DK146566B - PARTICULAR PHOSPHATE-FREE TEXTILE DETERGENT - Google Patents

Description

(19) DENMARK (W j

M (12) PUBLICATION (s) 146566 B

DIRECTORATE OF THE PATENT 06 BRAND

(21) Patent Application No. 4332/72 (51) Int.CI.3: C11D 3/08 (22) Filing Date: 01 ββρ 1972 C 11 D 3/60 (41) Aim. available: 02 Mar 1973 (44) Submitted: 07 Nov 1983 (86) International Application No :- (30) Priority: 01 Sep 1971US177145 12 Nov 1971 US198455 22 May 1972 US 255357 (71) Applicant: 'COLGATE-PALMOLIVE COMPANY; New York, US.

(72) Inventor: Paul Sheldon 'Grand; US.

(74) Plenipotentiary: Chae. Hude_ (54) Particulate, phosphate-free textile detergent

The invention relates to a particulate, phosphate-free textile detergent.

Ordinary highly effective detergent products for household use (for example, for automatic washing machines) contain relatively large q amounts of phosphates. A very effective product contains e.g. ca.

33% pentane sodium tripolyphosphate together with approx. 10% sodium linear

D

D alkylbenzenesulfonate ("LAS"), 2% soap, 2% non-ionic surfactant, 0.5% O carboxymethyl cellulose and 7.5% sodium silicate. In view of the widespread notion that the use of phosphates may be ecologically unfavorable, a large amount of LAS-containing dell products which have been substantially free of phosphates have been introduced. However, these do not have the high purity of the phosphate products mentioned above.

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"" 2 U6566, and often presents other problems, such as health risks, damage to automatic washing machines and unwanted grip on the washed, fabrics. The phosphate-free products or low phosphate products that have recently been brought to the market— , that includes products A - T, the percentages of which are given in the following Table I.

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Products containing relatively large amounts of sodium silicate are also known in the art. See, e.g. the discussions in the articles by Merrill and Getty "Alkyl Aryl Sulfonate-Builder Mixtures", Ind. and Eng, Chem, 42, 856ff (May 1950) and Schleyer "Silicates in Detergents", Soap and Chemical Specialties, November and December 1959. See also the description for Wixon's U.S.A. Patent No. 3,272,753 and Katstra's article "Formulating Detergents With Less Phosphate" in Soap and Chemical Specialties, February 1971.

In a recent article in Soap and Chemical Specialties, from June 1971, Louis McDonald states, with regard to alkali silicates in detergents: "Their primary disadvantage is that they are used at relatively high pH values, 11.6 or higher and that they should be used in soft water, otherwise they go with the hard water calcium and magnesium and precipitate a residue or foam on the material to be purified For washing, the alkali silicates have long been successfully used in soft water at high temperatures (82 ° C). at high pH values with fatty acid soaps ".

In accordance with the present invention, there has now been developed a substantially phosphate-free detergent product having a purification effect equal to or greater than the aforementioned highly effective strong phosphate-containing detergent. This novel product has been found to be very effective against a wide variety of stains and dirt sources, including clay and carbon dirt, skin dirt, natural and artificial sebum dirt, particulate dirt, etc., as well as yellow samples on clean clothes, for a variety of fabrics, including cotton, nylon, polyester (e.g., polyethylene terephthalate), etc. In contrast to the substantially phosphate-free products of the prior art, the invention thus provides a true substitute for the high-effective detergents with high phosphate content. This has also been proven by repeated attempts at ordinary household laundry workouts.

The novel materials or products of the invention do not give high pH values, and are effective in hard water, without the formation of residues or foam hubs to any appreciable degree. In fact, experiments with a calcium ion electrode and haze measurements indicate that, unlike conventional phosphate-containing products, the 146566 products of this invention do not associate with significant amounts of calcium ions.

It has now been found that this excellent effect can be achieved with a particulate, phosphate-free textile detergent according to the invention, characterized in that it consists essentially of (a) an olefin sulfonate or paraffin sulfonate surfactant, (b) a sodium silicate having a weight ratio : SiC₂ in the range of 1: 2 to 1: 3, (c) nonionic surfactant, which is a monoether of polyethylene glycol and a long chain alkanol, and (d) water-soluble antigenic precipitation polymer, the ratio a: b being in the range of about 1: 2. 2: 1 to 1: 2, the ratio a: c ranges from approx. 15: 1 to 4: 1, the ratio a: d is in the range of approx. 90: 1 to 6: 1 and the amount of c is at least approx. 4% of the total weight of a plus b.

