DE2320753A1 - GRAINY DETERGENT AND DETERGENT MIXTURE - Google Patents

Description

RIGHT / -! '-.' V / "'. H

E-. UJl ■ - ■ "■ ^ v. WALTER 8ElL

Al ~ r. "'I 1 - ■' rT-'g.i

YOU. JU:;. '.-..--, -..-'.- U ₁ Vi: ■? .-]. WOlFP

ΐ ·? Λί · \ ΖΓ · ϊ.ρ Ah \ MAIN HIGH

April 24, 1973

Our no.18 641

The Procter & Gamble Company Cincinnatio, Ohio, V.St.A.

Granular detergent and cleaning agent mixture

The present invention relates to granular detergent and cleaning agent mixtures which are surface-active Contain agents and detergent builders. Such mixtures are generally used as detergent mixtures containing builders designated. Case «a relatively large proportion of detergent builder relative to the surfactant Medium is used, the mixture is characterized as a high-performance mixture or heavy duty detergent, which is used in primarily for washing heavily soiled fabrics, as is usually the case contained in household linen are intended.

309845/1094

It is known that when using soaps in hard Water-insoluble calcium and magnesium soaps are formed, which impair the cleaning performance. The upper - surface-active properties of common non-soap-based surfactants (i.e. synthetic detergents) v / earth also due to the presence of mineral hardness, such as alkaline earth metals, adversely affected. The precipitation of soap and inactivation of surface-active substances Hardness components of water, especially calcium and magnesium, are a source of considerable waste in the use of such surfactants. Surfactants that react in this way and become ineffective vrden, are no longer available to exercise their nullifying effects.

One class of useful builder compounds exists in complex-forming detergent builders, which are the hardness constituents solubilize the water, especially calcium and magnesium. These include well-known inorganic phosphorus-containing condensed phosphates such as sodium tripolyphosphate and urodium pyrophosphate. This also includes organic ones nitrogenous compounds such as sodium nitrilotriacetate. However, there have been concerns in recent years occurred that, due to the phosphorus and nitrogen content of such compounds, adverse environmental influences, such as accelerated Eutrophication of some lakes and rivers can occur. Eutrophication is a natural process through that aquatic life is sustained by the Enables the growth of plant organisms in the water, thus creating food for the fish. Against accelerated however, ecological or excessive eutrophication exist Concerns. Due to excessive plant growth in lakes and rivers the oxygen that the fish need is consumed and thus a destruction of the correct ecological occurs Equilibrium in these waters. This excessive eutrophication is caused by unusually large amounts of

30984S / 1094

causes substances that end up in lakes and rivers. Phosphorus and nitrogen are two such chemical effective in nutrients Elements. This alone does not cause excessive eutrophication; there must be other nutrients such as carbon, may also be present. It is only the combination of nutrients that enables plants to grow stimulated in lakes and rivers.

It is known that phosphorus and nitrogen are normal constituents of all natural waters and come from normal ecological processes. These two elements are contained in natural waste products of sov ^T ell humans and animals and they also come from fertilizers, which are used in widely in agricultural technology application, to promote plant growth. Phosphorus and nitrogen that enter natural waters in the form of detergents are only part of the total.

The interest in maintaining the environment, as indicated by existing and proposed legal measures Expressed, has led to the endeavor to increase the amounts of phosphorus and nitrogen in the waterways regulate, but not necessarily eliminate them entirely. The intent of these legal measures is regulation the amounts of these nutrients to values that are considered to be appropriate for natural waters, through special \

• v
Jurisdictions.

The aim of the present invention is primarily to provide granular detergent and cleaning agent mixtures containing builders to create that have no or at most a low phosphorus value and a low nitrogen value, without relinquishing the generally recognized distributive effects that were previously associated with such complex-forming effects Builders have been obtained. Another object of the invention is to provide granular builder-containing

- 3 - ■

309845/109 /.

·. if ' 43981

tiger detergent and cleaning agent mixtures that are economical and can be produced rationally so as to use them their advantageous properties to the consumer in a reasonable manner Quantity and available at a reasonable price to deliver.

Another class of builder compounds can are referred to as precipitation builders, v / eil they cause the hardness constituents of the water, in particular Calcium and magnesium, in the form of inorganic crystalline precipitation products, precipitate out of the washing solution removed / grounded. Sodium carbonate is a common precipitation builder.

The above-mentioned terms complex-forming builder and precipitation builder generally refer to Builders, the predominant mechanism of which is the removal of metal ions from the V / aschlösung in the described 7v'is based. Complex-forming builders can thereby result in a small amount of precipitation and precipitation builders' can to a small extent to solubilize "contribute.

Another class of compounds found in builders Detergent and cleaning agent compositions are used are the silicates. Commercial laundries make particular use of the alkalinity and the pH puff recognition features that silicates yield to improve the cleaner. Silicates also reduce corrosion of aluminum parts used in washing machines. However, it is known that a product is used by the consumer used and accessible to children, should contain small amounts of alkaline components in order to avoid a hazard to exclude the health. Another goal of the The invention is therefore to provide safe amounts of the alkaline precipitation builders and silicates, which are combined in

30 98 45/1094

tion with the rest of the mixture will result in an effective cleaning.

According to the present invention, a granular Y / ash- and detergent mixture created, which contains the following components:

Component A, a biodegradable surfactant Medium, represents 17 to 26% by weight of the composition, from 20% to 65% by weight based on weight of component A, a hardness-resistant surfactant from the group

R (OGH ₂ GH ₂ ) _X OSO ₃ M,

wherein R is an alkyl group having 10 to 20 carbon atoms, χ 1 to 20 and
M mean an alkali metal, and

R ₃

are where

R ^ is an alkyl radical with 12 to 18 carbon atoms, R ₂ and Rz independently of one another are methyl, ethyl or ethanol radicals, *. - '

R ^ is an alkylene chain with 1 to 3 carbon atoms and X is an oxygen atom or a hydroxy radical

mean.

