NO144173B - DETERGENT. - Google Patents

Description

Common heavy-duty laundry detergents for household purposes, e.g.

for automatic washing machines, contains relatively large amounts of phosphates. Thus contains e.g. a powerful washing

average approx. 33% pentasodium tripolyphosphate together with approx. 10%

linear sodium alkylbenzene sulfonate ("LAS")/ 2% soap, 2% non-

ionic detergent active material, 0.5% carboxymethylcellulose and 7.5% sodium silicate. Due to the widespread belief that the use of phosphates may be ecologically undesirable, a number of LAS-containing detergents have been introduced which are essentially free of phosphates. However, these do not have the high cleaning power of the above-mentioned phosphate detergents and often present problems, such as health risks, damage to automatic washing machines and an unwanted grip on the washed clothes. The phosphate-free detergents or detergents with a low phosphate content that have recently been marketed include the detergents A-T whose percentage composition is given in the table I below.

Detergents containing relatively large amounts of sodium silicate are also known, see e.g. the mention in the articles by Merrill

and Getty "Alkyl Aryl Sulfonate-Builder Mixtures", Ind. and Eng.

Chem., £2, 856ff (May 1950), bg Schleyer "Silicates in Detergents", Soap and Chemical Specialties, November and December 1959, and also U.S. patent document no. 3272753 and the article by Katstra "Formulating Detergents With Less Phosphate" in Soap and Chemical Specialties, February 1971. US patent document 3272753 relates to liquid detergents, and the anionic detergent active materials

alers according to the US patent document and the aforementioned articles are alkylaryl sulfonates. In addition, a hydrotropic salt must be present in the detergent according to the US patent, and the detergent's pH is at least approx. 11.

French patent document 1590487 deals with dry, powdered detergent products containing anionic linear tridecyl-benzene sodium sulfonate, sodium sulfate, non-ionic condensation product of a primary alcohol and polyethylene oxide, sodium carboxymethylcellulose as antigen deposition agent, polyvinyl alcohol, soap, trisodium nitrilotriacetate as building material and smaller amounts of other ingredients. The known detergent product does not contain sodium silicate.

In a recent article in Soap and Chemical Specialties, June 1971, by Louis McDonald, it is expressed in connection with alkali metal silicates in detergents: "The main disadvantages of these are that they must be used at relatively high pH values of 11.6 or above and that they must be used in soft water. Otherwise, they will form a connection with the calcium and magnesium in hard water and lead to the deposition of a residue or cheese-like mass on the material being cleaned. The alkali metal silicates have long been used with good results together with fatty acid soaps for washing in soft water, at high temperatures (82°C) and at high pH values."

According to the invention, an essentially phosphate-free laundry detergent is provided which has an equally good or better cleaning power than the above-mentioned detergents with a high content of phosphate. The detergent according to the invention has been shown to be very effective against a number of different types of dirt, including clay and carbon dirt, skin dirt, natural and artificial skin fat dirt and particulate dirt etc., and also in yellowing tests of clean laundry, in connection with a number various textile materials, including cotton, nylon and polyester (e.g. polyethylene terephthalate) etc. In contrast to the known essentially phosphate-free detergents, the detergents according to the invention therefore represent a full-fledged replacement for detergents with a high phosphate content. This has also been proven using repeated tests in connection with ordinary household laundry. The new detergents according to the invention do not lead to high pH values and are effective in hard water without causing a significant formation of residues or cheese-like mass. Experiments performed with a calcium ion electrode and turbidity measurements

have shown that the detergents according to the invention, in contrast to ordinary phosphate-containing detergents, do not include compounds with significant amounts of calcium ions.

According to the invention, it has been shown that these excellent results can be achieved with a particulate detergent with a pH below 11 in the washing bath, and the detergent is characterized by

it essentially consists of the combination of (a) an anionic detergent-active olefin sulfonate or paraffin sulfonate, (b) sodium silicate, (c) a non-ionic detergent-active material and (d) a water-soluble antigen re-deposition polymer, the ratio of components (a) and (b) is 2:1 - 1:2, between the components

(a) and (c) 15:1 - 4:1 and between components (a) and (d) 90:1-

6:1, and the amount of component (c) is at least 4% of the total weight of component (a) plus component (b).

The amount of the non-ionic detergent active material is as

rule 4-10% of the total weight of the components (a) plus (b),

and the ratios (a) : (b) , (a) : (c) and (a) : (d) are preferably respectively 5:3-3:4, over 6:1 and over 8:1.

