl ether as a viscosity and gelling control agent to improve dispersibility of the composition in an automatic washing machine; and No. 597,948, filed April 9, 1984, relating to a non-8702063 t-2-aqueous liquid nonionic surfactant detergent composition comprising a suspension of polyphosphate builder salt and containing an alkanol ester of phosphoric acid to improve the stability of the suspension against settling during storage.

These patent applications are directed to liquid non-aqueous non-ionic laundry detergent compositions.

Liquid detergents are often thought to be easier to use than dry powdered or particulate products and are therefore considerably preferred by consumers. They are easy to measure, dissolve quickly in the wash water, are easy to apply to dirty clothes in concentrated solutions or dispersions, do not dust and usually take up less storage space. Furthermore, the liquid detergents may contain materials which cannot tolerate a drying treatment without damage, which materials are often often desired in the preparation of particulate detergent products. While liquid detergents have many advantages over unitary or particulate solid products, they also have certain inherent drawbacks that must be overcome to arrive at acceptable commercial detergent products. Some such liquid products show storage separation and others show cooling separation and are not readily redispersed. In some instances, the product viscosity changes and the product either becomes too thick to be poured or so thin that it appears watery. On standing, some clear products become cloudy and others form a gel.

An investigation was conducted into the behavior of nonionic liquid surfactant systems in which particulate matter is suspended. Of particular interest were non-aqueous liquid built-up laundry detergent compositions and the problem of settling of the suspended build-up material and other washing additives, as well as the problem of gel formation associated with nonionic surfactants. These phenomena affect, for example, product stability, pourability and dispersibility.

It is known that one of the major problems with built-up liquid laundry detergents is their physical stability. This problem arises from the fact that the density of the particles dispersed in the liquid nonionic surfactant is greater than the density of the liquid surfactant.

The dispersed particles therefore tend to settle.

There are basically two solutions to this problem: increasing the viscosity of the nonionic liquid and reducing the particle size of the dispersed solid material.

It is known that settling suspensions can be stabilized by the addition of inorganic or organic thickeners or dispersants, such as inorganic materials with a very large surface, for example finely divided silica, clay and the like, organic thickeners, such as cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc. Such increase in the viscosity of the slurry is, of course, limited by the requirement that the liquid slurry must be easily pourable and flowable even at low temperature. Furthermore, these additives do not contribute to the cleaning power of the mixture.

Grinding to reduce particle size provides the following advantages: 1. The specific surface area of the dispersed particles 20 is increased, thereby proportionally improving wetting of the particles by the non-aqueous carrier (liquid non-ionic material).

2. The average distance between dispersed particles is reduced with a proportional increase in the interaction between the 25 particles.

Each of these effects helps to increase the residual gel strength and the yield stress of the suspension, while at the same time significantly reducing the plastic viscosity by grinding.

The yield stress is defined as the minimum stress required to induce a plastic deformation (flow) of the suspension. If the suspension is considered to be a loose network of dispersed particles, if the applied stress is less than the yield stress, the suspension will behave like an elastic gel and no plastic flow will occur. If the yield stress is exceeded, the network breaks at certain points and the sample starts to flow, but with a very high apparent viscosity. If the shear stress 8702063-4- * is much higher than the yield stress, the pigments are partially flocculated by shear and the apparent viscosity drops. Finally, if the shear stress is very much greater than the yield stress value, the dispersed particles are flocked out completely and the apparent viscosity is very low, as if there is no interaction between the particles.

Therefore, as the yield stress of the slurry is higher, at low shear the apparent viscosity will be higher and the physical stability against settling of the plug pressure will be better.

The non-aqueous liquid laundry detergents based on liquid non-ionic surfactants not only have the problem of settling or phase separation, but further have the drawback that the non-ionic materials tend to form a gel when added to cold water . This is a particularly important problem in the ordinary use of European automatic household washing machines, where the user places the laundry detergent composition in a dispenser (eg a dispenser drawer) of the machine. During machine operation, the detergent in the dispenser is exposed to a stream of cold water, which transports the composition to the main mass of the wash solution.

Especially during the winter months, when the detergent composition and the water supplied to the dispenser are particularly cold, the detergent viscosity increases markedly and a gel is formed. As a result, during operation of the machine, a portion of the composition is not completely rinsed out of the metering device and a deposit of the composition will build up in 25 repeated wash cycles, which must eventually be rinsed out of the metering device by the user.

The phenomenon of gel formation can also be a problem when one wishes to wash with cold water, as can be recommended for certain synthetic and delicate fabrics or fabrics that can shrink in warm or hot water.

The tendency of concentrated detergent compositions to gel during storage is enhanced by storage of the compositions in unheated storage areas or by their transportation during the winter months in unheated transport vehicles.

870 2 06 3 -5-

Partial solutions have been proposed to the problem of gel formation in aqueous compositions which are substantially free of builders such as, for example, dilution of the liquid nonionic material with certain viscosity controlling solvents and gel inhibitors such as low alkanols, for example ethanol (see U.S. Patent 3,953,380), alkali metal formates and adipates (see U.S. Patent 4,368,147), hexylene glycol, polyethylene glycol and the like, as well as modification and optimization of the nonionic structure. As an example of modification of a non-ionic surfactant material, a particularly successful result was obtained by acidifying the terminal hydroxyl group of the nonionic molecule. Advantages of introducing a carboxyl group at the end of the nonionic molecule are inhibition of gel formation upon dilution, reduction of the pour point of the nonionic material and formation of an anionic surfactant upon neutralization in the wash. Optimization of the nonionic structure focused on the chain length of the hydrophobic lipophilic molecule portion and the number and arrangement of alkylene oxide (e.g., ethylene oxide) units of the hydrophilic molecular portion. For example, it has been found that a fatty alcohol ethoxylated with 8 moles of ethylene oxide has only a limited tendency to gel.