Olefin sulfonate surfactants are well known in the art. They generally contain long chain alkenyl sulfonates or long chain hydroxyalkanesulfonates (with the OH group of one carbon atom not directly bonded to the carbon atom bearing the group Δ SO 2). More commonly, the olefin sulfonate product comprises a mixture of these two compound types in varying amounts, often in association with long chain disulfonates or sulfone sulfonates. Such olefin sulfonates are described in many patents, such as the descriptions of U.S.A. patents Nos. 2,061,618, 3-409,637, 3-332,880, 3-420,875, 3,428,654, and 3,506,580 and British Patent Nos. 1,139,158 and Baumann et al's article in Fette-Seifen-Anstrichmittel 72, No. 4 , pp. 247-253 (1970). As disclosed in these patents and literature, the olefin sulfates can be prepared from straight-chain α-olefins, internal defines, defines wherein the saturation is a vinyl member's chain of ideas (e.g., dimers of α-olefins), etc., or more commonly mixtures of such compounds, the α-olefin usually being the main constituent. The sulfonation is usually carried out with sulfur trioxide under low partial pressure, e.g. SO 2 strongly diluted with inert gas such as air or nitrogen or SO 2 under vacuum. This reaction generally gives an alkenylsulfonic acid, often with a sultone. The resulting acidic material is then generally made alkaline and treated to open the sultone ring to form hydroxyalkanesulfonate and alkenyl sulfonate. The number of carbon atoms in the olefin usually ranges from 10 to 25, more commonly from 12 to 20, e.g. a mixture of mainly C12 and cxg with an average of approx. 14-carbon atoms or a mixture of mainly C 14 * 16 and C 18 with Pa about · 16 carbon atoms. The preferred olefin sulfonates are sodium salts, but it is within the scope of the invention to use other water-soluble salts such as ammonium or potassium salts.

In addition, a portion of or even the entire amount of the olefin sulfonate may be replaced by a paraffin sulfonate having 10-20 carbon atoms. These may be the primary paraffin sulfonates prepared by reacting long chain α-olefins and bisulfites (e.g., sodium bisulfite) or paraffin sulfonates with the sulfonate group distributed along the paraffin chain such as the products prepared by reacting a long chain paraffin with sulfur dioxide and oxygen under ultraviolet light. neutralization with NaOH or other suitable base (as in the US Patent Specifications Nos. 2,503,280, 2,107Q88, 3,260,741 and 3,372,188 and the disclosure to German Patent No. 735,091.

Very good results have been obtained in the use of paraffin sulfonates, whose average carbon chain length (e.g., 15-16) is substantially below that previously believed to be optimum in high-performance phosphate products. (See Black et al's article in Soap / Cosmetics Chemical Specialtien, November 1971, p. 37ff, especially Table 7 on page 42).

The sodium silicate used in this invention has a Na 2 O: SiO 1: 2 to 1: 5. It can be applied in powder or granular form or in liquid aqueous solution. It may be added to the mixture used in spray drying the product or it may be added afterwards to the spray-dried detergent balls or a portion may be included in said mixture and a portion may be added afterwards.

The nonionic surfactant used in the present invention is preferably a monoether of a polyethylene glycol and a long chain alkanol, wherein the alkanol has approx. 10-16 carbon atoms and the polyethylene glycol have 5-15 oxyethylene units.

Such polyethylene glycol monoethers are commonly prepared • V.

8 146566 by reacting the alkanol with ethylene oxide. The amount of ethylene oxide is preferably in the range of -60-651. A particularly suitable product is prepared by reacting 11 moles of ethylene oxide and 1 mole of a mixture of Cu and C15 straight chain primary primary alkanols, the mixture having an average of 14-15 (e.g. about 14.5) carbon atoms, which product sold under the name "Neodol 4511". However, another otherwise identical product may also be used in which said mole ratio is 13: 1 instead of 11: 1 ("Neodol 4515") or a similar product such as an adduct of seven moles of ethylene oxide and 1 mole of a mixture of alkanols with 12-15 carbon atoms ("Neodol 25-7"). Another non-ionic surfactant is an ether of polyethylene glycol and a mixture of ^ 16 $ 60 or $ 65 ethylene oxide ("Al-phonic 1618-60" or "Alfonic®L618-65"). In practice of the present invention in practice, the presence of the non-lonogenic surfactant has been found to be essential to achieve the high versatile purification effect that is similar to and better than that of high-performance high phosphate detergents in the substantial absence of carbonates.