The detergent preferably does not contain sodium carbonate,

but it will be understood that according to the invention, if desired, smaller quantities of sodium carbonate can be added which do not exert any significant effect on the properties of the detergent, e.g. 5% sodium carbonate, based on the weight of the olefin sulfonate. . Detergent olefin sulfonates are well known in the art. They generally contain long-chain alkenylsulfonates or long-chain hydroxyalkanesulfonates, the OH group being on a

carbon atom that is not directly bonded to the carbon atom that is bonded to the SO3~ group. The detergent-active olefin sulphonate is usually made up of a mixture of these two types of compounds in varying amounts, often together with long-chain disulphonates or sulphate sulphonates. Such olefin sulfonates are described in a number of patents, such as U.S. Pat. Patent Documents No. 2061618, No. 3409637, No. 3332880, No. 3420875, No. 3428654 and No. 3506580, in British Patent Document No. 1139158 and in an article by Baumann et al in Fette-Seifen-Anstrichmittel, 72, no. 4, pp. 247-253 (1979). As stated in these patents and in the published literature otherwise, the olefin sulfonates can be prepared from straight-chain α-olefins, internal olefins, olefins in which the unsaturation is located in a vinylidene side chain (e.g. dimers of α-olefins) etc. or, more commonly , from mixtures of such compounds in which the α-olefin usually forms the main component.

The sulphonation is usually carried out with sulfur trioxide at low partial pressure, e.g. with SO3 which is highly diluted with an inert gas, such as air or nitrogen, or with SO^ under vacuum. With this turnover, one is generally obtained. alkenyl sulfonic acid, often together with a sultone. The resulting acidic material is then usually made alkaline and treated to open the sulfone ring to form hydroxyalkanesulfonate and alkenylsulfonate. The number of carbon atoms in the olefin is usually 10-25, usually 12-20, e.g. a mixture of olefins with mainly 12, 14 and 16 carbon atoms and with an average of approx. 14 carbon atoms, or a mixture of olefins with mainly 14, 16 and 18 carbon atoms and with an average of approx. 16 carbon atoms. The preferred olefin sulphonates are the sodium salts, but according to the invention, other water-soluble salts, such as ammonium or potassium salts, can also be used.

Part or even the entire amount of the olefin sulfonate can be replaced with a paraffin sulfonate, such as a paraffin sulfonate with 10-20 carbon atoms. These can be made up of the primary paraffin sulphonates obtained by reaction of long-chain α-olefins and bisulphites (e.g. sodium bisulphite), or of paraffin sulphonates in which the sulphonate groups are distributed along the paraffin chain, such as the products obtained by reaction of a long-chain paraffin with sulfur dioxide and oxygen under ultraviolet light, followed by neutralization with NaOH or another proper base, such as e.g. described in US patent documents no. 2503280, no. 2507088,

no. 3260741 and no. 3372188 and in German patent document no. 735096.

Very good results have often been obtained by using paraffin sulphonates which have an average carbon chain length (e.g. of 15-16 carbon atoms) which is considerably shorter than the chain previously thought to be the optimum for heavy duty phosphate detergents (see the article by Black and Associates in Soap/Cosmetics Chemical Specialties, November 1971, pp. 37ff, especially Table V on page ^-2).

The sodium silicate used according to the invention has a weight ratio Na20:SiO2 of approx. 1:2-1:3. It can be supplied in the form of a powder or granule. or as a liquid aqueous solution. It can be added to the mixture from the mixing device ("crutcher") used for spray drying the product, or it can be added afterwards to the spray-dried grains or a part can be introduced into the mixture from the mixing device and a part can be added afterwards. It is also possible according to the invention, although this is less preferred, to use a sodium silicate with a weight ratio Na20:SiO2 of 1:1.6 to supply the entire amount or part of the sodium silicate content.

