DK146324B - PARTICULAR PHOSPHATE-FREE TEXTILE DETERGENT - Google Patents

Description

(19) DENMARK (Wj

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DIRECTORATE OF

PATENT- 06 TRADE MARKET

(21) Patent Application No. 4283/72 (51) Intel.3: C11D 3/08 (22) Filing Date: 30 Aug 1972 (41) Aim. available: 02 Mar 1973 (44) Submitted: 05 sap 1903 (86) International Application No :- (30) Priority: 01 sap 1971 US 177145 12 Nov 1971 US 190454 22 May 1972 US 255356 (71) Applicant: 'COLGATE- PALMOLIVE COMPANY; New York, US.

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

(74) Plenipotentiary: Chas. Huda (54) Particulate, phosphate-free textile detergent

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

Ordinary effective household detergents (for example, for automatic washing machines) contain relatively large amounts of phosphates. An effective agent contains e.g. ca. 33% penta = j sodium tripolyphosphate together with approx. 10% linear sodium alkylbenzene = sulphonate ("LAS") »2% soap, 2% non-ionic detergent, 0.5% carboxy = 4 methylcellulose and 7.5% sodium silicate. Given the widespread notion that the use of phosphates may be ecologically undesirable, many LAS-containing cleansers have been introduced which are essentially one free of phosphates. However, these do not have the high purity of the above-mentioned phosphate-containing agents, and often present other problems, such as health hazards, damage to automatic washing machines, and unwanted sensation when feeling the washed substance. The phosphate free agents or low phosphate agents so far negotiated include agents A to T, whose percentages are listed in the following Table I.

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Substances containing relatively large amounts of sodium silicate are also known. See, e.g. the discussions in the article by Merrill and Getty "ALKYL ARYL SULFONATE-BUILDER MIXTURES", Industrial and Engineering Chemistry 42 856ff (May 1950), and Schleyer "SILICATES IN DETERGENTS", Soap and Chemical Specialties, November and December 1959. See also US Patent no. 3 * 272,753 and the article by Katstra "FORMULATING DETERGENTS WITH LESS PHOSPHATE" in Soap and Chemical Specialties, February 1971.

A recent article in Soap and Chemical Specialties, June 1971 by Louis McDonald states regarding alkali silicates in cleansers:

Their main disadvantage is that they must be used at relatively high pH values up to 11.6 or higher and that they should be used in soft water. If not, they are associated with calcium and magnesium or hard water and deposit a residue or limestone on the material being cleaned. In laundry, the alkali silicates have long been used with good results in soft water at high temperatures (82 ° C) and at high pH values together with fatty acid soaps.

According to the present invention, there has now been developed a substantially phosphate-free laundry detergent having a purification power equal to or greater than the aforementioned high-phosphate effective detergents. This new remedy has been found to be very effective against many different types of dirt including clay and carbon dioxide, skin dirt, natural and artificial skin grease dirt, particulate dirt, etc. and in yellowing tests against many different fabrics including cotton, nylon, polyester (eg poly = ethylene terephthalate), etc. Thus, in contrast to the hitherto known essentially phosphate-free agents, it provides a genuine substitute for the effective high-phosphate cleansers. This has also been demonstrated by repeated tests with usual household dirt clothing.

The detergent according to the invention is characterized in that it consists essentially of (a) a surfactant of the general formula RO (C20 O) O 0. wherein R is alkyl of 10-20 carbon atoms, n is 2-6, and M is a solubilizing salt-forming cation, or of the general formula R R -CH-CH-R ^ wherein M has

CH, O0S0OM

2 1 3 3 has the same meaning as above, and R and R are either hydrogen or alkyl groups, 2 1 with the total number of carbon atoms in R and R being approx. (B) sodium lysate having a weight ratio of Na 2 O: SiO 2 of 1: 2 to 1: 3, (c) a nonionic surfactant which is a monoether of polyethylene glycol and a long chain alkanol; and (d) water-soluble polymer to prevent re-deposition of debris, the ratio a: b being approx.