Component B, a complexing detergent ingredient, constitutes at least 15% by weight of the mixture, this being complex-forming builder 0 to 10 wt .-% condensed phosphate and 10 to 35 wt .-% sodium nitrilotriacetate, based based on the weight of the mixture.

- 5 -
30984S / 1 094

V 4-3981

Component C is sodium silicate with a weight ratio of SiO ₂ : Na ₂ O of 1.6: 2.3 and represents not less than 12% by weight of the mixture, and

Component D, a phosphorus-free precipitation builder for detergents, is present in such an amount that the sum of components B and D is not less than 20 % by weight of the mixture and the sum of components C and D is not greater than 45% by weight of the mixture. -% of the mixture.

The interaction of the various components of the approach can be explained as follows:

Component A is a surfactant of which a significant proportion is a hardness resistant surfactant. These are specifically surface-active Agents which, when used in hard water, have superior detergent and dispersing properties compared to common surfactants. The term cleaner refers to the capacity to remove particulate and greasy dirt from a substrate. Dispersing power is the ability of the particulate and greasy dirt that has been removed from a substrate by detersive "'painting, in suspension in a washing solution to keep. When a common surfactant forms a precipitate or an insoluble complex with hardening ions, the surfactant is converted into a relatively unusable form and does not function as intended Way.

Generally, it may be a function of detergency builders be referred to as removal, by complex formation or precipitation, of the hardness ions from the washing solution, so that these are no longer able to react in an undesirable manner with the surfactant. Hardness is mainly analytical as a mixture of calcium and magnesium ions

309845/1094

expressed as g GaCO ^ / 1 H _p O (grains / US gallon = gr. ^ per gallon H _? O). If a large amount of an effective builder is available, most of the hardness ions present in even very hard water are removed from the solution in conventional ash procedures the surfactant is protected from the hardness ions only in soft water or water of medium hardness, ie at a hardness of about 0.14 g / l or below (about 8 grains / gallon or below).

The mixtures according to the invention contain a significant proportion of surface-active agent that acts against hardness is constant. In hard water, this hardness-resistant surfactant works after the detergency builder is used up and yet hardness ions remain, its intended cleaning power and dispersing power functions v / more effective than conventional surfactants.

A class of surfactants, "which is the above Have the properties described are Alkyloxyäthersulfate. These have the general formula S (CCHpOHp) OSO, M, wherein R is an alkyl group with 10 to 20 carbon atoms, χ 1 to 20 and M is an alkali metal, preferably sodium, are. Alkyloxyethylene ether sulfates are biodegradable.

Alkyloxyäthersulfate are usually by Condensation of x moles of ethylene oxide CHp — CHp with fatty alcohol

ROH produced, whereby an alkyloxyethylene ether R (OCHpCH ₂ ) _x -OH is formed, whereupon it is sulfated with agents such as sulfuric acid, H ₂ SO ^, or sulfur trioxide, SOr _5. These compounds are described in U.S. Patent No. 3,332,876. However, the oxyethylene ether condensation reaction does not lead to one

- 7 -309845/1094

S ■ 43981

Product where χ is a single number. Rather, a distribution is obtained in which the alkyloxyethylene ether contains a mixture of special compounds, such as R (OGH ₂ CH ₂ ) XjOH, R (OGH ₂ GH ₂ ) ₂ OH, R (OGH ₂ GH ₂ ) ^ OH, etc., ie in which χ = 1, 2, 3 etc. Different distributions of χ are obtained depending on whether this reaction is accelerated by basic or acidic catalysts, but in each case a distribution is obtained and in each case the resulting alkyloxyethylene ether is converted into a surface-active agent after sulfation, which is in the wash - and detergent mixtures according to the invention is effective. The average value of χ for such a distribution is the number of moles of ethylene oxide that reacted with each mole of fatty alcohol. Alkyloxyethylene ether sulfates in which the average value of χ is 1 to 6 are preferred, and those in which the average value of χ is about 3 are particularly preferred.

Other surface-active agents which are effective in the context of the invention are the quaternary zwitterionic ammonium sultaines < _N

^R 2

R.
X

R _{1 is} an alkyl radical with 12 to 18 carbon atoms, R ₂ and R-ζ independently of one another are methyl, ethyl or ethanol radicals,

R ^ is an alkylene chain with 1 to 3 carbon atoms and X denotes a hydrogen atom or a hydroxyl radical. Sultaines of this composition are organic degradable.

309845/1094

ί 43981

Such connections are characterized by the presence of both positive as well as negative charge, which are internally neutralized (i.e. zwitterionic). You can in as described in detail in U.S. Patent No. 2,129,264 and DT-PS No. 1,018,421. Preferred Connections are:

(a) where E ^ contains 16 carbon atoms, Eo and E,

. Mean methyl, B ^ is ethylene and X is hydrogen if it is 3- (N, N-dimethyl-2il - hexadecylammonio) propane-1-sulfonate;

(b) v: orin E ^ contains 18 carbon atoms, Ep and E ^ Mean methyl, E ^ is ethylene and X is a hydroxyl radical means bonded to the second carbon atom, which is 3- (N, N-dimethyl-N-octadecylammonio) -2-hydroxypropane-1-sulfonate acts.

Suitable sources for the long alkyl chain of either the alkyloxyethylene ether sulfates or the zwitterionic suItains are natural fats and oils, such as coconut oil or tallow, which are produced using known sodium reduction or hydrogenation processes converted into fatty alcohols. Alternatively, the source can be a synthetic fatty alcohol, which has been produced by the Ziegler process, which is described in CA-PS No. 720,808.

Fatty alcohols of a particular chain length from these two sources are within the scope of the present invention to be regarded as equivalent. In both processes, however, a mixture of chain lengths is used in commercial use preserved, i.e. a segment length distribution arises. These Distribution differs depending on the source material and for certain purposes this difference can be important be"

- 9 -309845/1094

• ίο ·

The amount of surface-active agent, component A, required to obtain effective cleaning performance is 17 to 26% by weight of the mixture. About 20 % are preferred. Table 1 below shows a "comparison of about 25% component A versus about 20% component A in otherwise comparable granular batches. This illustrates the superiority of the latter with" avoidance of caking.