The non-ionic detergent-active material used according to the invention is preferably a monoether of a polyethylene glycol and a long-chain alkanol, of which the alkanol contains 10-16 carbon atoms and the polyethylene glycol 5-15 oxyethylene units. Such monoethers of polyethylene glycol are usually prepared by reacting the alkanol with ethylene oxide. The relative amount of ethylene oxide is preferably 60-65%. A particularly suitable product is prepared by reacting 11 mol of ethylene oxide and 1 mol of a mixture of straight-chain, primary n-alkanols with 1^--15 carbon atoms, e.g. average approx. l<*>+.5 carbon atoms, and this product is sold under the trademark "Neodol" h^ ll. An otherwise identical product ("Neodol" <1>+513) can also be used in which the molar ratio is 13:1 instead of 11:1, or a similar product, if an addition product ("Neodol" 25-7)

of 7 mol of ethylene oxide and 1 mol of a mixture of alkanols with 12-15 carbon atoms. Another non-ionic detergent-active material is an ether of polyethylene glycol and a mixture of alcohols with 16-18 carbon atoms and containing approx. 60% or 65% ethylene oxide (Alfonii<®>1618-60 or Alfonic<®>1618-65). Another non-ionic detergent active material is made from a condensation product of a long-chain alkanol, propylene oxide and ethylene oxide and is sold under the trade name Plurafac^B26. According to the invention, it has been shown that the non-ionic, washing-active material is of significant importance in order to

now generally good washing properties which are equivalent to or better than the washing properties of detergents with a high phosphate content, essentially in the absence of carbonates.

The detergent preferably also contains small amounts of a fluorescent whitening agent. Such whitening agents are well known and may be of the coumarin type as described in U.S. Pat. Patents No. 2590^-85, No. 2600375, No. 2610152, No. 26>+7132, No. 26^+7133, No. 279156*+ and No. 2882186, of the triazolylstilbene types as described in U.S. Pat. patent documents No. 2668777, No. 268M-966, No. 2713057, No. 278<I>+I83, No. 278<l>+197, No. 2817665, No. §907760, No. 2927866 and No. 2993892, of the stilbene-cyanurin types as described in U.S. Pat. patent documents no. 2V73V75,

No. 2526668, No. 2595030, No. 2618636, No. 265806<*>+, No. 2658065,

No. 2660578, No. 2666052, No. 269<1>+06<1>+ and No. 28V0557, of the acylamino-stilbene types as described in U.S. Pat. patent documents no. 2081+1+13,

No. 2<1>+68<1>+31, No. 2521665, No. 2528323, No. 2581057, No. 262306<*>+,

Nos. 2671+601+ and Nos. 26767982, or of various types as described in U.S. Pat. patent documents no. 29111+15 and no. 303l!+60. The quantity of the whitening agent can be e.g. about. 0.05-1$, e.g. 0.1-0.5$. A suitable combination of whiteners contains (a) a naphthotriazole stilbenesulfonate whitener consisting of sodium 2-sulfo-1+-(2-naphtho-1,2-triazolyl)-stilbene, (b) another ivory whitener consisting of bis-( aniline-diethano]aminetriazinyl)-stilbenesulphonic acid, (c) another stilbene whitening agent consisting of sodium bis-(aniline mor'fqlintriazinyl)-stilbenesulphonate and (d) an oxazol hyite agent having a 1-phenyl-2-benzoxazolethylene structure and consisting of 2- styrylnaphth-|. 1,2 d]-oxazole, in the ratios a:b:c:d of approx. 1:1:3:1,2.

Other ingredients that can be used include antifoaming agents. For this purpose, soap, a high molecular weight amide or an antifoam amine, such as N,N-dilauryl (or dicoco alcohol) amine, can be used in small amounts of e.g. 0.5-8$ of the total detergent. Other useful antifoam agents are silicones, e.g. a dimethylsiloxane polymer, which can be used in very small amounts, e.g. 0.1$, as the only antifoam agent

or together with other antifoam agents. Sodium sulfate is usually also present as a dilution forge1. When the detergent is relatively concentrated, the amount of sodium sulphate is usually well below 25% of the total detergent. Larger amounts of this dilution forged 1 may be present in less concentrated detergents which are intended for addition in large portions to washing machines.

The detergent may possibly also contain smaller amounts of sodium perborate. This ingredient has proven particularly useful for increasing the washing power of detergents that contain less than the optimum amounts of olefin sulphonate and silicate. The detergent can thus contain 5-15% sodium perborate tetrahydrate (which is equivalent to

0.5-1.5$ active oxygen in the detergent), and improved results are obtained even when washing is carried out at room temperature or as low temperatures as e.g. <1>+9°C or 60°C which is far below the temperatures where sodium perborate is known to produce an effective bleaching effect. Other peroxygen compounds which emit active oxygen in solution in a similar way to perborate can replace the perborate in whole or in part. Such compounds are well known in the art, and e.g. sodium percarbonate (e.g. Na2C02.1.5H2O2) can be used.