Preferably, the product also contains a low fluorescent brightening agent. Such clearing agents are well known. They may be coupling types as described in U.S.A. U.S. Pat. U.S. Pat. U.S. Pat. U.S. Pat. U.S. Patent Nos. 2,911,415 and 3,031,460. The amount of clarifying agent may e.g. range from approx. 1/20% to 1%, e.g. 1/10% to 1/2%. A suitable combination of clearing agents comprises (a) a naphthotriazole stillbenzulfonate clarifier, sodium 2-sulfo-4- (2-naphtho-1,2-triazolyl) stillbene, (b) another stillbene clearing agent, bis (anilinodiethanolaminotriazinyl) stillbendisulfonate , (c) another stilbene clarifier, sodium bis (anilinomorpholinotriazinyl) stilbene disulfonate, and (d) an oxazole clear agent having a 1-phenyl-2-henzoxazolethylene structure, 2β-styrylnaphtha- [1,2-d] -oxazole in the proportions a: b: c: d of approx. 1: 1: 3: 1.2.

Other ingredients that may be included are antifoaming agents. For this purpose, soap or high molecular weight amide or amine = antifoaming agents such as Ν, Ν-dilauryl (or dicocosalcohol) amine may be used in small amounts, e.g. 1/2 to $ 8 of the total product. Other antifoaming agents are silicones, e.g. dimethylsiloxane polymer which can be used in a very small amount (for example, $ 0.1) as the sole antifoaming agent or in combination with other antifoaming agents. Sodium sulfate is generally also used as a diluent. When the product is a relatively concentrated product, the amount of sodium sulfate is usually well below $ 25 of the total product. Larger amounts of this diluent may be included in less concentrated products, intended to be added in larger doses to the washing machine.

The product may optionally contain smaller amounts of sodium perborate. The presence of this component has been found to be particularly beneficial in raising the purification effect for products which otherwise contain less than the optimal amounts of olefin sulfonate and silicate. Thus, the product may contain approx. 5-15 $ sodium perborate tetrahydrate (which corresponds to about 0.5-1.5 $ active oxygen in the product) and excellent results have been found even when the washing is carried out at room temperature (e.g., 48.8 ° C or 6 ° C C) well below the temperatures at which sodium perborate is considered to be effective for bleaching. Other peroxygen compounds which provide active oxygen in solution in a manner similar to perborate may replace part or all of the perborate amount. Such compounds are well known in the art. Na = triumper carbonate (e.g., Na 2 CO 1, 1.5 H 2 O 2) can e.g. is used.

The following examples serve to further illustrate the present invention. In this text, all parts are parts by weight, unless otherwise stated.

Example 1.

(a) A suitable product contains 40 $ olefin sulfonate, 50% sodium sis = licate (NagOiSiOg weight ratio 1; 2.35), 4 $ "Neodol 45-11", 2 $ sodium = carboxymethylcellulose (water soluble, usual detergent grade), the rest is sodium sulfate and approx. 5 $ water.

10 146566

This composition can be used in the form of spray-dried balls.

Thus, all of the ingredients can be mixed thoroughly in a conventional mixer, adding the olefin sulfonate as an aqueous dispersion containing approx. 40-45 $ active ingredient (the remainder being water with some sodium sulfate and small amounts of usual impurities obtained by sulfonation) and the sodium silicate added as an aqueous liquid containing $ 56.5 water. The mixture can be passed to spray nozzles located at the top of a spray tower, provided with hot air for drying, and the resulting hollow balls can be collected at the bottom of the tower.

(b) Example 1a is repeated except that sodium carboxymethylcellulose is omitted from the mixture and is instead added in granulated form to the spray dried balls. When this mixture is dissolved in deionized water, the solution at a 0.15 $ concentration exhibits a pH of 9.9.

(c) Example 1a is repeated except that the product contains 2 $ "Armeen ^ 2C" (dicocosamine) to reduce the tendency of the material to foam in an automatic washing machine.

(d) Example 1b is repeated, except that the product contains 5 $ soap (a sodium soap of $ 80 tallow fatty acids and 20 $ coconut oil fatty acids) to reduce the tendency of the material to foam in an automatic washing machine.

Example 2.

Example 1 is repeated except that the olefin sulfonate amount is 25 $ and the sodium silicate amount is 25 $.

Example 5

Example 1 is repeated except that the olefin sulfonate amount is $ 32 and the sodium silicate amount is $ 26.