Only a part of component A is a hardness resistant surfactant as defined above. In particular, the hardness-resistant surfactant according to the invention makes up between 20 and 65 % of the weight of component A. Preferred areas of application of the hardness-resistant surface-active agent are between 25 and 60% by weight of component A. The remainder of component A can be any suitable biological degradable surfactant such as sodium linear alkyl sulfonate, commonly referred to as LAS, or sodium alkyl sulfate.

The considerations that have led to the selection of an appropriate amount of the hardness-resistant surfactant are as follows. At least 20 % by weight of component A is required to obtain effective cleaning performance according to the invention after the detergent builder has been consumed. Further hardness-resistant surface-active agents lead to an increase in cleaning performance, but have a disadvantageous effect on the flowability, hardness and caking resistance characteristics of the granules of the detergent mixture. Foaming is also reduced. V. ^r ie described in detail later, component G, ie silicate, also has a strong effect on these properties. Thus, up to a proportion of härteunempfindlichem surfactant of 65 wt -.% Of component A, these effects due to increased play art silicate within the above-mentioned, in the Siiicat-

- 10 -.

3 0 9 8 4 5/109 Ä

41 4th

application of the circumstances discussed 'are compensated.

The attractiveness of household v / ash and. Detergent mixtures for consumers is partly determined by the amount of foam that occurs in the ''. vas chm as chine. It's dated commercial Very important point of view is to deliver the foam value that is desired by the consumer.

In the mixtures according to the invention, foam formation can be regulated by a reasonable spray of component A and by using foam suppressors. If a high foam level is desired, a relatively large amount of surfactant can be used within the range contemplated in the present invention, and the type of surfactant used can be selected in view of its higher foaming properties. In general, 10 to 14 carbon atoms in the long alkyl chain of the surfactant according to the invention give higher foam levels than corresponding surfactants having 16 to 20 carbon atoms. In the most preferred range from G ^ ₁ , to C, g, a synthetic fatty alcohol starting material is preferred for high-foaming mixtures, since its distribution has relatively high proportions of C ^ - and G ^^ - components, while fatty alcohol from a sebum source for little foaming mixtures are preferred, since their distribution has in particular a high proportion of C ^ g component. It is also possible to further reduce foam formation by adding a foam suppressor based on a fatty acid or a mixture of fatty acid and non-ionic surface-active agent, as described in GA-PS ¹ η No. 579,174 and Hr. 609,202.

Component B is a complexing detergent builder that contains either 5 to 10 % condensed phosphate and

- 11 -

309845/1094

10 to 25 % sodium nitrilotriacetate or, if a phosphorus-free batch is desired, 15 "to 35 % sodium nitrilotriacetate, all percentages being based on the weight of the mixture. The condensed phosphate can be alkali metal tripolyphosphate or alkali metal pyrophosphate. Sodium tripolyphosphate is preferred.

The most widespread granular detergent and cleaning agent mixtures for high-performance household laundry that have hitherto been in use contained about 50% by weight of sodium tripolyphosphate. This compound has the formula Nac-Ρ, Ο ^ Λ and about 25.3 % of its weight is made up of the element phosphorus; this detergent mixture therefore contained about 12.6 % phosphorus. In contrast, the use of sodium tr! Polyphosphate according to the invention, which makes up 5 to 10% by weight of the mixture, contributes only to about 1.26 % to 2.53% phosphorus, based on the weight of the ', vase- and detergent mix. This means a significant reduction in the phosphorus content of the mixture and, accordingly, a significant reduction in the phosphorus content of the detergent wastewater, which makes up part of the natural watercourses. These phosphorus levels are within the limits proposed by various government bodies for environmental protection.

-1

Sodium nitrilotriacetate has the formula M (OHoC00Na) ^. It is commercially available as a monohydrate, but all references to the compound in the present invention are to the anhydrous form. The element nitrogen is approximately 5 »4-5 wt .-% of Natriumnitrilotriacetats. The application of Hatriumnitrilotriacetat in the invention, the mixture of 10 wt .-% makes up to 35, delivers approximately 0,54- to 1.90 ° / o nitrogen, based on the weight of the detergent and cleaning agent mixture. These numerical values are not only low in themselves, but the nitrogen that enters the waterways as washing wastewater has it

- - 12 -

309845/1094

has a proportionally smaller effect on the environment than phosphorus, because the element nitrogen occurs in natural sources in greater quantities than the element phosphorus.

It is generally assumed that the complex formation is a molar puncture, ie that the number of moles and the amount of grams of a complex-forming builder in a VJasch situation is decisive for its complex-forming capacity. Therefore, detergent and cleaning agent mixtures which contain 35% by weight of sodium nitrilotriacetate have a comparable complex formation capacity compared to the widely used mixtures as mentioned above and which contain 50% by weight of sodium tripolyphosphate. All mixtures according to the invention are "low builder" when compared to this standard containing 50% sodium tripolyphosphate *. While each molecule of sodium tripolyphosphate contains 3 phosphorus atoms, each molecule of I sodium nitrilotriacetate contains only one nitrogen atom. The mixtures according to the invention therefore make only small contributions to nutrient elements, based on atomic or weight. ,;

Component 0 is sodium silicate. Tenn them in one An amount of at least 12% by weight of the mixture is present, it solidifies the granules of the detergent mixture and free-flowing and free from caking, even after storage. 15 to 23% silicate is preferred and about 20% Silicates are particularly preferred. This function of the silicate counteracts the opposite effect of the hardness-resistant Proportion of component A is related. In usual grains of Y / ash and detergents that big Containing quantities of sodium tripolyphosphate, silicates have been used in a small proportion, often 6 to 10%, to regulate the pH and the corrosion of aluminum parts used in washing machines to a minimum to belittle. The properties of pourability and des

- 13 309845/1094

Non-caking of such mixtures are obtained with hydradation of the anhydrous tripolyphosphate by water of crystallization to form the hexahydrate form, Na ₁ -P ^ CL ₀ .6TL ₃ O. This acts as an effective moisture sensor and converts moisture adsorbed from the atmosphere into solid, highly crystalline tripolyphosphate hexahydrate.