3: 1 to 1: 3, the ratio a: c is approx. 15: 1 to 4: 1 and the ratio a: d is approx. 90: 1 to 6: 1 and the amount of (c) is at least approx. 4% of the total weight of (a) plus (b).

The surfactant of the formula RO (C2H4O) ^ O ^ M, where R is a fatty alkyl of 10 to 20 carbon atoms, n is 2 to 6, and M is a solubilizing salt-forming cation, such as alkali metal, ammonium, lower alkylamino or lower alkanolamino, is called the following AES. Preferably, n is approx. 1/5 to 1/3 of the number of carbon atoms in R, and the alkyls have 12 to 15 carbon atoms. Of these, the most preferred is a mixed alkyl containing 12, 13, 14 and 15 carbon atoms in the chains. The mixture is preferably one with at least 10% of each chain length and no more than 50% of any chain length. Preferably the detergent is biodegradable and for this purpose the fatty alkyl is joined at the end with the polyoxyethylene chain and only a minor amount (preferably more than about 10%) of the carbon atom content of the alkyl is not in a straight carbon chain and the presence of the intermediate compound of the alkyl to the ethoxy chain is less, usually less than 10%, this compound being preferably concentrated near the end of the alkyl chain. The salt-forming cation M may be any suitable solubilizing metal or radical, but will most often be an alkali metal or ammonium. If alkyl = amine groups or lower alkanolamine groups are present, the alkyls and alkanols therein will usually contain one to four carbon atoms and the amines and alkanolamines may be mono-, di- or trisubstituted, e.g. monoethanolamine, diisopropanolamine, trimethylamine.

Examples of AES scavengers are mixed C 1- normally primary alkyl trie thenoxy sulfate sodium salt, which is a particularly preferred material for this purpose, myristyl triethene oxy sulphate potassium salt, n Primary alkyl mixed tri- and tetraethenoxy sulfate, sodium salt, stearyl pentaethenoxy sulfate, trimethylamine salt, and mixed C ^ q_1212 standard primary alkyl triethenoxy sulfate, potassium salt.

Also, preferably in smaller amounts, the corresponding branched chain cleaners and center alkoxylation cleaners, such as those described above, but modified to have ethoxylation at a carbon atom within the chain, e.g. at a carbon atom located 4 carbon atoms from the end of the chain or less, the carbon atom content of the higher alkyl being the same. Similarly, the bond of a normal alkyl may be at one secondary carbon atom one or two carbon atoms removed from the end of the chain.

The surfactant of the general formula R2 - CH - CH - R1 ch3o oso3m 2 in which M has the meaning given above and R and r1 are either hydrogen or alkyl groups, the total number of carbon atoms in B? and R · is approximately 10 to 20, hereinafter referred to as MAS. Preferably, the detergent is biodegradable and for this purpose the alkyl groups are preferably linear and not branched. Preferably, R and R together have about 12 to 18 carbon atoms and most conveniently ca.

14 to 15 carbon atoms.

It will be seen that AES and MAS scavengers lead to a class of water-soluble long-chain aliphatic sulfate scavengers and an ether bond wherein an oxygen atom in the sulfate group and oxygen in the ether bond are directly bonded to neighboring carbon atoms.

The sodium silicate used according to the invention has a weight ratio of Na 2 O: SiO 2 of 1: 2 to 1: 3. It can be applied in powder or granular form or in liquid aqueous solution. It may be added to the mixture used for spray-drying the product, or it may be added afterwards to the spray-dried cleaner beads, or a portion may be included in the mixture in the mixer, and a portion may be added afterwards.