There is still a need to improve the bleaching properties and the stability and gel inhibition of non-aqueous liquid compositions for the treatment of fabrics containing a bleach and a bleach activator.

According to the invention, a highly concentrated stable non-aqueous liquid laundry detergent composition containing a per-salt bleaching compound and a calcium cyanamide bleach activator is prepared.

A preferred persalt bleaching compound is sodium perborate-30 monohydrate.

The calcium cyanamide bleach activator is used in place of the conventionally used organic bleach activators, such as tetraacetylethylenediamine (TAED), which form an acid detrimental to the detergent. The calcium cyanamide acts as an activator for the persalt bleach and increases the alkalinity of the aqueous wash liquor and improves detergent.

870 2 0 6 Λ -6-

The system of the invention formed by the persalt bleach and the calcium cyanamide bleach activator can be used in phosphate-containing and low-phosphate detergent build-up salt compositions.

To improve the viscosity properties of the composition, a nonionic surfactant with terminal acid group can be added. To further improve the viscosity and storage properties of the composition, viscosity improving and anti-gelling agents, such as alkylene glycol coloalkyl ethers, and an anti-settling agent, such as an alkanol ester of phosphoric acid, may be added. In a preferred embodiment of the invention, the detergent composition contains sodium perborate monohydrate as a bleaching agent, calcium cyanamide as a bleach activator, a nonionic surfactant with terminal acid group, an alkylene glycol coloalkyl ether, and an alkanol ester of phosphoric acid stabilizing anti-settling agent.

The conventional peroxygen bleaching compounds, for example sodium perborate, percarbonate, perphosphate and persulfate, can be used as bleaching agents.

In one embodiment of the invention, the build-up components of the composition can be milled to a particle size of less than 100 µm, for example less than 40 µm, and preferably less than 10 µm, to further improve the stability of the build-up component suspension. in the liquid nonionic surfactant detergent.

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

In one aspect, the invention provides a liquid laundry treatment composition comprising a suspension of a peroxygen bleaching compound and a detergent build-up salt, for example, a phosphate build-up salt, in a liquid nonionic surfactant material, said bleach activator composition having an effective amount of 35 contains calcium cyanamide.

Another aspect provides the invention with a concentrated liquid laundry detergent composition which has good lower temperature bleaching properties, exhibits improved detergent properties, is stable, does not settle on storage, and does not form gel on storage and in use. The liquid compositions of the invention are easy to pour, easy to measure and easy to put in the washing machine and are easily dispersible in water.

In a further aspect, the invention provides a method for dosing a liquid nonionic laundry detergent composition 10 into and / or with cold water without gel formation. In particular, a method is provided for filling a vessel with a non-aqueous liquid laundry detergent composition, wherein the detergent is at least predominantly composed of a liquid nonionic surfactant, and for dispensing the composition from the vessel. 15 in an aqueous wash bath, the dosing being effected by directing a stream of unheated water onto the composition such that the composition is fed through the stream into the wash bath.

The use of the calcium cyanamide bleach activator in the composition in place of the commonly used organic bleach activators, for example TAED, provides good low temperature bleaching properties while increasing the alkalinity of the aqueous wash liquor and improving the detergent of the composition.

The concentrated non-aqueous liquid non-ionic surfactant laundry detergent compositions of the invention have the advantages of being stable, not settling on storage, and not forming a gel on storage. The liquid compositions are easy to pour, easy to measure and easy to put in the washing machines and are easily dispersible in water.

The non-aqueous liquid non-ionic laundry detergent compositions of the invention contain a persalt bleaching compound and calcium cyanamide bleach activator as essential ingredients of the composition.

The persalt bleaching compounds are well known, are dispersed as solids in the nonionic surfactant, and are readily soluble upon addition of the detergent composition to the wash water. The persalts or oxygen bleaches are 8702063-8 compounds which form hydrogen peroxide in aqueous solution. Preferred examples are sodium and potassium perborates, percarbonates, perphosphates and potassium monopersulfate. The perborates, in particular the sodium monohydrate, are particularly preferred.

Hydrogen peroxide and the precursors which form hydrogen peroxide are good oxidizing agents for removing stains from textiles, especially stains caused by wine, tea, coffee, cocoa, fruits and the like. Hydrogen peroxide and its precursors generally appear to be quick and most effective at relatively high temperatures, for example about 80-100 ° C.

To take advantage of the low temperature effective detergents and low temperature wash cycles now commonly used for temperature sensitive fabrics, the persalt or peroxygen bleach is used in conjunction with a bleach activator.

Organic bleach activators such as tetraacetylethylenediamine (TAED) have been used heretofore. The use of such organic bleach activators increases the acidity of the aqueous wash liquor and thereby adversely affects the detergent composition.

The calcium cyanamide bleach activator is used as an activator for the persalt bleaching compounds. The calcium cyanamide reacts in the aqueous wash with the hydrogen peroxide produced by the persalt bleaching compound to form a low temperature bleaching molecule portion.

The calcium of the calcium cyanamide in the aqueous washing liquid increases the alkalinity of the washing liquid and improves the detergent of the detergent composition. The addition of calcium cyanamide as a bleach activator to the detergent composition can lower the effective operating temperature of the peroxide bleaches to temperatures as low as about 60 ° C. In detergent compositions requiring lower operating temperatures, small amounts of the commonly used bleach activators, such as TAED, may be added.