If tripolyphosphate is not present or only in small amounts Is present and this moisture binder is absent or in such small amounts that it is ineffective is, causes moisture in the detergent granules during storage are exposed to the fact that the grains become soft and lumpy and caking occurs during storage so that it is difficult for the housewife to pour the product out of the detergent box and measure it. Even the residual moisture that remains after the process of spray drying the grains is often at such mixtures are sufficient to make them soft and lumpy to such an extent that they can flow through the packaging machine is delayed. This requires spray drying to a lower moisture content than otherwise would be necessary, thereby reducing the capacity of the spray dryer is decreased and economic losses occur.

Physical properties of the grainy 77ascn and Detergents can be measured using a cake formation test. This test, described below, is used contributes to the tendency of the detergent granules to cake Applying pressure as opposed to remaining as free flowing Determine the product. Ss was found to have the ability of the grains in a satisfactory manner in the manufacturing and packaging processes of detergent manufacture and maintaining discrete particles in the box of detergent and cleaning agent during storage time can be predetermined. This test consists of the

309846/1094

IS 43981

Storage of food and detergent granules during a for a certain period of time in cartons of the 7th detergent and cleaning agent under predetermined conditions of temperature and humidity, the formation of a compacted mass of the grains by compressing them into a cylinder under standardized conditions and then removing them the surrounding walls and measurement of the force required to break the resulting cake. It is obvious, that mixtures that require numerically high forces are bad; Mixtures that require low forces, can be described as good.

Data for four embodiments of the present invention are given in Table 1 below. A comparison of approaches (a) and (b) shows that by increasing the silicate content from 10 to 20 %, a substantial reduction in the caking of the grains is achieved. A comparison of runs (b) and (c) shows that a reduction in the amount of surfactant leads to a large reduction in the cake-forming properties. In approaches (a), (b) and (c) the ingredients sodium carbonate and sodium sulfate were varied freely, that is, when the silicate content or the surfactant was reduced, carbonate or sulfate was added to make the total amount of the mixture. A comparison of approaches (c) and (d) shows that replacing large amounts of sodium sulfate with sodium carbonate has only a minor effect on cake firmness, ie "that these additives are almost equivalent in this respect.

Tab. 1: ./.

- 15 309845/1094

43981

Table 1

Composition (wt .-%): total a A η s a t ζ: d Cake firmness, force in
break." 25.3 b C. 20.1 Surface active
Middle * Storage time ** 4
in days: 7.6 25.1 19.9 7.5 Sodium tripolyphosphate 8th 11.7 7.5 7.5 11.6 Sodium nitrate triacetate 15th 10.1 11.6 11.6 20.1 Sodium silicate, wt.
Ratio of SiO _P :
Na ₂ O = 2.28 ^ 22nd
f 25.1 20.1 19.9 0 sodium 29 16.65 14.9 23.2 36.7 Sodium sulfate 0.75 16.55 13.1 0.6 Sodium toluenesulfonate 0.5 0.75 0.6 0.5 Aminostilbene fluorescence
material 2.3 0.5 0.5 2.9 water 100.0 3.0 3.7 100.0 kg (Ib) 100.0 100.0 to crush 1.08
(2.4) , to the cake 0
(0) 1.50
(3.3) 0.82
(1.8) 0
(0) 0
(0) 1.72
(3.8) 1.00
(2.2) 0
(0) 0.18
(0.4) 1.72
(3.8) 1.36
(3.0) 0
(O)- 0.36
(0.8) 1.95
(4.3) 1.22
(2.7) 0
(0) 0.59
(1.3) 1.54
(3.4) 0
(0)

Surface-active agent containing a mixture of 55 % sodium alkyloxyethylene ether sulphate with an alkyl group derived from tallow and an average of 3 oxyethylene residues and 45 % sodium linear alkyl sulphonate

- 16 -

309845/1094

having an alkyl group averaging 12 carbon atoms.

** Storage "at 27 ° 0 and 80 % relative humidity in standard detergent cartons with a capacity of approximately 1800 cm3 (110 cubic inches). In standard size; made from folding box board" coated with wax on the outside ".

Silicates can be obtained in either liquid or solid form and any of these forms can find use in the mixtures of the invention, but the solid form is preferred because it reduces the evaporation load in the spray drying tower. All references to amounts of silicate relate to silicate solids, ie the sum of the anhydrous components SiO ₂ and Na 2 O.

Silicates are also characterized by their weight ratio of SiOp to Na ₂ O. It is evident that silicates which have low SiOo to ITa _{2 O ratios have a higher Na 2} O content for a given solids content and therefore give higher alkalinity. They also contribute less effectively to the hardness and pourability properties of granular detergent and cleaning agent mixtures. The lower tert of the silicate ratio for the mixtures according to the invention is 1.6.

On the other hand, high SiO ₂ to NapO ratios adversely affect the processing of the detergent sludge in the production of detergent and cleaning agent mixtures. It is known that. Silicates "having a ratio of about 2.0 and below form simple ions in solution and that colloidal polymeric ion aggregates occur in increased amounts when the ratio is increased above about 2.0.