The nonionic surfactant used in the present invention is a mono ether of a polyethylene glycol and a long chain alkanol wherein the alkanol has approx. 10 to 16 carbon atoms and the polyethylene glycol has approx. 5 to 15 oxyethylene units. Such polyethylene glycol monoethers are generally prepared by reacting the alkanol with ethylene oxide. Preferably, the amount of ethylene = oxide is in the range of 60 to 65%. A particularly suitable product is prepared by reacting 11 moles of ethylene oxide with 1 mole of a mixture of C14 and C15 straight-chain normal primary alkanoias, which mixture has an average of 14-15 (e.g., about 14 , 5) carbon atoms, which product is sold under the name "Neodol® 4511". Alternatively, another identical product may be used in which said mole ratio is 13: 1 instead of 11: 1 ("Neodol® 4513") or a similar product such as an addition product of 7 moles of ethylene oxide and a mole of a mixture of alkanois having 12 to 15 carbon atoms ("Neodol 25 - 7").

Another non-ionic detergent is an ether of polyethylene glycol and a mixture of C16 to C18 alcohols containing about 50 or 65% ethylene oxide ("Alfonic 1618-60" or "AlfoniG 1618-65"). In practice, the presence of the non-ionic surfactant has been found to be essential to achieve the good versatile cleaning ability equal to or better than the high efficiency of high phosphate detergents.

In the admixture with AES (and / or MAS) and sodium silicate, the presence of the nonionic surfactant has surprisingly been shown to increase the ability of the agent to remove clay dirt from fabrics (e.g., from fabrics containing blends of cotton and polyester) and to reduce the repositioning of such debris on these substances during the wash. In contrast, the addition of non-ionic surfactant in other detergent systems essentially has no effect on the removal of clay soil.

The agent also preferably contains a small amount of fluorescent brightener. These agents are well known. They may be of the coumarin type, as disclosed in U.S. Patent Nos. 2,590,485, 2,600,375, 2,610,152, 2,647,132, 2,647,133, 1,791,564, and 2,882,186, the triazolylstilbene type as shown in U.S. Patents

Nos. 2,668,777, 2,684,966, 2,713,057, 2,784,183, 2,784,197, 2,817,665, 2,907,760, 2,927,866, and 2,993,892, the type of bonyanic acid type as disclosed in U.S. Patent Nos. 2,473,375, 2,526 .668, 2,595,030, 2,618,636, 2,658,064, 2,658,065, 2,660,578, 2,666,052, 2,694,064, and 2,840,557, the acylamino-stilbene type as disclosed in U.S. Patent Nos. 2,084,413, 2,468. 431, 2,521,665, 2,528,323, 2,581,057, 2,623,064, 2,674,604, and 2,676,982, or mixed types as disclosed in U.S. Patents Nos. 2,911,415 and 3,031,460. The amount of detergent may be e.g. in the interval approx. 1/20% to 1%, e.g. 1/10% to 1/2%.

9 U6324

A suitable combination of clarifiers includes (a) a naphtho = triazole-stylbenzulfonate, sodium 2-sulfo-4- (2-naphtho-1,2-triazolyl) -stilbene, (b) another stilbene clarifier, bis (anilinodiethanol = aminotriazinyl) stilbendisulfonic acid , (c) another stilbene clarifier, sodium bis (anilinomorpholinotriazinyl) stilbene disulfonate and (d) an oxazole clarifier with a 1-phenyl-2-benzoxazolethylene structure, 2-styrylnaphtha / 1,2 d / oxazole, in the relative amounts of 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 amides or amines, such as Ν, Ν-dilauryl (or di-coconut alcohol) amine, may be used in small amounts, e.g. to 8% of the total agent. Other foam suppressants are silicones, e.g. dimethylsiloxane polymer which can be used in very small amounts (eg 0.1%) as the sole foam suppressant or in combination with other foam suppressants. Sodium sulphate is generally also present as a diluent. When the agent is relatively concentrated, the amount of sodium sulfate will generally be less than 25% of the total agent. Larger amounts of this diluent may be present in less concentrated agents intended to be added in larger doses to the washing machine.