In the preferred embodiment of the invention, calcium cyanamide is the only bleach activator or a major component, ie, greater than 50%, of the bleach activator used in the detergent composition.

8702063 -9-

Only small amounts of calcium cyanamide bleach activator are required for activation of the peroxygen bleaching compound. Suitable amounts of calcium cyanamide are, for example, 1-15% by weight, preferably 1-8% by weight, and most preferably 2-6% by weight, based on the total weight of the nonionic liquid surfactant composition.

The bleach activator usually reacts with the peroxygen compound to form a peroxyacid bleach in the wash water.

Preferably, a high complexing power sequestrant is added to inhibit any undesired reactions between the peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions.

Suitable sequestering agents for this purpose include the sodium salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DETPA), diëthyleentriaminepentamethyleen-15-phosphonic acid (DTPMP), commercially available under the trademark Dequest 2066, and ethylenediaminetetramethylenephosphonic acid (EDITEMPA). The sequencing agents can be used alone or as a mixture.

To prevent loss of peroxide bleach, eg, sodium perborate, due to enzyme-induced decomposition, eg, by catalase enzyme, the compositions may also contain an enzyme inhibitor compound, ie, a compound capable of enzyme-induced decomposition of the peroxide bleaching agent. Suitable inhibitor compounds are described in U.S. Patent 3,606,990.

Of particular interest as inhibitor compounds may be mentioned hydroxyl amine sulfate and other water-soluble hydroxylamine salts. Suitable amounts of the hydroxylamine salt inhibitors can be as low as 0.01-0.4%. Generally, however, suitable amounts of the enzyme inhibitors range up to about 15%, for example, 0.1-10%, based on the weight of the composition.

In addition, stabilizers may be added to the composition, for example an acidic organic phosphorus compound with an acidic POH group, such as a partial ester of phosphorous acid and an alkanol.

The nonionic surfactant detergents may be built with only polyphosphate builder salts or may have a low polyphosphate content.

8702nS3 -10-

The nonionic synthetic organic detergents to be used according to the invention can be selected from a wide variety of known compounds. As is known, the nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group. They are typically prepared by condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (which is hydrophilic in nature). Virtually any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen bonded to the nitrogen 10 can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups. Typical suitable nonionic surfactant surfactants are described in U.S. Pat. Nos. 4,316,812 and 3,630,929.

Usually, the nonionic detergents are poly-layer alkoxylated lipophiles in which the desired hydrophilic-lipophilic balance has been obtained by addition of a hydrophilic poly-lower alkoxy group to a lipophilic molecule moiety. A preferred class of the nonionic detergents to be used is the poly-layer alkoxylated higher alkanols in which the alkanol contains 9-18 carbon atoms and in which the number of moles of alkylene oxide of 2 or 3 carbon atoms is 3-12. Such materials are preferably used in which the higher alkanol contains 9-11 or 12-15 carbon atoms and which contains 5-8 or 5-9 lower alkoxy groups per mole. Preferably the lower alkoxy group is ethoxy, but in some cases it may be desirable that the ethoxy is mixed with propoxy, often in a minor (less than 50%) amount.

Examples of such compounds are those in which the alkanol has 12-15 carbon atoms and contains about 7 ethylene oxide groups per mole, for example Neodol 25-7 and Neodol 23-6.5, which products are marketed by Shell Chemical Company. Neodol 25-7 is a condensation product of a mixture of higher fatty alcohols with an average of 12-15 carbon atoms and about 7 moles of ethylene oxide, and Neodol 23-6.5 is a corresponding mixture in which the carbon content of the higher fatty alcohol is 12-13 and the number of ethylene oxide groups on average 8702063 -11- is about 6.5. The higher alcohols are primary alkanols.

Other examples of such detergents are Tergitol 15-S-7 and Tergitol 15-S-9, both linear secondary alcohol ethoxylates, manufactured by Union Carbide Corp. be placed on the market. Tergitol 15-S-75 is a mixed ethoxylation product of a linear secondary alkanol with 11-15 carbon atoms and 7 moles of ethylene oxide, and Tergitol 15-S-9 is a similar product, but with 9 moles of ethylene oxide.

Also suitable components of the nonionic detergent are higher molecular weight nonionic materials, such as Neodol 45-11, which are condensation products of higher fatty alcohols having 14-15 carbon atoms and about 11 ethylene oxide groups per mole. Such products are marketed by Shell Chemical Company.

Other suitable nonionic materials are represented by the commercially known nonionic products commercially available under the trade name Plurafac. The Plurafacs are 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 with a terminal hydroxyl group. Examples are (A) C23 "c15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, (B) c13-c15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, (C) C 1 -C 4 g fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide, and (D) a 1: 1 mixture of products (B) and (C).