The usual technical process for spray drying granular detergent and cleaning agent mixtures is on the well known in the relevant field. It will be a slurry

- 17 -309845/1094

preparation that contains all of the components borrowed from the approach. This slurry is continuously pumped into a spray tower, wherein the slurry; finely divided and the resulting spray product is dried by means of heated air. It is evident that the success and effectiveness of this procedure depends, inter alia, on achieving good spreading to provide adequate surface area for drying, and on minimizing the amount of water to be removed during drying is a consideration from the point of view of the V ^.: ärmebilanz. It has been found that for the detergent mixtures according to the invention a silicate ratio of 2.3 is the practical minimum that can be tolerated, while maintaining reasonably low viscosities for spray drying. A silicate ratio of about 2.0 is maintained The flow conditions in washing and cleaning agent slurries are complex and conventional viscometers designed for non-Newtonian liquids with low viscosity do not give a satisfactory measure of the pumpability and atomization of washing and cleaning agent slurries a satisfactory practical measure for these factors is the amount of power required to stir a detergent slurry under standard conditions. * '

The data given in Table 2 were obtained by putting the respective slurries in a Laboratory mixer mixed and 'the power consumption of the stirrer and its H speed were determined. In particular voltage and amperage determined by a standard laboratory model mixer V Lightnin (trademark from Mixing Equipment Company), and the corresponding speed / min of the stirrer is measured. It it was observed, as can be seen from Table 2, that the vis-

- 18 3098AB / 109A

The viscosity of the sludge, which was produced from a mixture of detergents and detergents with a silicate ratio of 2.4-3, was drastically increased within a narrow range of decreasing moisture content: from 28 to 27 % this effect was observed at about 57 ° C and between 27 and 25 % a similar effect was found at around 71 ° C. This viscous phase was a sticky, dough-like, non-pumpable mass. In marked contrast, the viscosity of both slurries prepared from I detergent and detergent mixtures according to the invention, ie those having a silicate ratio of 2.00, was increasingly uniform and regular down to very low moisture levels of the slurry.

Table 2:

Power consumption of detergent and cleaning agent slurries. * '

(Watt)
Temperature = 57 ° C

Moisture
keep the up
slurry:
(%)
(a ¹ ) Approaches) Silicate-**
relationship
2.00 _(cl) Approach (noun) 24-
² 5
26th
27
28
29 Silicate-**
relationship
² '^ (b) 280
240
205
170
135
110 Silicate-**
relationship
2.00 _(d0 > 300
120
95 270
230
190
155
130
105

- 19 -309845/1094

2320753 W). - 71 ⁰ O (d) 230 Ports. Tab. 2: 170 190 (äÖ Ο ') 140 150 temperature 115 115 24 100 90 25th > 300 90 75 26th 230 80 27 125 28 90 29 75

The solids fractions of batches (e) and (f) had
the following compositions:

Approach (s):. Approach (noun)

Composition (Qew .- ^) s

Surface active Middle ***

Sodium tripolyphosphate sodium nitrilotriacetate

Sodium! Iicat (ratio as defined in the table above)

Sodium carbonate Sodium sulphate

Sodium toluenesulfonate

.Total

20.9 - 20.9 7.8 7.8 12.2 24.3 20.9 20.9 10.5 O 26.6 25.0 1.1 1.1

100.0

100.0

* Mixed under standard conditions at 1000 tlmdr / min. ** Weight ratio SiO ₂ ί Na ^ O.

♦ * ♦ The surface-active agent contains a mixture of 30 % sodium alkyloxyethylene ether sulphate with an alkyl group which is derived from tallow and an average of 3 oxyethylene residues, and 70 % sodium linear alkyl sulphonate with an alkyl group which has an average of 12 carbon atoms.

*; ■ - 20 -

30984S / 1094

A difference in the moisture content of the sludge that is as low as 2 % is of great importance for technical practice. Assuming that the dem. If the detergent mixture to be subjected to spray drying has a moisture content of 4 % , the number of kg of water required to evaporate per kg of solid is 12% higher if it is a slurry with a moisture content is 28 % compared to a slurry with a moisture content of 26 %. This has the direct effect of a 12% greater vaporization load for the spray tower, which is a clear, economic disadvantage.

Thus, as discussed above, the limits of the silicate ratio according to the invention in the range 1.6 to 2.3 are critical, with about 2.0 being preferred. Furthermore, the specified amount of silicate, which is a minimum of 12 %, is critical in order to maintain the bulk properties of the detergent granules. The upper limit of the silicate content is also critical; however, this is also a function which depends on the application of component D, as explained in detail below.

Component D is a detergent builder. Examples of this class of builders are the alkali metal salts of carbonate, sesquicarbonate and bicarbonate be mentioned. The salts that are formed by these precipitation builders in hard water are finely divided crystalline particles - which are largely due to the action of the detergent and cleaning agent mixtures surfactant used are suspended. Even the lesser part that can adhere to the tissues, occurs as a finely divided white crystalline precipitate, which clearly differs from hardness precipitation in the form of calcium and Magneaium soaps distinguish which are sticky and represent gelatinous compounds attached to the tissues

- 21 309845 / 109A

ν 4 «

and at the Y / as chm as chine in an objectionable "form can adhere, which is commonly known as soap precipitation ". Even with the exclusive use of synthetic detergents, i.e. surface-active agents, in the formulation of a builder-containing 7 / ash and cleaning agent mixture 'Calcium and magnesium soaps are formed during the washing process by neutralizing the fatty acids contained in the Contains dirt from naturally soiled clothing such as shirts, socks, and underwear.

A precipitant builder such as sodium carbonate, complements are well-equipped 'it toffleistung the complexing Geriststüf fes. This effect is particularly important when the amounts of the condensed phosphate and / or nitrilotriacetate are selected so that they are close to the lower limits of the respective ranges described above. Because of this combined effect of complexing and precipitation builders, it is appropriate to define the mixtures according to the invention in such a way that the sum of these two components is given which are required to give effective detergency builder performance. The lower limit of the sum of components B and D is 20% by weight of the mixture. The sum of these components is preferably at least 25% by weight of the mixture. If the amount of detergent complex builder component B employed is close to the maximum value, it is not essential to supplement with a precipitation builder. If necessary, however, this can be done with the proviso discussed below. Ylexm. on the other hand, the application amount of component B is close to the minimum value contemplated by the invention, a detergent builder is necessary to achieve the objects of the present invention.