If desired, the agent may contain smaller amounts of sodium perborate. Other peroxy compounds given active oxygen in solution in a similar manner to perborate may be used in whole or in part in place of perborate. These compounds are well known, e.g. sodium percarbonate or sodium persulfate. When the peroxy compound is sodium perborate = tetrahydrate, the weight ratio of AES (and / or MAS) to this compound is usually at least 1: 1.5, e.g. in agents containing approx. 15 to 40% AES (and / or MAS), the amount of sodium perborate may be in the range of 5 to 25%. Other peroxy compounds can be used in amounts that give the same relative amounts of active oxygen over AES (and / or MAS). A typical sodium percarbonate has the formula Na 2 CO 2, 1H 2 O 2.

The following examples further illustrate the invention. All quantities are by weight unless otherwise stated.

10 146324

Example 1.

(a) An appropriate agent contains 40% AES, 33% sodium silicate (Na is sodium sulfate and approx. 5% water. AES is a sodium salt of the sulphate of ethoxylated mixed C12 - C15 normal primary alkanols containing an average of 3 ethoxy groups per molecule.

This composition can be used in the form of spray-dried beads. Thus, the ingredients can be thoroughly stirred together in a conventional mixer, adding AES as an aqueous dispersion containing approx. 40 to 45% active ingredient (the remainder is water together with sodium = sulphate and small amounts of usual impurities produced by sulphonation) and the sodium silicate is added as an aqueous liquid containing 56.5% water. The mixture can be fed from the mixer to the spray nozzles at the top of a spray tower which is supplied with hot air for drying, and the resulting hollow beads can be collected at the foot of the tower and the sodium carboxymethyl cellulose can be added to these beads afterwards.

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

(c) Example 1a is repeated except that the composition contains 5% soap (a sodium soap of 80% sebum 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 amount of AES is 31% and the amount of sodium silicate is 39%.

Example 3

Example 1 is repeated except that the amount of AES is 25% and the amount of sodium silicate is 30%.

11 146324

Example 4

Example 1 is repeated except that the amount of AES is 32.5% and the amount of sodium silicate is 20%.

Example 5

Example 1 is repeated except that the amount of AES is 17.5% and the amount of sodium silicate is 40%.

Example 6 »

Previous examples are repeated except that the amount of sodium carboxymethyl cellulose is varied in the range 0.5 to 3%.

Example 7.

The foregoing examples are repeated except that the agents contain afterwards added granular sodium perborate tetrahydrate in such an amount that the final product contains 5 to 25% of this component.

Example 8.

Example 1 is repeated except that, instead of half of the AES, there is an equal amount of weight of a methoxyalkyl sulfate which is the sodium salt of the monomethyl ether sulfate of mixed vicinal glycols of 16 - 17 carbon atoms supplied by Monsanto as "DMESn.

Example 9

Example 1 is repeated, but the methoxyalkyl sulfate of Example 12 is used in place of AES and the following amounts are used: 25% methoxyal = cooling sulfate, 10% sodium silicate, 4% Neodol 4511, 2.5% sodium carboxy = methylcellulose, the rest being sodium sulfate and ca. 5% water.

Example 10.

Example 9 is repeated except that the amount of methoxyalkyl = sulfate is 17.5% and the amount of sodium silicate is 20%.

Example 11.

12 146324

Example 9 is repeated except that the amount of methoxyalkyl = sulfate is 32.5%, the amount of sodium silicate is 20% and the amount of sodium carboxymethyl cellulose is 2%.

Example 12.

Example 9 is repeated except that the amount of methoxyalkyl = sulfate is 40% and the amount of sodium silicate is 30% and the final agent contains 15% ("subsequently added) sodium perborate tetrahydrate.

Example 13

Example 9 is repeated except that the amount of methoxyalkyl = sulfate is 32.5%, the amount of sodium silicate is 20% and the final agent contains 15% (afterwards added) sodium perborate tetrahydrate.

In wash samples at 49 ° C, the presence of the sodium perborate is found to result in an increase in the cleanliness of the skin.

Example 14.