Other liquid non-ionic materials are marketed by Shell 25 Chemical Company under the brand name Dobanol:

Dobanol 91-5 is an ethoxylated C 1 -C 6 fatty alcohol with an average of 5 moles of ethylene oxide and Dobanol 25-7 is an ethoxylated C 12 “C 15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

To obtain the best balance of hydrophilic and lipophilic molecular moieties in those preferred poly-layer alkoxylated higher alkanols, the number of lower alkoxy groups is usually 40-100% of the number of carbon atoms in the higher alcohol, preferably 40-60% thereof and the nonionic detergent preferably contains at least 50% of such poly-lower alkoxy higher alkanol, which is preferred. Higher molecular alkanols and various other normally solid nonionic detergents and surfactants may contribute to gel formation of the liquid detergent and are therefore preferably omitted or limited in the compositions of the invention, although minor amounts thereof can be used because of their cleaning properties and the like. In the nonionic detergents, both preferred and less preferred, the alkyl groups present are generally linear, although branching is permissible, for example, on a carbon atom adjacent to or 2 carbon atoms away from the terminal carbon of the straight chain and on the other side of the ethoxy chain, if 10 such branched alkyl groups have a length of no more than 3 carbon atoms. Normally, the content of carbon atoms in such a branched configuration is minor, rarely more than 20% of the total carbon atom content of the alkyl. While linear alkyl groups terminally bonded to the ethylene oxide chains are particularly preferred and are believed to provide the best combination of detergent, biodegradability, and non-gelling properties, medial or secondary bonding to the ethylene oxide in the chain may also take place. This is usually in only a minor number of such alkyl groups, generally less than 20%, but may also be larger, as in the said Tergitols. When propylene oxide is present in the lower alkylene oxide chain, it will usually be less than 20% thereof, preferably less than 10%.

When higher levels of non-terminal alkoxylated alkanols, propylene oxide-containing poly-layer alkoxylated alkanols, and nonionic detergents with less favorable hydrophilic lipophilic balance are used than described above, and when other nonionic detergents are used in place of the Preferred nonionic materials described herein may be that the resulting product does not exhibit such good detergent, stability, viscosity and non-gelling properties as the preferred compositions, but application of the viscosity angeliculant compounds of the The invention can also improve properties of detergents based on such nonionic materials. In some instances, such as using a higher molecular poly-layer alkoxylated higher alkanol, often for its detergent, the amount thereof can be controlled or limited by the results of 8702063-13 tests to obtain the desired detergent, yet the product does not form a gel and has the desired viscosity. It has also been found that it is seldom necessary to use higher molecular weight nonionic materials for their detergent properties, as the preferred nonionic materials described herein are excellent detergents and allow the desired viscosity in the liquid detergent without gel formation at low temperatures.

Another useful group of nonionic surfactants is the products marketed by British Petroleum under the trade name Surfactant T. The Surfactant T products are obtained by ethoxylation of secondary fatty alcohols with a narrow ethylene oxide distribution. Surfactant T5 contains an average of 5 moles of ethylene oxide, Surfactant T7 contains an average of 7 moles of ethylene oxide. Surfactant T9 averages 9 moles of ethylene oxide and Surfactant T12 averages 12 moles of ethylene-15 oxide per mole of secondary fatty alcohol.

The preferred nonionic surfactants for the compositions of the invention include the C12-C15 secondary fatty alcohols ethoxylated with 7-9 moles of ethylene oxide and the C-CL. fatty alcohols ethoxylated with 5-6 moles of ethylene oxide.

Mixtures of two or more of the liquid non-ionic surfactants can also be used, and in some cases this offers advantages.

The viscosity and gel-forming properties of the liquid detergent compositions can be improved by including in the composition an effective amount of a liquid nonionic surfactant with terminal acid group. These products consist of a nonionic surfactant compound, which is modified by converting a free hydroxyl group thereof into a molecular moiety with a free carboxyl group, such as an ester or a partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.

As described in U.S. Patent Application 597,948, filed April 9, 1984, the nonionic surfactants modified by introducing a free carboxyl group, which products can be characterized as polyether carboxylic acids, can lower the temperature at which the liquid nonionic compound forms a gel with water.

8702063 -14-

The addition of the nonionic surfactant with terminal acid group to the liquid nonionic surfactant promotes the dosability of the composition / especially the pourability, and lowers the temperature at which the liquid nonionic surfactant in water forms a gel without reducing settling stability. The nonionic surfactant with terminal acid group reacts in the washing machine water with the alkalinity of the dispersed build-up salt phase of the detergent composition and acts as an effective anionic surfactant.

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

The nonionic surfactant with terminal acid group can be prepared as follows: Product (A) with terminal acid group. 400 g of product (A), which is a C 1 -C 2 s alkanol, which has been alkoxylated by introducing 6 ethylene oxide and 3 propylene oxide units per alkanol unit, are mixed with 32 g succinic anhydride and at 100 ° C for 7 hours heated. The mixture is cooled and filtered to remove unreacted bam-tartaric acid material. Infrared analysis shows that about half of the nonionic surfactant has been converted to its acidic half-ester.

Dobanol 25-7 with terminal acid group. 522 g of Dobanol 25-7, which is the ethoxylation product of an alkanol with about 7 ethylene oxide units per molecule of alkanol, is mixed with 100 g of succinic anhydride and 0.1 g of pyridine (which acts as an esterification catalyst) and left for 2 hours. Heated to 260 ° C and then cooled and filtered to remove unconverted succinic acid material. Infrared analysis shows that virtually all free hydroxyl groups of the capillary surfactant have reacted.

8702063 -15-

Dobanol 91-5 with terminal acid group. 1000 g Dobanol 91-5, which is the ethoxylation product of a C 8 -C 20 alkanol, containing about 5 ethylene oxide units per molecule of alkanol, is mixed with 265 g succinic anhydride and 0.1 g pyridine catalyst for 2 hours at 260 ° C C heated and then cooled and filtered to remove unconverted succinic acid material. Infrared analysis shows that virtually all free hydroxyl groups of the surfactant have reacted.