The upper limit that can be applied when using the component C, silicate, in detergent and cleaning agent mixtures

- 22 308845/1094

is related to the application of component D, the precipitation builder. This is because both not only alkaline compounds are, but also a very large and almost equal capacity for buffering the pH - "* ertes im Range from 9 »5 to 11.5, i.e. the usual area for high-performance detergent and cleaning agent mixtures. Alkalinity makes a positive contribution to cleaning power, especially with mixtures containing nitrilotriacetate contain, but must be adjusted to a value at which there is no potential danger if the washing and detergent mixture is accidentally eaten or comes into contact with the eyes. It goes without saying correct that alkalinity is only one factor in a number of factors that should be considered in assessing the safety of Detergent and cleaning agent mixtures for use by the consumer must be taken into account. The invention Mixtures have proven useful in testing granular laundry and detergent products, for household use are intended to be proven to be safe.

Based on the above considerations, it is appropriate that the sum of components O and D make up no more than 45% by weight of the mixture. The sum of these components is preferably no more than 35% by weight of the mixture. Thus, if a minimum level of silicate, namely 12%, is used, it is permissible to use an amount as high as 33 % builder. However, if it is desired to use 30% silicate, the maximum allowable precipitation builder is 15% and preferably only 5 %. . -

A preferred embodiment of the present invention provides for the use of 6 to 9% sodium tripiophosphate and 10 to 13 % sodium nitrilotriacetate as component B and sodium carbonate in such an amount that the sum of components B and D is between 28 and 32 % ,

- 23 -

309845/1094

• ■ ZH 4-98-1

all percentages being based on the weight of the mixture. Another preferred embodiment provides .6 to 9 % sodium tripolyphosphate and 22 to 25 % sodium nitrilotriacetate as component B and sodium carbonate in such an amount that the sum of components B and 1) is between 28 and 32 % , the same as above all percentages relate to the weight of the mixture.

Additions. Additives, as they are commonly found in laundry detergents and Detergent mixtures used can be used in addition to the larger components according to the invention will. Enzymes can be used in the form of protease, amylase and / or lipoxidase. Others if necessary Components to be used for special purposes are borax, foam suppressors, foam boosters, hydrotropes, Anti-corrosion agents, anti-redeposition agents, dyes, fluorescent substances, perfumes and the like .. sodium sulfate and a few Percentage of water are common constituents of the mixtures according to the invention, as they are in conventional laundry detergent and cleaning agent mixtures represent.

Oxygen bleaches such as sodium perborate can be incorporated into the mixtures of the invention. Another useful oxygen bleaching agent is a complex of sodium carbonate and hydrogen peroxide, sometimes referred to as 2Na ₂ CO ^ .3HoOo and sometimes, for the sake of simplicity, but imprecisely, also as sodium percarbonate. If this complex is used, its sodium carbonate content, Na ₂ CO -, to be considered as part of component D.

The following specific examples illustrate The invention:

- 24 309845/1094

JK

Example 1: Sprayed Dried Grainy? Tableings will decrease with the following combinations manufactured. The approaches (g)> (^) -, (i) and (j) were at Hand of 7. "as cn- and Carrying methods tested with multiple repetitions - whereby it has been found that they have good cleaning properties. Approaches (i) and (k) were made with respect to stain removal tested for typical household 3-leaks, such as spinach, butter, and clay, and found was found to have good stain removing properties.

Approach: (s) (H) Ci-) CD) Ck) Composition
in wt .-? 4: Surface active
Middle * 20 ι 20th 20th 20th 20th Sodium tripolyphOS
phat 7.5 7.5 7.5 7.5 7.5 Sodium nitrilotriacid
acetate 11.6 ■ 11.6 11.6: 23.2 23.2 Sodium silicate,
Weight ratio
SiO ₂ : Na ₂ O = 2.0 20.0 20.0 20.0 20.0 20.0 Sodium 23.0 ] 0; 10.0 0 0 Sodium sulfate ^: 13.2 36.5 25.4 22.7: 23.7 water 2.0 2.0 3.1 4.2 3.2 Lower inventory
share ♦ * 2.4 2.4 2.4 2.4 2.4
100.0 100.0 100.0 100.0 100.0

* The surface-active agents of batches (g) and (h) contained 55 % sodium alkyloxyethylene ether sulfate, v / or in which the alkyl radical is derived from tallow, with an average of 3 oxyethylene radicals; and 45 % sodium linear alkyl benzene sulfonate having an alkyl group having an average of 12 carbon atoms.

- 25 309845/1094

The surfactants of formulations (i) and (k) contained " ² O % sodium aikyloxyethylene ether sulfate, in which the alkyl radical is derived from tallow and with an average of 3 oxyethylene radicals; and 70 % tiatrium linear alkylbenzenesulfonate with an alkyl group which is on average Has 12 carbon atoms »

The surface-active agents of approach (j) contained 30 % iiatriumalkyloxyäthersulfat, "-orin 70 % of the alkyl radical of tallow and 70 % of the alkyl radical of synthetic fatty alcohol (manufactured according to GA-PS ITr. 720,808, with 16 carbon atoms in Mitteiletv; a) and there are on average 3 oxyethylene radicals; and 70 % sodium linear alkylbenzene sulfonate with an alkyl group which has an average of 12 carbon atoms.

Smaller components, which are the same in all approaches, containing 1.0 % sodium sulfonate, 0.15% perfume, 0.5 % aminostilbene fluorescent and unsulfated or respectively. unsulfonated material.

B e i s ρ i e 1 2: Further examples of grainy '"ash- and detergent mixtures according to the invention which have good cleaning power and dirt and stain removal properties have, the approaches are in Table 1 above (a), (b), (c) and (d); and in Table 2 the approach (f) and Approach (s) with a content of silicate, which is a Gewients-

SiO ₂ : lia ^ O ratio of 2.00.