Example 4

Example 1 is repeated except that the amount of olefin sulphonate is 25 $, the sodium silicate amount is 30 $ and granular sodium perborate tetrahydrate is subsequently added to the spray dried balls in such an amount to provide approx. 15 $ NaBO ^^ HgO in the final product.

Example 5

Example 4 is repeated except that the olefin sulfonate amount is 30 $ and the sodium silicate amount 40 $.

Example 6

Each of the foregoing examples is repeated except that in mixing the product, 6/10 of the total sodium silicate = amount is added to the aqueous mixture mixer, as described in Example 1, and 4/10 of the total sodium silicate amount can be added afterwards to the spray-dried beads in the form of sodium silicate grains having a weight ratio of Na 2 O: SiO 2 of 1: 2 and a moisture content of $ 18.5.

Example 7

Examples 1-5 are repeated using a sodium silicate in which the NagOiSiOg weight ratio is 1: 2.0.

Example 8.

Each of the foregoing examples is repeated except that the product contains 1 $ fluorescent clarifier.

The olefin sulfonate used in the preceding examples is prepared from an olefin mixture containing 78 $ α-olefins, 7-8 $ inner olefins, 14-15 $ olefins with a draw = CH 2 group (ie, with a vi = nylidene group) and 0 , $ 1 paraffins, which blend contains 1.7 $ C- ^ 2 olefins, 65 $ C- ^ olefins, 33.2 $ olefins and 0.1 $ C ^ g ole = veneers. The reaction is carried out in the usual manner: The olefin is sulfonated with SO 2 vigorously diluted with air using slightly more than 1 mole SO the corresponding sodium salts, and the resulting alkaline mixture is heated at elevated temperature (e.g., 171 ° C) by overpressure to convert the liner sulfonation to form sultones to the corresponding sodium hydroxyalkanesulfonates and alkenyl sulfonates. Similar results are obtained in the previous examples with olefin sulfonates prepared similarly from (a) a 1: 1: 1 mixture of 1-dodecene, 1-tetradecene and 1-hexadecene, or (b) 1-hexadecene or (c) a 10: 40: 40: 10 mixture of 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicose.

Example 9

The products of Example 1b were added in 0.15% concentration to water with a hardness of 150 ppm (expressed in the usual manner, such as ppm of calcium carbonate, ppm = parts per million). This water is a mixture of distilled water, CaCl2 and MgCL2, the latter constituents being present in amounts which provide 56 ppm of Ca ion and 14.6 ppm of Mg ion in the water. After careful mixing over a period of 10 minutes, the concentration of unbound calcium (as indicated by the potential of a calcium electrode in contact with the solution) is measured pH and turbidity. The tooth temperature is maintained at 50 ° C during this period. The following Table II gives the results and results for some commercial detergents:

label II

Potential of Ca

Detergent pH Fuzziness ($) electrode (millivolt) _

Example 1b 9.7 3.0 -9.0 Highly commercial detergent product with high phosphate content 9.1 8.0 -58

Another commercially available detergent with high phosphate content 8.9 15s0 -45

Sample A from Table I

(at $ 0.175 concentration) 10.4 84.0 -42

Sample H from Table I 10.0 64.0 -64

Sample B from Table I 10.5 27.0 -27 In the experiments listed above, all the detergents are used at a concentration of $ 0.15 unless otherwise indicated.

13 146568

The haze is measured with a standard colorimeter (Model 401 from Photovolt Corp, New York), using incandescent light with a green filter.

Ted this cloudiness measurement (after 10 minutes) the hard water itself shows a cloudiness of 0, the same hard water containing 0.045 $ ^ 2 ^ 2 exhibits a cloudiness of 66, and the same hard water containing 0.05 $ LAS shows a cloudiness of approx. . 90th