Instead of or together with pyridine, other esterification catalysts can also be used, such as an alkali metal alkoxide, for example sodium methoxide.

The acidic polyether compound, i.e. the nonionic surfactant with terminal acid group, is preferably added dissolved in the nonionic surfactant. In the liquid non-aqueous non-ionic surfactant material used in the compositions of the invention, fine particles of inorganic and / or organic detergent builder salts are dispersed and suspended.

The detergent compositions of the invention contain water-soluble and / or water-insoluble detergent build-up salts. Water-soluble inorganic alkaline build-up salts, which can be used alone with the detergent compound or in conjunction with other builders, include alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates and silicates (ammonium or substituted ammonium may also be used). -25 salts are used). Examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexameta phosphate, sodium sesquicarbonate, sodium mono- and diorthophosphate and potassium bicarbonate. Sodium tripolyphosphate is particularly preferred.

Since the compositions of the invention are generally highly concentrated and can therefore be used in relatively small doses, it is desirable to supplement an optional phosphate builder salt (such as sodium tripolyphosphate) with an auxiliary builder, such as a poly-low carboxylic acid or a polymeric carboxylic acid with high calcium-binding capacity to inhibit crusting, which could otherwise be caused by the formation of an insoluble calcium phosphate.

8 / Ü2063 -16-

A suitable low polycarboxylic acid includes alkali metal salts of lower polycarboxylic acids, preferably the sodium and potassium salts. Suitable low polycarboxylic acids contain 2-4 carboxyl groups. The preferred sodium and potassium salts of low polycarboxylic acids are the salts of citric acid and tartaric acid. Most preferred are the sodium salts of citric acid, especially trisodium citrate. The mono-sodium and disodium citrates can also be used, as can the monosodium and disodium tartrates. The alkali metal salts of low polycarboxylic acids are particularly good build-up salts; because of their high capacity to bind calcium and magnesium, they inhibit crusting, which could otherwise be caused by the formation of insoluble calcium and magnesium salts.

To obtain a detergent composition that does not contain phosphate, the polyphosphates can be completely replaced by one or more of the auxiliary build-up salts.

Other organic builders are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their alkali metal salts. More specifically, such builder salts may consist of a copolymer, which is the reaction product of approximately equal molecular amounts of methacrylic acid and maleic anhydride, which is completely neutralized to form its sodium salt. The build-up salt is commercially available under the brand name Sokalan CP5. This build-up salt, even when used in small amounts, inhibits crusting.

Examples of organic alkaline sequestering builder salts which can be used with the detergent builder salts or together with other organic and inorganic builder salts are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, e.g. sodium and potassium ethylenediamine tetraacetate (EDTA), sodium and potassium nitrilotriacetates (NTA) and triethanolammonium N- (2-hydroxyethyl) nitrilo-30 diacetates. Also mixed salts of these aminopolycarboxylates can be used.

Other suitable organic or auxiliary builders of the organic type are carboxymethyl succinates, tartronates and glycolates.

The polyacetal carboxylates are of special value. The polyacetalcarboxylic xylates and their use in detergent compositions are described in U.S. Patent Application 767,570, filed August 19, 1985, and in U.S. Patents 4,144,226, 4,315,092, and 4,146,495.

8702063 -17-

The alkali metal silicates are suitable build-up salts, which also serve to adjust or control the pH and render the composition anti-corrosive to washing machine parts. Sodium silicates with Na2O / SiO2 ratios of 1.6 / 1 - 1 / 3.2, especially 1/2 - 1 / 2.8, are preferred. Potassium silicates with the same proportions can also be used.

Other typically suitable building materials are described, for example, in U.S. Patents 4,316,812, 4,264,466 and 3,630,929. The inorganic builder salts can be used with the nonionic surfactant detergent compound or together with other inorganic builder salts or with organic builder salts.

Furthermore, the water-insoluble crystalline and amorphous aluminosilicate zeolites can be used. The zeolites generally have the formula

15 (MO) · (Al_0) · (SiO) * wHO

2 X 2 3 y 2z 2 where x = 1, y = 0.8-1.2 and preferably 1.2 = 1.5-3.5 or more and preferably 2-3 and w = 0-9, preferably 2.5-6, and M preferably represents sodium. A typical zeolite is type A or similar structure, with type 4a being particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 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 1,504,168, U.S. Patent 4,409,136 and Canadian Pat. Nos. 1,072,835 and 1,087,477. An example of suitable amorphous zeolites can be found in Belgian patent 835,351.

Other materials, such as clay, especially of the water-insoluble types, may be useful adjuvants in compositions of the invention. Bentonite is particularly suitable. This material is mainly montmorillonite, which is a hydrated aluminum silicate, in which about 1/6 of the aluminum atoms can be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium and the like can be loosely combined. Bentonite in its more purified form (ie, free from grit, sand and the like), suitable for detergents, contains at least 50% montmorillonite and has 870 2 063 -18- a cation exchange capacity of at least 50-75 meq / 100 g bento not. Particularly preferred bentonites are the Wyoming or Western U.S. bentonites, produced by Georgia Kaolin Co. as Thixo-jels 1, 2, 3 and 4 are marketed. These bentonites are known to soften textiles, as described in British Pat. Nos. 401,413 and 461,221.