According to the invention, smaller amounts of other building salts can also be introduced into the present detergents. Among such salts can be mentioned trisodium nitrile triacetate ("NTA"), disodium hydroxyethyl nitrile diacetate ("HEIDA"), sodium citrate, sodium boron glucoheptanoate and even phosphates, such as pentasodium tripolyphosphate or tetrasodium pyrophosphate, sodium polycarboxylates, e.g. low molecular weight polymaleates (usually below 1000, e.g. <*>+00, 600 or 800), or polyphosphonic acids, such as NtCR^PO^)^ (Dequest® 2000) , (H^O^PCR^) - N-CH2CH2-N-(CH2P03H2)2, CH^CCB^)-^ NCCHgPO^H^ ( Dequest® 2011) , CH^CH (PCUH)2, CH2(0H) P0^H2 or its sodium salts (e.g. .Dequesi?™' 2006). Such added building salts can be present in an amount below approx. 20$, preferably under 15$, e.g. about. 5, 10 or 12$, of the total weight of sodium silicate plus olefin sulfonates and less than half of the weight of the sodium silicate. In the examples, all amounts are based on weight unless otherwise stated.

Example 1

(a) A suitable detergent contained <1>+0$ olef insulf onate, 1+0$ sodium silicate with a weight ratio Na20:SiO2 of 1:2.35, h% "Neodol" <1>+5-11, 2$ sodium carboxymethylcellulose which was water-soluble and of the usual detergent quality, and the rest sodium sulphate and approx. 5$ water. The above-mentioned mixture can be used in the form of spray-dried grains. All components can thus be vigorously stirred in a conventional mixing device ("crutcher"), as the olefin sulfonate is added as an aqueous dispersion containing hO- h^ fo active ingredient (with the remainder consisting of water, some sodium sulfate■and small amounts of common impurities formed during sulfonation) , and the sodium silicate is added in the form of an aqueous liquid containing 56.5$ of water. The mixture can be transferred from the mixer to spray nozzles arranged at the top of a spray tower which are supplied with hot air for drying, and the resulting hollow grains can be collected at the bottom of the tower. (b) Example 1(a) was repeated, but with the change that sodium carboxymethylcellulose was omitted from the mixture from the mixer and instead added in the form of granules to the spray-dried granules. When this mixture was dissolved in deionized water at a concentration of 0.15%, the solution obtained a pH of 9.9. (c) Example Ka) was repeated, but with the change that the mixture contained 2% of a dicocosamine (Armeer* 2C) to reduce foaming in an automatic washing machine. (d) Example Kb) was repeated, but with the change that 5% soap (sodium soap of 80% tallow fatty acids and 20% coconut oil fatty acids) was introduced into the agent to reduce foam formation in an automatic washing machine.

Example 2

Example 1 was repeated, but with the change that the amount of olefin sulphonate was 25% and the amount of sodium silicate 25%.

Example 3

Example 1 was repeated, but with the change that the amount of olefin sulphonate was 32% and the amount of sodium silicate 26%.

Example <*>+

Example 1 was repeated, but with the change that the amount of olefin sulphonate was 25%, the amount of sodium silicate 30% and that granular sodium perborate tetrahydrate was also subsequently added to the spray-dried grains in such a quantity that approx. 15$ NaBO-^.^B^O was included in the final product.

Example 5

Example <1>+ was repeated, but with the change that the amount of olefin sulphonate was 30% and the amount of sodium silicate h0%.

Example . 6 -

Each of the above examples was repeated, but with the change that during the mixing, 6/10 of the total amount of sodium silicate was added to the mixing apparatus in the aqueous form described in example 1, and h/10 of the total amount of sodium silicate was subsequently added to the spray-dried grains or spheres in the form of sodium silicate grains with a weight ratio Na20:SiO2 of 1:2 and with a water content of 18.5$.

Example 7

Examples 1-5 were repeated using a sodium silicate with a Na23:SiO2 weight ratio of 1:2.0.

Example 8

Each of the above examples was repeated, but with the change that 1% fluorescent whitening agents were introduced into the mixture.