The calcium electrode used for the measurement is a calcium activity electrode No. 92-20 sold by Orion Research Inc. from Cambridge, Massachusetts, and is described in detail in the published instruction manual (copyright 1966) for this instrument. This electrode elicits an electrical potential over a thin layer of water-immiscible liquid ion exchanger. This fluid is mechanically held by a thin porous inert membrane disc. The liquid ion exchanger, a calcium salt of an organophosphoric acid, exhibits a very high specificity for calcium ions. An internal calcium solution of chloride = chloride contacts the inner surface of the membrane. The calcium ion in this solution provides a stable potential between the membrane interior and the filling solution, while the chloride ion provides a stable potential between the Ag-AgCl reference electrode and the filling solution. Thus, changes in potential are due only to changes in the calcium ion activity of the sample. The electrode only responds to the ionized or unbound calcium in the sample. The electrode does not react to the portion of calcium which is bound to complexing agents such as citrates, polyphosphates and some proteins. According to the manufacturer, this electrode exhibits Nern potential potential down to 10 "moles / liter of calcium ion according to the following equation: ft ψ E = Ex +" 2P "loglotACa ++ ^ where E = the electrode potential, E = approximately 90, etc. with a saturated x µR KC1 calomel reference electrode, ~ £ p ~ = Nearest potential factor for a divalent sensor electrode (29.58, etc. at 25 ° C), A ^ a ++ = calcium = ionic activity.

When the calcium electrode potential measurements listed in Table II were made, the relative scale was first set so that the hard water potential per se is minus 5 millivolts. For purposes of comparison, it is found that the same instrument with the same measurements gives the following readings when testing 0.045 $ 14 146566 solutions (adjusted to pH 10.0 with NaOH) for the following compounds in the same hard water (with a 150 ppm hardness: Trisodium salt of nitrile triacetic acid ("NTA") -75 millivolts, penta = sodium tripolyphosphate -55 millivolts, sodium citrate -42 millivolts, sodium acetamide nitrile diacetate -56 millivolts, iminodiacetic acid -12 millivolts, sodium oxalate -38 As a further comparison, samples of water even similarly adjusted to pH 10.0 with NaOH (with the hardness changed by changing the total amount of CaCl 2 and MgCl 2, but not their mutual ratio) give the following readings: (as CaCO 2) -20 millivolts, 25 ppm hardness -27.5 millivolts, 300 ppm hardness + 50 millivolts. This should be compared to -5 millivolts for the water with a hardness of 150 ppm and approx. -80 millivolts for the water with a hardness of 0. In each case-. they are measured after 10 minutes of stirring as previously mentioned.

It will be seen that products of the invention provide relatively low. turbidity (e.g., well below 30% and generally below 25%, for example, in the range of 5 - 15%) and binds relatively little calcium (e.g., they exhibit calcium electrode potentials greater than -25, e.g. range from -5 to -15).

Example 10.

Example ld is repeated except that the sodium silicate amount is lowered to $ 33.

Example 11.

Example 1d is repeated, except for the following changes in the amount ratios: The olefin sulfonate amount and the sodium silicate amount are both lowered to $ 25 and the soap amount is lowered to 1%.

Example 1.2.

Example 1d is repeated, except for the following changes in the amount ratios: The olefin sulfonate amount is reduced to $ 18, the sodium silicate amount is reduced to $ 25 and the soap amount is increased to $ 6. It should be noted that in this example, the ratio of total amount of anionic detergent (olefin sulfonate plus soap) to nonionic detergent is approx. 6: 1. The product provides a low amount of foam in an automatic washing machine and exhibits excellent cleaning effect on cotton fabrics.

Examples 1-3.

Example 12 is repeated, instead of the olefin sulfonate, a sodium paraffin sulfonate having the following chain length distribution (determined by analysis) is used: C5 $, C- ^ 16 $ ·, C- ^ 30 $, C- ^ g 30 $, C- ^ γ $ 15, C18 $ 4; this paraffin sulfonate also contains approx. $ 10 (based on total amount of A.I.) disulfonates.

Example 14.

In each of the foregoing examples, a mixture of two compatible blue dyes of different shades is incorporated, but of substantially the same substantivity to the fabric, so that the washed fabrics (when dried) have been given a faint blue hue. The dyes are more special so that if used independently respectively, the fabric gives a green-blue and reddish-blue color. Specifically, the detergent products contain $ 0.001 of Geigy Direct Brilliant Sky Blue 6B "(reference # 24410, C.I. Direct Blue 1) and $ 0.0003 of $ 0.10myigy Solophenyl Violet 4Bl" (reference # 29120, C.I. Direct Violet 66).

Instead of the specially mentioned blue dye set described above, a mixture of $ 0.002 Verona Alizarine Brilliant Sky Blue RW and $ 0.001 Verona Sirius Supra Blue BR1 can be used.

Example 15

In each of the foregoing examples, a small amount (such as 0.1-0, 4 $, e.g. 0.2 or 0.3 $) of a bleach stable fluorescent brightener such as 4,4'-bis is incorporated. - (4-phenyl-2H-1,2,3-triazol-2-yl) -2,2'-stilbenedisulfonic acid or a salt thereof (eg, an alkali metal salt, especially potassium salt).