The inclusion in the detergent composition of an effective amount of low molecular weight amphiphilic compounds, which function as viscosity regulators and gel inhibitors for the nonionic surfactant, significantly improves the storage properties of the composition. The viscosity-controlling and gel-forming inhibitors lower the temperature at which the nonionic surfactant forms a gel upon addition to water. These agents can be, for example, low molecular weight alkylene oxide-low monoalkyl ether-amphiphilic compounds. The amphiphilic compounds may be considered analogous in chemical structure to the ethoxylated and / or propoxylated fatty alcohol liquid nonionic surfactants, but have relatively short hydrocarbon chain lengths (C-CQ) and low ethylene oxide content (about 2-6 ethylene oxide-20). groups per molecule).

Suitable amphiphilic compounds are represented by the general formula R1 2 1 · RO (CHCH-O) H 2 n 8702063 2 where R represents a C 1 -C 8 alkyl group and R represents hydrogen or methyl and 2 is a number with an average value of 1-6.

Specifically, the compounds are C-C-alkylene glycol mono-C-C 2 3 2 5 alkyl ethers.

More specifically, the compounds are mono-, di- or tri-C 1-6 alkylene glycol mono-C 1-6. alkyl ethers.

Specific examples of suitable amphiphilic compounds are ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether and dipropylene glycol monomethyl ether.

Diethylene glycol monobutyl ether is particularly preferred.

The inclusion in the composition of these alkylene glycol monoalkyl ethers reduces the viscosity of the composition such that it is easier to pour, improves settling stability, and improves dispersibility of the composition when added to hot water or cold water.

The compositions of the invention have improved viscosity and stability properties and remain stable and pourable at temperatures of 5 ° C and below.

In an embodiment of the invention, a stabilizing agent, which is an alkanol ester of phosphoric acid, can be added to the composition. Improvements in the stability of the composition can be achieved by incorporating a small effective amount of an acidic organic phosphorus compound with an acidic POH group, such as a partial ester of phosphorous acid and an alkanol. As disclosed in U.S. Patent Application 597,948, filed April 9, 1984, the acidic organic phosphorus compound having an acid -POH group can increase the stability of the builder suspension in the non-aqueous liquid nonionic surfactant. The acidic organic phosphorus compound can be, for example, a partial ester of phosphoric acid and an alcohol, such as an alkanol with a lipophilic character, for example, with more than 5 carbon atoms, such as 8-20 carbon atoms.

A specific example is a partial ester of phosphoric acid and a c16 "c18 alkanol (Empiphos 5632, Marchon). This product consists of about 35% monoester and 65% diester.

The inclusion of relatively small amounts, for example 0.3% by weight, of the acidic organic phosphorus compound makes the suspension stable against settling on standing, while the suspension remains pourable and while at the low stabilizer concentration, for example less than 1% , the plastic viscosity generally decreases.

Other bleach activators may be added to the composition as desired, such as tetraacetylethylenediamine, pentaacetyl glycose, acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetyl derivative, tetraacetyl derivative.

Other suitable classes of activators are described, for example, in U.S. Patents 4,111,826, 4,422,950, and 3,661,789.

The second bleach activator or auxiliary bleach activator may be added to supplement the calcium cyanamide bleach activator and to further reduce the temperature at which the peroxygen bleach becomes effective, for example below 60 ° C.

Furthermore, various other detergent additives or adjuvants may be present in the detergent product to impart further desirable properties of a functional or aesthetic nature. For example, minor amounts of soil suspending or anti-redeposition agents may be added to the mixture, for example, polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose.

A preferred anti-redeposition agent is sodium carboxy-methylcellulose with a CMC / MC ratio of 2: 1, which is commercially available under the trade name Relatin DM 4050.

Small amounts of fragrance can also be included in the composition, for example Duet 787, a perfume marketed by International Flavors and Fragrances. Duet 787 can be added in amounts of 0.3-1.0%, preferably 0.2-2.0%, for example 0.5-2%, such as 0.3-1.0%, based on the weight of the composition.

In addition, optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners are stilbene, triazole, and benzidine sulfone compositions, especially sulfonated-substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidenesulfone, and the like, with stilbene and triazole combinations being most preferred. A preferred brightener is Stilbene Brightener N4, a dianilino dimorpholinostilbene polysulfonate.

Enzymes can also be added, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin and pepsin, as well as enzymes of the amylase type, enzymes of the lypase type and mixtures thereof. Preferred enzymes are protease suspension, esperase suspension and amylase. A preferred enzyme to use is Esperase SL8, a proteolytic enzyme.

Anti-foaming agents, for example a silicon compound, such as Silicane L 7604, a silicone, can be added in small effective amounts.

Other additives include bactericides, for example, tetrachloro-35-salicylanilide and hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbing agents, such as sodium carboxymethyl cellulose, pH modifiers and pH buffers. color-safe bleaching agents, perfume and blue agents such as ultramarine blue.

In an embodiment of the invention, the stability of the build-up salts in the composition during storage and the dispersibility of the composition in water are improved by grinding and reducing the particle size of the solid builders to less than 100 µm, preferably less than 40 ym and preferably to less than 10 ym. The solid builder salts, for example sodium tripolyphosphate, are generally supplied in particle sizes of about 100, 200 or 400 µm. The nonionic liquid surfactant phase can be mixed with the solid build-up salts before or after grinding.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solids is treated in a friction type mill, in which the particle sizes of the solid ingredients are reduced to less than 10 µm, for example to an average particle size of 2 -10 ym or even less (eg 1 ym). Preferably less than 10%, especially less than 5% of all suspended particles have a particle size of more than 10 µm. Compositions in which the dispersed particles have such small dimensions have improved stability against separation or settling on storage. Addition of a nonionic surfactant with terminal acid group can decrease the yield stress of such dispersions and improve the dispersibility of the dispersions without correspondingly reducing the stability of the dispersions against settling.