The olefin sulfonate used in the above examples was prepared from an olefin mixture containing 78% α-olefins, 7-8% internal olefins, 1h-15% olefins with a pendant =CH2 group (i.e.

with a vinylidene group) and 0.1$ paraffins, the mixture containing 1.7$ olefins with 12 carbon atoms, 65$ olefins with 1<*>+ carbon atoms, 33.2$ olefins with 16 carbon atoms and 0.1$ olefins with 18 carbon atoms. The reaction was carried out in the following usual way: the olefin was sulphonated with SO^ which was strongly diluted with air, a little over 1 mol of SO^ being used per moles of olefin, after which the acidic mixture was made alkaline with an excess of aqueous NaOH to convert alkenylsulfonic acids formed during the sulfonation into the corresponding sodium salts, and the resulting alkaline mixture was heated at an elevated temperature (e.g. 171° C) at superatmospheric pressure to convert sultones which had been formed during the sulphonation to the corresponding sodium hydroxyalkanesulphonates and -alkenyl sulphonates. Similar results were obtained by repeating the above examples

using olefin sulphonates prepared in the same way from (a)

a 1:1:1 mixture of 1-dodecene, 1-tetradecene and 1-hexadecene, from (b) 1-hexadecene or from (c) a l:^:^:! mixture of 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

Example 9

The detergent according to example 1 (b) was in a concen-

tion of 0.15$ added to water with a hardness of 150 parts per million (expressed in the usual way as ppm calcium carbonate). The water was a mixture of distilled water, CaCl2 and MgCl2, the latter components being present in such quantities that the water contained 36 ppm Ca ions and 1<*>+.6 ppm Mg ions. After vigorous mixing for 10 minutes, the concentration of unbound calcium (as indicated by the electrical potential of a calcium electrode in contact with the solution), pH and turbidity were measured. During the experiment, the water temperature was kept at 50°C. The results obtained are reproduced in Table II together with the results for certain commercially available detergents.

For the experiments reproduced above, all detergents were used in a concentration of 0.15$ if nothing else is indicated.

The opacity was measured with a standard color measuring device (model

k-01 from Photovolt Corp., New York) using lamp light and et

green filter. In this turbidity measurement (after 10 minutes) the hard water itself showed a turbidity of 0, the same hard water containing 0.0h5% Na2C0^ a turbidity of 66 and the same hard water containing 0.03$ LAS a turbidity of approx. 90-

The calcium electrode used for the measurement was a model 92-20 calcium activity electrode sold by Orion Research Inc., Cambridge, Massachusetts, and is described in detail

in the published instructions for use for this instrument. The electrode develops an electric potential over a thin layer of a water-immiscible ion exchange liquid. The liquid is held mechanically in place by means of a thin, porous, inert membrane disk. The ion exchange liquid, which is

a calcium salt of an organophosphoric acid, exhibits a very high specificity for calcium ions. An internally filled solution of calcium chloride came into contact with the internal surface of the membrane disk. The calcium ions in the solution provide a stable potential between the inside of the membrane and the filled solution, while the chloride ions provide a stable potential between the Ag-AgCl reference electrode and the filled solution. Changes in the potential are thus only due to changes in the calcium ion activity in the sample. The electrode is only affected by the ionized or unbound calcium in the sample and not by the part of the calcium that is bound to complexing agents, such as citrates, polyphosphates and some proteins. According to the manufacturer of this electrode, this has a Nernst potential structure down to 10_1+ mol of calcium ions per litres, in accordance with the following equation:

where E = the electrode potential, Ex = approx. 90 mV with a saturated KC1-

calomel reference electrode,

= the Nernst potential factor of the divalent electrode probe

(29.58 mV at 25 C), and

A^a<++><=> the calcium ion activity.

For measuring the calcium electrode potentials reproduced in Table II, the relative scale is first adjusted so that the potential for the hard water as such becomes -5 mV. For the sake of comparison, it must be

it is noted that the same instrument with the same regulation gives the following readings in connection with 0.0<1>+5$-i solutions (regulated to a pH of 10.0 with NaOH) of the following compounds in the same hard water (with a hardness of 150 ppm): trisodium salt of nitrile triacetic acid .C'NTA") = -75 mV, pentasodium tripolyphosphate = -55 mV, sodium citrate = - K2 mV, sodium acetamide nitrile diacetate = -36. mV, iminodiacetic acid = -12 mV and sodium oxalate =. - 38 mV. For further comparison, experiments in connection with the water as such which had been adjusted to a pH of 10.0 by means of NaOH (with hard-

the heat changed by changing the total amount of "CaClv) Pg Mg Sig", but not the relative amounts between these) the following readings: 50 ppm hardness (as CaCO^) = -20 mV, 25 ppm hardness - -27, 5 mV and 300 ppm hardness = +5 mV. This can be compared with the -5 mV that was obtained for the water with a hardness of 150 ppm, and with the approx. -80 mV

which was obtained for water with a hardness of 0. In each case the measurements were made after 10 minutes of stirring, as mentioned above.