B el s pi e 1 3: Essentially the same results are obtained when the surface-active agents of the preparations of Examples 1 and 2 are replaced by equal amounts of 3 - (!?, Ί'-dimethyl-lf-hexadecylammonio) -propane-1 sulfonate or 3- (LTI, K-dimethyl-N-octadecylammonio) -2-hydroxypropane-i-3ulfonat replaced »7'enn these approaches are used in cold 'Yasser with a temperature between 4 ° and 38 G ⁰ G, the cleaning and stain removal properties are particularly good compared to those of conventional laundry detergent and cleaning agent mixtures which are used at the same temperature.

- 26 -

309845/1094

Example 4 Substantially the same Errebnisse receive earth v ^r, when the number of Oxyätnylenrente the surfactant of Example 3 is not .1, but has the value 1, 2, 4, 5 od. 6. Cleaning and stain removal results are also obtained when the alkyl group of the surface-active agents of Example 1 is derived from coconut oil, from a mixture of coconut oil and tallow in a weight ratio of 60:40 or from a mixture of tallow and synthetic fatty alcohol (prepared according to the procedure of CA. -PS No. 720,803, ^ o. Where the length of the /, Ikyl radical is on average about 14 carbon atoms) in a weight ratio of 60:40.

Example 5: Other granular detergent and cleaning agent mixtures which have good cleaning stain removal properties are made according to the following approaches:

Approach: (D (HL) (n) (O) (P) (q) (r) (S) composition
(in wt .-> j) i surfaces
active participation
tel * 17th 17th 17th 21 21 21 26th 26th Sodium tri-
pply phosphate 5 5 VJl 8th 10 10 Sodium pyro
phosphate VJl 5 Potassium tripo
lyphosphate 5 Sodium nitrate
lotriacetate 10 25th 18th 22nd 22nd 10 10 25th

Cont .: ./.

- 27 -

3 0 9845/109

Cont .: (D (m) (n) Co) - (P) (q) (Γ) (S) Approach: Sodium- silicate: Weight ratio ratio - by SiOo to NapO: 15th 25th 20th 1.7 15th 12th 2.0 20th 25th 2.3 sodium 5 25th 15th carbonate Λ r \ potassium IU IU carbonate Sodium bi 15th 5 carbonate Sodium sul fat and. . water -: ι
I. OO - I; . Rest on

The surfactant contains a mixture of 40 % sodium alkyloxyethylene ether sulfate with an alkyl group derived from tallow and an average of 3 oxyethylene residues; and 60 % sodium linear alkyl sulfonate with an alkyl group averaging 12 carbon atoms.

Preferred embodiments of the invention:

B ei s ρ i e 1 6: Solid, free-flowing, non-cake-forming, granular, spray-dried ?; Ash and detergent mixtures v / urdeη with the compositions given below manufactured. The flow properties of the detergent slurries were, as evidenced by the good pumpability and

- 28 -

30984 6/1094

ZS 43981

Sprayability in the spray drying process results in good. These blends showed good cleaning and stain removal performance while washing.

Approach; (away)

Composition (in% by weight) Surfactant * Sodium Nitrilotriacetate Sodium Silicate, G-ev; .- Ratio SiOp: NapO = 2.0

Sodium perborate (anhydrous) sodium sulfate

Smaller components **

20.0 20.0 23.2 23.2 20.0 20.0 2.9 0 24.5 27.4 9.4 9.4

100.0 100.0

* The surfactant contains 30 % sodium alkyloxyethylene ether sulfate, in which 30 % of the alkyl radical of tallow and 70 % of the alkyl radical of synthetic fatty alcohol (prepared according to the method of CA-PS No. 720,808) with an average of about -16 carbon atoms are derived and where im There are an average of 3 oxyethylene residues; and 70 % sodium linear alkylbenzenesulfonate with an average of 12 carbon atoms in the alkyl chain.

· ** Contains water, 1.0 % sodium toluene sulphonate, 0.1% perfume, 0.5% aminostilbene fluorescent substance, and non-sulphated or non-sulphonated material.

V / if 20 or 25 % sodium nitrilotriacetate is ended in the above batches, results that are approximately the same are obtained.

Example 7: Other free-flowing granular 7; ash- and detergent mixes are prepared according to the approaches below. The flow properties of the Detergent slurries are good and the properties of the Cleaning and staining the mixes while washing are equally good.

- 29 309845/1094

30th 2320753 17 ** (e) Cf) 24 * 45981 (c) 30th 20th Approach: 21 *** .21 ** Cb) composition
(in% by weight ) ·. 17 * 22nd 22nd ■ Surfaces
active agent 15th 26 *** Sodium nitrilo-
triacetate 20th 12th 20th 25th 35 Sodium silicate
Weight ratio
SiO ₂ : Na ₂ O: 15, 3 3 · 1.6 25th 2.0 35 2.3 15th Sodium perborate 5 ■ sodium 15th 5 Potassium carbonate 10 Sodium bicarb
onat - 100 Sodium sulfate
and water Rest on

The surfactant is a mixture of 40 % sodium alkyloxyethylene ether sulfate with an alkyl group derived from tallow and containing an average of 3 oxyethylene residues and 60 % sodium linear alkyl sulfonate with an alkyl group containing an average of 12 carbon atoms.

The surfactant is a mixture of 60 % sodium alkyloxyethylene ether sulphate, in which the alkyl group is derived from tallow and with an average of 3 oxyethylene groups, and 45 % sodium linear alkyl benzene sulphonate with an alkyl group containing an average of 12 carbon atoms.

*** The surfactant is a mixture of 25

Sodium alkyloxyethylene ether sulphate, in which the alk7 / 1 radical is derived from tallow, with an average of 3 oxyethylene radicals, and 70 % sodium linear alkylbenzenesulphonate, the alkyl group of which has an average of 12 carbon atoms.

- 30 -

309845 / 109A

Example 8: Essentially the same results are obtained if the surface-active agents according to the batches of Examples 6 and 7 are mixed with the same amounts of 3- (N, Ή -dimethyl-F-hexadecylammonio) propane-1-sulfonate or 3- (N, N-dimethyl-N-octadecylammonio) -2-hydroxypropane-1-sulfonate can be replaced. If these approaches are used in cold water at a temperature between 4 and 38 C, the cleaning and stain removal properties are particularly good compared to those of conventional detergent and cleaning agent mixtures that are used at the same temperature.