When grinding, the solids content is preferably (e.g., at least 40%, such as about 50%) that the solids are in contact with each other and are not significantly shielded from each other by the nonionic surfactant. After grinding, any remaining amount of liquid nonionic surfactant can be added to the ground mixture.

Mills in which grinding balls (ball mills) or similar mobile grinding elements are used give very good results. For example, a laboratory mill with steatite grinding balls with a diameter of 8 mm can be used. For larger-scale work, a continuous working

870 2 0. Z

The mill are used, in which grinding balls with a diameter of 1 mm or 1.5 mm operate in a very small gap between a stator and a high speed rotating rotor (e.g. a CoBall mill); when using such a mill, it is desirable to first pass the mixture of nonionic surfactant and solids through a mill that does not grind as finely (eg, a colloid mill) to reduce the particle size to less than 100 µm (eg to about 40 µm), before the material is ground to an average particle diameter of less than about 10 µm in the continuous ball mill.

In the preferred liquid laundry detergent compositions of the invention, typical levels (percent based on the total weight of the composition, unless otherwise stated) of the ingredients are as follows:

Liquid nonionic surfactant detergent: 10-60%, such as 20-50%, for example 30-40%.

Nonionic surfactant with terminal acid group as viscosity improving agent: 0-20%, such as 3-15%, for example 4-10%.

Detergent build-up salt, such as sodium tripolyphosphate: 10-60%, such as 15-50%, for example 25-35%.

Copolymer of polyacrylate and polymaleic anhydride alkali metal salt, for example Sokalan CP5, anti-encrusting agent: 0-10%, such as 2-8%, for example 3-5%.

Alkylene glycol monoalkyl ether anti-gelling agent: 5-30%, such as 5-20%, for example 5-15%.

Phosphoric acid alkanol ester, stabilizing agent: 0-2.0% or 0.1-1.0%, such as 0.2-0.5%.

Bleach: 5-30%, such as 2-20%, for example 5-15%.

Calcium cyanamide bleach activator: 1-15%, such as 1-8%, for example, 2-6%.

Bleach sequestrant, e.g. Dequest 2066: 0-3.0%, preferably 0.5-2.0%, e.g. 0.75-1.25%.

Anti-redeposition agent, for example Relatin DM 4050: 0-4.0%, preferably 0.5-3.0%, for example 0.5-1.5%.

Optical brightener: 0-2.0%, preferably 0.05-1.0%, for example 0.15-0.75%.

8702065 -23-

Enzymes: 0-3.0%, preferably 0.5-2.0%, e.g. 0.75-1.25%.

Perfume: 0-3.0%, preferably 0.10-1.25%, e.g. 0.25-1.0%.

Several of the aforementioned additives can be added, if desired, to achieve the desired function of the added materials.

The calcium cyanamide bleach activator is preferably used with the alkylene glycol monoether and / or the nonionic surfactant with terminal acid group. In some cases, advantages can be achieved by using both the alkylene glycol monoether and the nonionic surfactant with terminal acid group.

The additives should, of course, be chosen to be compatible with the main components of the detergent composition.

As noted in this application, all levels and percentages refer to the weight of the entire mixture or composition unless otherwise stated.

In an embodiment of the invention, the detergent composition is formulated as follows:

Wt% 20 Non-ionic surfactant detergent 30-40

Surfactant with terminal acid group, viscosity enhancer 0-20

Phosphate detergent build-up salt 10-60

Anti-crusting agent 0-10 25 Alkylene glycol monoalkyl ether, anti-gelling agent 5-15

Phosphoric acid alkanol ester, stabilizer 0-2.0

Anti-redeposition agent 0-4.0

Alkali metal perborate bleach 5-15

Calcium Cyanamide Bleach 1.0-8.0 30 Bleach Sequestrant 0-3.0

Duet 787 0-3.0

Optical brightener 0.15-0.75

Enzymes 0.75-1.25

Perfume 0-3.0 8702063 ♦ -24-

The invention is further illustrated by the following examples.

EXAMPLE I

A concentrated non-aqueous liquid nonionic surfactant detergent composition is formulated as follows.

Wt. %

Non-ionic surfactant 38.8

Reaction product of Dobanol 91-5 with succinic anhydride 5.0 10 Sodium tripolyphosphate 29.6

Diethylene glycol monobutyl ether, anti-gelling agent 10

Phosphoric acid alkanol ester (Empiphos 5632) 0.3

Sodium perborate monohydrate 9.0

Calcium cyanamide 4.5 15 Anti-redeposition agent (Relatin DM 4050) ^ 1.0

Optical brightener 0.2

Perfume (Duet 787) 0.6

Enzyme (Esperase) 1.0 100.0 20 (1) CMC / MC 2: 1 mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose.

The mixture is ground for about 1 hour, reducing the particle size of the suspended builder salts to less than 40 µm. The composition thus obtained appears to be stable on storage and does not form a gel, is readily dispersible in water and has good bleaching properties and improved detergent properties.

8702063 τ -25-

VCX) FIGURE II

A concentrated non-aqueous liquid nonionic surfactant detergent composition is formulated as follows.