It appears that the preferred detergents according to the invention give

a relatively low turbidity (e.g. well below 30$ and usually below 25$, e.g. within the range 5-15$) dg bind relatively little calcium (e.g. they give calcium electrode potentials above approx. -25 mV , e.g.

within the range -5 to -15 mV).

Example 10

Example 1 (d) was repeated, but with the change that the amount of sodium silicate was reduced to 33%.

Example 11

Example 1 (d) was repeated, but with the change that the amounts of olefin sulfonate and sodium silicate were both reduced to 25% and the amount of soap to 1%.

Example 1?

Example 1 (d) was repeated, but with the change that the amount of olefin sulphonate was lowered to 18$, the amount of sodium silicate to 25$ and the amount of soap increased to 6$. It appears that in this example the ratio between the total amount of anionic detergent-active material (olefin sulphonate plus soap) and non-ionic detergent-active material was approx. 6:1. The detergent produced low foam formation in an automatic washing machine and had excellent cleaning power on cotton clothes.

Example- 13

Example 12 was repeated, but instead of the olefin sulfonate, a sodium paraffin sulfonate with the following chain length distribution (determined by analysis) was used: 5$ C^ in 16$ C±l+, 30$ C-^, 30$ C"l6, 15$ C±7 and h% C-j^g This paraffin insulfonate also contained about 10$ (based on the total content of active ingredients) disulfonates.

Example 14

In the detergents according to each of the above examples, a mixture of two compatible blue dyes with different shades, but with essentially the same adhesion to the fabric tby, was introduced, so that the washed tby (after drying) acquired a faint blue color tone. More specifically, the dyes had the property that if they had been used independently of each other, they would have colored the toy or greenish blue and root blue. The dyes added and their amounts were 0.001$ "Direct Brilliant Sky Blue 6B" (reference no. 2M+10, color index direct blue 1) and 0.0003$ "Solophenyl Violet <i>+BL"

(reference no. 29120, color index direct violet 66).

Instead of this particular pair of blue dyes, a mixture of 0.002$ "Verona Alizarine Brilliant Sky Blue.:RW" and 0.001$ "Verona Sirius Supra Blue BRL" can be used.

Example . 15

In the detergents according to each of the above examples, a small amount (such as 0.1-0,<*>+$, e.g. 0.2 or 0.3$) of a fluorescent whitening agent stable to bleaches was introduced, which *+,*+'-bis-(<1>+-phenyr-2H-1,2,3-triazol-2-yl)-2,2'-stilbenisulfonic acid or a salt thereof (e.g. an alkali metal salt, especially potassium salt).

Example 16

Instead of the blue dyes according to example 14, ultra-marine blue was used in an amount of approx. 0.06$. In a particularly good detergent there was also present 10$ of sodium perborate and approx. 0.3$ of a fluorescent whitening agent stable against bleaching agents, such as the whitening agent described in example 15.

The available detergents can be used both in warm water.

(e.g. with a temperature of <1>+9°C, 60°C or above)' and in cold water (e.g. with a temperature of 38°C, 27°C, 21°C or below ). The water can be bare or hard (e.g. with a hardness, expressed

as calcium carbonate, of 50, 100, 150 or 200<:>ppm).' The amount of detergent added to the washing water is usually such that a concentration of washing-active sulphonate in the water of 0.02-0.1$ is obtained. The detergents according to the examples (in which the content of detergent-active sulfonate is l5-<1>+5$, the sodium silicate content approx.-.20-*+0$, the content of non-ionic, detergent-active material up to approx. -3$) is specially prepared for use in a concentration of 0.1-0.2$, more precisely approx. 0.15$,

of the entire detergent in the wash water, and for use during a normal wash cycle, e.g. washing with the tbyet in motion for 5-20 minutes, usually approx. 10 minutes, followed by a suitable, removal of washing water from the tbyet, e.g. by centrifugation, and rinsing. The detergents according to the invention give excellent results in connection with toys consisting only of cotton and with toys containing synthetic fibres, such as fibers with low moisture absorption, e.g. nylon or polyethylene terephthalate, alone or mixed with cellulose fibers, such as cotton or rayon.