Each of the foregoing examples is repeated except that in the mixing of the composition, 6/10 of the total amount of sodium = silicate can be added to the mixer in aqueous form as described in Example 1, and 4/10 of the total amount of sodium silicate can be added. afterwards to the spray-dried beads in the form of grains of sodium = silicate having a weight ratio NagOtSiO ^ of 1: 2.00 and a water content of 18.5%.

Example 15

Examples 1 - 13 are repeated using a sodium silicate in which the Na 2: SiO 2 weight ratio is 1: 2.0.

Example 16.

Each of the preceding examples is repeated except that the agent contains 1% fluorescent brightener.

Example 17

13 146324

Example 11 is repeated except that the methoxyalkyl sulfate has (a) a total of 18 carbon atoms in the alkyl chain or (b) a total of 20 carbon atoms in the alkyl chain.

Example 1β.

The agents 1 Examples 4 and 11 are added at a concentration of 0.15% to water with a hardness of 150 parts per minute. million parts (expressed in the usual manner as parts calcium carbonate per million parts). This water is a mixture of distilled water, CaCl2 and MgCl2, the latter being found in amounts which provide 36 parts of Ca million parts and 14.6 parts Mg ion per million parts in the water. After thorough mixing for 10 minutes, the concentration of unbound calcium (shown by the potential of a calcium electrode in contrast to the solution) is measured pH and turbidity. The water temperature is maintained at 50 ° C. The following Table II gives the results, as well as the results for certain commercially available detergents.

Table II.

Average pH Uncertainty (%) Potential of Ca-electric - _ _ ___________ deflection (millivolts) _

Example 4 9.4 2.0 -9.7 • Example 11 9.4 3.0 15.2 High Effective Household Detergent High Phosphate 9.1 8.0 -58

Another similar household detergent 8.9 15.0 -45

Agent A from Table I (in concentration of 0.175%) 10.4 84.0 -42

Mean H from Table I 10.0 64.0 -64

Agent B from Table I 10.5 27.0 -27 14 146324 In the above tabulated experiments, all the detergents are used at a concentration of 0.15%, unless otherwise stated.

The haze is measured with a standard colorimeter (Model 401 from Photovolt Corporation of New York), the use of incandescent light bulbs with a green filter. In this cloud measurement (after 10 minutes) the hard water itself shows a cloudiness of 0, the same hard water containing 0.45% NagCO ^ exhibits a cloudiness of 66 and the same hard water containing 0.03% LAS shows a cloudiness of approx. 90th

The calcium electrode used for the measurement is a calcium activity electrode model 92-20 sold by Orion Research Incorporated Cambridge, Massachusetts and is described in detail in the published guidance (copyright 1966) for this instrument. This electrode develops an electrical potential over a thin layer of water immiscible liquid ion exchange. This fluid is kept mechanically rigid with a thin porous inert membrane disc. The liquid ion exchanger, a calcium salt of an organophosphoric acid, exhibits very high specificity for calcium ions. An internal calcium chloride filling solution is in contact with the inside of the membrane disc. The calcium ion in this solution provides a stable potential between the inside of the membrane and the filler solution, while the chloride ion provides a stable potential between the Ag - AgCl reference electrode and the filler solution. Thus, changes in potential are solely due to changes in the calcium ion = activity of the sample. The electrode only responds to ionized or unbound calcium in the sample. The electrode does not react to the portion of calcium bound to complexing agents such as citrates, polyphosphates and some proteins. According to the manufacturer, this electrode exhibits Nernst potential behavior down to 10 ”moles per minute. per liter of calcium ion according to the following equation:

RT

E = lx + "2F- L0G10 ÆCa-H7 where E is the electrode potential, E = about 90 mm with a saturated KC1 Λ calomel reference electrode

RT

—Th? - = Nearest potential factor for a di valent sensing electrode (29.58 mv at 25 ° C) λ a ++ = activity of calcium ion.