Wt. % 5 Non-ionic surfactant material, Product D 13.5

Surfactant T7 10

Surfactant T9 10

Reaction product of Dobanol 91-5 with succinic anhydride 5 10 Sodium tripolyphosphate 29.6

Anti-crusting agent (Sokalan CP5) 4.0

Diethylene glycol monobutyl ether 10

Phosphoric acid alkanol ester (Empiphos 5632) 0.3

Sodium perborate monohydrate 9 15 Calcium cyanamide 4.5

Bleach Sequestrant (Dequest 2066) 1.0

Anti-redeposition agent (Relatin DM 4050) ^ 1.0

Optical brightener (stilbene) 0.5

Enzyme (Esperase suspension) 1.0 20 Duet 787 0.6 100.0 (1) CMC / MC 2: 1 mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose.

The mixture is ground for about 1 hour, reducing the particle size of the suspended builder salts to less than 40 µm. The composition thus obtained appears to be stable on storage and does not form a gel, and is readily dispersible in water.

The bleach is active at 60 ° C on immediate black. The calcium cyanide concentration of 4.5% gave an ARd = 5.3, while in the absence of the activator the ARd was 0.8. The pH of the aqueous wash water without the bleach activator was 9.6, with 4.5% calcium cyanamide activator 9.9, and 4.5% TAED activator 9.0.

The mixtures of Examples I and II can be prepared to a small particle size without grinding the build-up salts and suspended solids, but the best results are obtained by grinding the mixture 8702 063-26 to reduce the particle size of the suspended solid material.

The builder salts can be used in the form in which they are supplied, or the builder salts and suspended solids 5 can be ground or partially ground before mixing with the nonionic surfactant. The grinding can be performed partially before mixing and then completed after mixing or the entire grinding treatment can be performed after mixing with the liquid surfactant. The compositions containing solid particles of less than 40 μπι are preferred.

8702065

Claims (19)

1. Detergent composition for the treatment of fabrics, characterized by a non-ionic surfactant material, an inorganic peroxygen compound as bleach and calcium cyanamide as bleach activator. Composition according to claim 1, characterized by a viscosity regulating and anti-gel-forming agent. 3. A composition according to claim 2, characterized by at least one viscosity regulating and anti-gel-forming agent selected from alkylene glycol monoalkyl ether and nonionic surfactant with terminal acid group. Composition according to claims 1-3, characterized by a suspension of insoluble inorganic build-up salts. Composition according to claim 4, characterized in that the build-up salt comprises alkali metal polyphosphate. Composition according to claims 4-5, characterized in that the insoluble inorganic build-up salt contains 10-60% of a polyphosphate detergent build-up salt. 7. A composition according to claims 1-6, characterized by one or more detergent auxiliaries selected from anti-encrusting agent, sequestering agent, anti-redeposition agent, optical brightener, enzymes and perfume. Composition according to claims 1-7, characterized by 10-60% of a non-ionic liquid surfactant. Composition according to claim 3, characterized by 5-30% of an alkylene glycol monoalkyl ether. 10 Phosphoric acid alkanol ester 0.2-0.5 Sodium perborate monohydrate as bleach 5-15 Calcium cyanamide 2-6.0 Bleach sequestrant 0.75-1.25 Anti-redeposition agent 0.5-1.5 Composition according to claim 4, characterized in that the inorganic build-up salt has a particle size of less than 40 µm. Composition according to claims 1-10, characterized by 0.1-0.5% by weight of a phosphoric acid alkanol ester as a stabilizing anti-settling agent, based on the total composition. 12. Non-aqueous build-up laundry detergent composition, which can be poured at high and low temperatures and does not form a gel when mixed with cold water, characterized by at least one liquid nonionic surfactant in an amount of 10-60% by weight, at least one inorganic detergent build-up salt, suspended in the non-ionic surfactant in an amount of 10-60 wt%, an inorganic peroxygen bleach in an amount of 5-15 wt%, calcium cyanamide as bleach activator in an amount of 1-8 wt%, a nonionic surfactant with terminal acid group 5 as a gel-inhibiting additive, in an amount of 0-20 wt%, and a compound of the formula R2 R1 © (CHCH 0) H 2 n 1 2 wherein R represents a C 1 -C 8 alkyl group and R represents hydrogen or methyl and Z on is a number having an average value of 1-6 as a gel-inhibiting additive in an amount of 5-30% by weight. Composition according to claim 12, characterized by one or more detergent auxiliaries selected from anti-encrustant, sequestrant, anti-redeposition agent, optical brightener, enzymes and perfume. Composition according to claim 12, characterized by: Composition according to claim 12 / characterized by:% by weight Nonionic surfactant material 30-40 Nonionic surfactant with terminal 5 acid group as viscosity improving agent 3-15 Sodium tripolyphosphate 25-35 Copolymer of polyacrylate and polymaleic anhydride sodium salt 3 -5 Diethylene glycol monobutyl ether 5-15 15% by weight Nonionic surfactant 20-50 Nonionic surfactant with terminal acid group as viscosity improving agent 3-15 Sodium tripolyphosphate 15-50 20 Copolymer of polyacrylate and polymalelic anhydride sodium salt 2-8 Diethylene glycol monoalkyl ether 5-20 Phosphoric acid alkanol ester 0.1-1.0 Sodium perborate monohydrate as bleach 2-20 25 Calcium cyanamide 1-8 8702063 • f -29- A method for cleaning dirty fabrics, characterized in that the dirty fabrics are brought into contact with the detergent composition according to claim 1. Method according to claim 16, characterized in that the soiled fabrics are brought into contact with the detergent composition according to claim 12. Method according to claim 16, characterized in that the soiled fabrics are brought into contact with the detergent composition according to claim 14. 19. A method according to claim 16, characterized in that the soiled fabrics are brought into contact with the detergent composition according to claim 15. 8702063