The washed toy does not get an unwanted grip, and the detergents

are very safe to use and suitable for automatic washing machines. In comparative experiments with bundles of laundry, it has also surprisingly been shown that as further washing takes place (as the laundry is subjected to a third, fourth and fifth etc. soiling and a corresponding third, fourth and fifth etc. washing at the same time detergent), the detergents according to the invention give better results compared to ordinary coarse detergents with a high phosphate content.

A smaller amount of other ingredients can be introduced into the present detergents, e.g. germicides, activators for peroxygen compounds, textile softeners, enzymes, perfumes, coloring materials and antistaining agents, etc. Examples of germicides include tetrachlorosalicyl anilide and hexachlorophene, as examples of enzymes, alkaline proteases (such as the subtilisin protease sold under the name Alcalase ®, eg 0.1-1%, eg about 0.5% Alcalase<®> P

with a proteolytic enzyme activity of 1.5 Anson units per grams, in the form of pelletized, finely divided spheres of a mixture of non-ionic, detergent-active material and the enzyme which is a subtilisin enzyme with a proteolytic activity measured at a pH of 7.3, but which has its highest activity at a pH of 8-9 and amylases (e.g. α-amylase), and on activators for peroxygen compounds, the activators forming peracetic acid, perbenzoic acid or other peracid compounds in the wash water, the activator compounds described in U.S. U.S. Patent No. 3,532,634 which also discloses various suitable peroxygen compounds. Bleaching can also be carried out by introducing solid materials into the detergents which react with the washing water to form hypochlorite chlorine or hypobromite bromine. Among such materials can be mentioned N-bromo- and N-chloroimides, such as the heterocyclic imides such as trichlorocyanuric acid, tribromocyanuric acid, dibromocyanuric acid, dichlorocyanuric acid^

acid and salts thereof with water-solubilizing cations, such as sodium or potassium cations. Although clothes washed with the available detergents generally have the desired soft grip,

for certain purposes, it may be desirable to introduce softeners into the detergents that work during the wash cycle, e.g. 1,2-alkane diols with 15-18 carbon atoms. Another suitable additive is borax.

Other suitable additives are fat solvents, such as ethylene oxide addition products with a low content of ethylene oxide, such as addition products of long-chain alkanols, e.g. the addition products of 3 or 4 moles of ethylene oxide and 1 mole of a mixture of alkanols with 12-15 carbon atoms (such as "Neodol" 25-3 or "Neodol" 25-4).

Further suitable additives are those which can be used as "carriers" for a liquid, non-ionic, detergent-active material to thereby make granular detergents flow better. Of such additives, absorbent silicon dioxide grades or other finely divided mineral<p>wolves, such as Cab-O-Sil<®>, Satintone^ , granular TPF or also sodium carbonate in small quantities can be mentioned.

The detergent-active materials preferably used according to the invention are of course soluble in water in the same way as the sodium silicate.

Claims (3)

X. Particulate, phosphate-free detergent with a pH below 11 in the wash bath, characterized in that it essentially consists of the combination of (a) an anionic, detergent-active olefin sulfonate or paraffin sulfonate, (b) sodium silicate, (c) a non-ionic, detergent-active material and (d) a water-soluble antigen deposition polymer, the ratio between components (a) and (b) being 2:1-1:2, between components (a) and (c) 15:1-4:1 and between components (a ) and (d) 90:1-6:1, and the amount of component (c) is at least 4% of the total weight of component (a) plus component (b). 2. Detergent according to claim 1, characterized in that it has a pH below 10 in the washing bath and that the water-soluble antigen deposition polymer is sodium carboxymethylcellulose and the amount of component (c) is 4-10% of the total weight of component (a) plus component (b). 3. Detergent according to claim 1 or 2, characterized in that the olefin sulfonate is a mixture of long-chain sodium alkenyl sulfonates and long-chain sodium hydroxyalkanesulfonates with 12-20 carbon atoms, the paraffin sulfonate is a sodium paraffin sulfonate with 10-20 carbon atoms, the sodium silicate has a weight ratio Na20:SiC>2 of 1:2-1:3, and the non-ionic detergent-active material is a monoether of a polyethylene glycol and a long-chain alkanol where the alkanol has 10-16 carbon atoms and the polyethylene glycol has 5-15 oxyethylene units.