15 146324

In performing the measurements of the calcium electrode potential listed in Table II, the relative scale is first set so that the potential of the hard water as such is -5 millivolts. For comparison purposes, it is noted that the same instrument, with the same setting, gives the following readings when tested on 0.045% solutions (adjusted to a pH of 10.0 with Na OH) of the following compounds in the same hard water (with 150 parts hardness per million parts): trisodium salt of nitrilotriacetic acid -75 millivolts, penta = sodium tripolyphosphate -55 millivolts, sodium citrate -42 millivolts, sodium acetamidonitrilodiacetate -36 millivolts, iminodiacetic acid -12 millivolts, sodium oxalate -38.4 millivolts. For further comparison, tests on water itself, similarly adjusted to a pH of 10.0 with NaOH (with the hardness changed by changing the total amount of CaCl 2 and MgCl 2, but not their relative amounts), the following readings: 50 parts hardness (as CaCO million parts -20 millivolts, 25 parts hardness per million parts -27.5 millivolts, 300 parts hardness per million parts +5 millivolts. This should be compared with the -5 millivolts for the water with a hardness of 150 parts per hour. million parts and approx. -80 millivolts for water of hardness 0. In each case, the measurements are made after 10 minutes of stirring as previously mentioned.

It will be seen that preferred substantially carbonate-free agents of the invention give relatively low turbidity (e.g., slightly below 30% and generally below 15%, e.g., in the range up to 5%) and bind relatively little calcium (e.g. for example, they exhibit calcium electrode potentials of more than about -25, such as about -5 to -20).

Example 19.

In each of the foregoing examples, a mixture of two compatible blue dyes of different shades is incorporated, but with substantially the same substantivity to the fabric, so as to give the washed substance (when dried) a slight blue hue. In particular, the dyes are such that if used independently, they dye the fabric greenish blue and reddish blue respectively. Specifically, the cleaners include 0.001% Geigy "Direct Brilliant Sky Blue" 6B (reference number 24410, C.I. Direct Blue l) and 0.0003% Geigy "Solophenyl Violet" 4BL (reference number 29120, C.I. Direct Violet 66).

Instead of the specially mentioned blue dyes mentioned above, a mixture of 0.002% "Verona Alizarine Brilliant Sky Blue" RW and 0.001% "Verona Sirius Supra Blue" BRL can be used.

Example 2Q

In each of the foregoing examples, a small amount (such as 0.1 to 0.4%, e.g. 0.2 or 0.3%) of a pale stable fluorescent brightener such as 4,4'-bis (4- -phenyl-2H-1,2,3-triazol-2-yl) -2,2-stilbendisulfonic acid or a salt thereof (eg, an alkali metal, especially the potassium salt).

Example 21.

Instead of the blue dyes in Example 19, ultramarine blue is used in an amount of approx. 0.06%. In a particularly suitable agent there is also 10% sodium perborate and approx. 0.3% of a pale stable fluorescent brightener such as that described in Example 20.

When using the detergent of the invention, the wash water may be hot (e.g., 49 ° C, 60 ° C, or higher) or cold (e.g., 38 ° C, 27 ° C, 21 ° C, or lower). The water may be soft or hard (for example, with a hardness expressed as calcium carbonate of 50, 100, 150 or 200 parts per million parts). The amount of the agent added to the wash water is generally such that it gives a concentration of AES or MAS in the range of approx. 0.025% to 0.09% in the water. The agents of the Examples are specially formulated for use at a concentration in the range of approx. 0.1 to 0.2%, especially approx. 0.15% of the entire composition in the wash water and for use in the usual washing cycle, e.g. 5 to 20 minutes (usually about 10 minutes) of washing with stirring followed by appropriate removal of the wash water from the fabrics (eg by centrifugation and rinsing). The agents of the invention give excellent results with fabrics containing synthetic fibers such as low moisture absorption fibers , eg. nylon or polyethylene terephthalate, alone or in admixture with cellulose fibers such as cotton or rayon. The washed clothes do not have an unwanted grip, and the means have a high degree of safety and compatibility with automatic washing machines.