Example 9: Essentially the same results are obtained when the number of oxyethylene residues of the surface-active agents of Examples 1 and 2 is not 3, but has the numerical value T, 2, 4, 5 or 6.

Good cleaning and stain removal results are also obtained when the alkyl group is the surfactant Means of Examples 1 and 2 from coconut oil, from a mixture of coconut oil and tallow in a weight ratio 60:40 or from a mixture of tallow and synthetic fatty alcohol (produced according to the procedure the CA-PS ITr '. 720,808), the length of the alkyl radical being on average about 14 carbon atoms »in a weight ratio of 60:40.

Example 10: A solid, free-flowing, non-cake-forming, granular, spray-dried detergent and cleaning agent mixture is produced with the composition (i) given below. The flow properties of the detergent slurry are good. The mixture of the composition (j) is prepared for testing by mechanically mixing 15 parts of sodium carbonate with 100 parts of the mixture of the composition (i). Both compositions perform well in laundering in terms of stain removal, cleaning, and in preventing redeposition of soil on fabrics.

- 31 -

309845/1094

Approach: (i) (j)

composition
(in% by weight): ~

Surface active mit- oc η oa η tel * ⁵ V ' ^y

Sodium nitrilotriacetate 23.2 x 20.2

Sodium Silicate, Gevr.-

SiO ₅ : Na _P 0 ratio = 20.0. 17Λ 2.0 .

Sodium carbonate 0 13.0

Best ** 31.8 27.7

100.0 100.0

* The surface-active agent contained 55 % sodium alkyloxyethylene ether sulphate, in which the alkyl group is derived from tallow and which has an average of 3 oxyethylene groups, and 45 % sodium linear alkylbenaene sulphonate with an alkyl group which has an average of 12 carbon atoms.

** Sodium sulfate, water and minor ingredients.

- 32 -

Claims (1)

SS 45981 Patent claims: - i) Granular detergent and cleaning agent mixture, containing as component A a "biodegradable, surface-active agent, which makes up 17 to 26 Qev .-% of the mixture, of which 20 wt .-% to 65 C-ew .-%, Based on the weight of component A, hardness-resistant, surface-active agent from the group R (OGH ₂ CH ₂ ) _x OS0 ^ M wherein R is an alkyl group having 10 to 20 carbon atoms, χ 1 to 20 and
M is an alkali metal
symbolize, and J X wherein R / is an alkyl radical with 12 to 18 carbon atoms, R ₂ and R, independently of one another, are each a methyl, ethyl or ethanol radical, R ^ is an alkylene chain with 1 to 3 carbon atoms and X is hydrogen or a hydroxyl radical mean, are, as component B a complex-forming detergent builder which makes up at least 15% by weight of the mixture and makes up 10 % condensed phosphate and 10 to 35 % fat tri'um nitrilotriacetate, based on the weight of the mixture, as component C sodium silicate, which is not less than Gev; .- fi of the 'mixture, the weight ratio - 33 309845/1094 nis of SiO ₂ to ITa ₂ O 1.6 to 2 ,? is, and as component D-phosphorus-free precipitated detergent framework in a quantity of 0 to 33% by weight of the mixture in such a proportion that the sum of components B and I) is not less than 20 % by weight of the mixture and the The sum of components C and D does not exceed 45% by weight of the mixture. -2. Detergent and cleaning agent mixture according to claim 1, characterized in that the hardness-resistant surface-active agent of component A is based on 25% by weight to 60% by weight on the weight of component A, and a product of the formula where R is an alkyl group having 14 to 18 carbon atoms and χ is 1 to 20, the mean value being 1 to 6; Component C makes up 15 to 23% by weight of the mixture and the phosphorus-free precipitation detergent builder of component D is sodium carbonate in an amount such that the sum of components B and D is not less than 25% by weight of the mixture and the sum of components G. and D is no greater than 35% by weight of the mixture. 3. Washing and cleaning agent mixture according to claim 1 or 2, characterized in that component A makes up about 20% of the mixture and the hardness-resistant surface-active agent of component A has the formula R (OCHoCH ₀ ) OSO ₇ Na wherein χ is 1 to 20, on average about 3, and Component C represents approximately 20% by weight of the mixture and has a weight ratio of SiOp to NapO of about 2.0. "■■■ -" ■ - 34 - ■ ^; 3098AS / 1094 SS 43981 4. Washing and cleaning agent mixture according to claim 3, characterized in that the hardness-resistant surface-active agent of component A JO accounts for up to 55 % of component A. 5- Detergent and cleaning agent mixture according to one of the Claims 1 "to 4, characterized in that the condensed phosphate of component B is sodium tripoly-phosphate. 6. detergent and cleaning agent mixture according to claims 4 and 5, characterized in that the complex-forming detergent builder of component B 6 to 9 % sodium tripolyphosphate and 10 to 13% sodium nitrilotriacetate, based on the weight of the mixture ^ and the sum of components B and D makes up from 28 to 33% by weight of the mixture. 7. ■ pTasch- and cleaning agent mixture according to claims 4 and 5, characterized in that the complex-forming detergent builder of component B 6 to 9 % sodium tripolyphosphate and 22 to 25 % sodium nitrilotriacetate, based on the weight of the mixture * ¹ and the sum of Components B and D makes up from 28 to 32% by weight of the mixture. 8. Phosphorus-free detergent mixture according to claim 4, characterized in that the complex-forming detergent builder of component B makes up 20 "to 25% by weight of sodium nitrilotriacetate, based on the weight of the mixture. - 35 309845/10 <K S6 9. Phosphorus-free detergent and cleaning agent mixture according to claim 8, characterized in that it also contains up to 3 % sodium perborate or sodium percarbonate. For The Procter & Gamble Company Cincinnati, Ohio, V.St.A. (Lawyer) 0.98 45/109 U