Example 1 g.

Instead of the blue dyes from Example 14, ultramarine blue is used in an amount of approx. 0,06 $. A particularly suitable product also includes 10 $ sodium perborate and approx. 0.3 $ of a bleach stable 16 fluorescent brightener such as that described in Example 23. ~

When using the products of this invention, the wash water may be hot (e.g., 48.8 ° C, 60 ° C, or a higher temperature) or cold (e.g., 37.7 ° C, 26.6 ° C, 21 , 9 ° C or a lower temperature). The water can be soft or hard (eg having a hardness expressed as calcium carbonate of 50, 100, 150 or 200 parts per million). The amount of product added to the wash water is usually such that a sulfonate detergent concentration is provided in the range of from $ 0.02 to $ 0.1 in the water. The products of the Examples (wherein the sulfonate tens content is in the range of about $ 15 to $ 45, the sodium silicate content is in the range of about $ 20-40, the nonionic surfactant content is in the range up to about $ 6, and the sodium carboxymethyl cellulose content is in the range specially prepared for use at a concentration in the range of about 1 to 3 $). 0.1 to 0.2 $, especially approx. $ 0.15 of the total product in the wash water and for use during the usual wash period, e.g. 5-20 minutes (most preferably about 10 minutes) with washing / movement, followed by removal of wash water from the laundry in the usual manner (eg by centrifugation) and rinsing. The products of this invention give excellent results with 100% cotton fabrics and with fabrics containing synthetic fibers such as low moisture absorption fibers, e.g. nylon or polyethylene tereph = thai alone or in admixture with cellulose fibers such as cotton or rayon. The washed clothes do not have an unwanted grip and the products, especially those which contain virtually no alkali metal carbonate, have a high degree of safety and compatibility with automatic washing machines.

In comparative washing test rows, it was surprisingly found that as the test progressed (the clothes are subjected to their third, fourth, fifth, etc., and their corresponding third, fourth, fifth washing with the same given product) the products of the invention give better and better results in comparison with the usual potent phosphate detergent.

The products may also include smaller amounts of other ingredients, e.g. germicidal agents, activators for peroxygen compounds, fabric softeners, enzymes, perfumes, coloring agents, antiplet agents etc. Examples of germicidal agents are tetrachlorosalicylanilide and hexachlo = rophen, examples of enzymes are alkaline proteases (such as Alcalas ^ 1 for example 0.1-1 $, e.g.

(S) "Alcalase P" having a proteolytic enzyme activity of 1.5 Anson units per gram in the form of prilled fine beads of a mixture of nonionic detergent and the enzyme, the enzyme being a subtilisin enzyme whose proteolytic action is measured at a pH value of 7.3, but exhibiting its maximum effect at a pH of approx. 8-9) and amylases (e.g., α-amylase), examples of activators for peroxygen compounds which form peracetic acid, perbenzoic acid or other peracidic forms in the wash water, are the activator compounds mentioned in the description to U.S.A. No. 3,532,634, which also discloses various suitable peroxygen compounds. Bleaching can also be accomplished by including in the product solids that can react with the wash water to form hypochlorochlorine or hypobromite bromine. Among these are N-bromo and N-chloroimides, such as the heterocyclic imides such as trichlorocyanuric acid, tribromocyanuric acid, dibromo cyanuric acid, di-chlorocyanuric acid and salts thereof with water-soluble cations such as sodium or potassium. Although fabrics washed with the products of this invention generally have a pleasantly soft, non-rigid grip, for some purposes it may be desirable for the products to include plasticizers, e.g. 1,2-alkanediols having 15-18 carbon atoms. Another suitable additive is borax.

Other additives are fat solvents such as the low ethylene oxide ethylene oxide adducts such as the long chain alkanols adducts, e.g. the adducts of 3 or 4 moles of ethylene oxide and 1 mole of a mixture of C12 to Calkanols (such as "Neodol 25-3" or "Neodol 25-4").

Other additives are also those which can serve as carriers for liquid non-ionic surfactant and provide the granular products with enhanced flowability, among which are absorbent silicas and other finely divided mineral powders such as Cab-o-silk, satin tone .

Other water-soluble higher polymers which serve as antigenic precipitating agents may also be used. In any of the above examples, e.g. instead of the sodium carboxymethyl cellulose ("CMC"), a similar amount of polyvinylpyrrolidone ("FVP") or a mixture of