17 146324

The compositions of the invention can be used for washing with or without bleaching. The wash water can e.g. contain added sodium hypochlorite (eg 200 parts per million parts of available chlorine added by the addition of 4 cmr of 5.25% aqueous NaOCl solution to the wash water).

In this connection, it is noted that the agents of the invention generally have a pH slightly higher than the pH of the usual effective phosphate-containing detergents (see Table II) and the higher pH may decrease the bleaching rate but prolong the period of action of hypochlorite, and may also reduce its attack on detergents in the detergent.

A highly suitable clarifier for use in the compositions of the preceding examples contains (a) disodium 4,4'-bis / 4-anilino-6- (2 * -hydroxyethyl) methylamino-s-triazine-2-ylamino7-2,2 '-Stylbenzenesulfonate, (b) a naphthotriazole stilbenzulfonate clarifier, sodium 2-sulfo-4- (2-naphtho-1,2-triazolyl) stilbene, (c) another stilbenalphant, sodium bis (anilino-morpholino-triazinyl) stilbene disulfonate, with or without (d) an oxazole clarifier with a 1-phenyl-2-benzoxazole = structure, 2-styrylnaphtha / l, 2d7oxazole in relative amounts (a) 0.7, (b) 0.05 (c) 0, 2 and (d) 0.05, with the total amount of detergent, e.g. is approximately. 1%.

Also, smaller amounts of other ingredients can be added to the agents, e.g. germicidal agents, activators for peroxy compounds, fabric softeners, enzymes, perfumes, coloring agents, metals for preventing tarnishing of metals, etc. Examples of germicidal agents are tetrachlorosalicylanilide and hexachlorophen. Examples of enzymes are alkaline proteases (such as the subtilisin protease which is marketed as alkalase, for example 0.1 to 1%, for example about "Alcalase P" ® with a proteolytic enzyme activity of 1.5 Anson units per grams of prilled, fine beads of a mixture of nonionic detergent and the enzyme, which is a subtilisin enzyme whose proteolytic activity is measured at a pH of 7.3 but exhibits its maximum activity at a pH of about 8-9) and amylases (e.g., α-amylase). Examples of activators for peroxy compounds which generate peracetic acid, perbenzoic acid or other peracids in the wash water are the activator compounds mentioned in US Patent No. 3,532,634 which also include various suitable peroxy compounds. Bleaching can also be effected by including in the agent solid materials which react with the wash water to form hypochlorichloro or hypobromite bromine, among which are N-bromine and N-chloroimides such as the heterocyclic imides such as trichloroacetic acid, tribromocyanuric acid, dibromo = cyanuric acid, dichlorocyanuric acid and salts thereof with water-solubilizing cations such as sodium or potassium. The fabrics washed with the compositions of the invention generally have a desirable soft, non-rigid grip, but it may be desirable for certain purposes to include fabric softeners in the compositions, 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 addition products such as the long chain alkanols addition products, e.g. addition products of 3 or 4 moles of ethylene oxide and 1 mole of a mixture of C12 to C15 alkanols (such as "Neodol 25.3" or "Neodol 25-4").

Still other additives are those which can serve as carriers for liquid non-ionic cleansers and provide improved flowability of granular cleansers. Among these are absorbent silica or other finely divided mineral powders, such as Cab-o-sil and satinton, may also be used other water-soluble high polymers which serve as a means of preventing re-deposition of dirt. In any of the above examples, e.g. Instead of sodium carboxymethyl cellulose, an equal weight of polyvinylpyrolidone (FVP) or a 50/50 mixture of CMC / FVP or an equal weight amount of polyvinyl alcohol (FVA) or a 50/50 mixture of CMC and FVA is used. Other water-soluble high polymers which may be used are sodium starch glycolate, copolymers of maleic anhydride and vinyl monomers such as ethylene or methyl vinyl ether, sodium cellulose sulfate or sodium hydroxyethyl carboxymethyl = cellulose, glyodine, starches etc.

The surfactants used according to the invention are, of course, water-soluble and so is the sodium silicate.