DE2433485A1 - ALUMINOSILICATE ION EXCHANGERS SUITABLE FOR USE IN DETERGENTS - Google Patents

Description

For use in detergents suitable aluminosilicate

Ion exchanger.

The present invention relates to aluminosilicate ion exchangers, in particular ion exchangers made from aluminosilicates, the divalent and polyvalent cations quickly and effectively remove from water. The aluminosilicates according to the invention are quick and effective water softeners, they can be used in detergents as G-builders and thereby replace the previously used water-soluble structural substances.

It has long been known that various naturally occurring Aluminosilicates, usually in the form of clay minerals, which Calcium hardness from water through gelation or otherwise can remove, see e.g. Rao, in Soap, 3, No. 3, pp. 3-13 (195o); Schwartz et al., "Surface Active Agents and Detergents", Vol. 2, p. 297 ff. (1966). /

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The zeolites, especially naturally occurring aluminosilicate zeolites, have been proposed for "use in detergents, see U.S. Patents 2,213,641 and 2,264,103.

Various aluminosilicates have been proposed for use as detergent additives, see e.g. U.S. PSS 923 850 and 1 419 625 and GB-PSS 339 355, 461 103, 462 591 and 522 O97. Synthetic zeolites which are particularly suitable for adsorbing gases are described in US Pat. No. 2,882,243. U.S. Patent 3,310,373 relates to the preparation of crystalline aluminosilicates and U.S. Patent 3,674,426 relates to the use of eye metal oxic acids to increase the Adsorption properties of the synthetic zeolites according to US Pat. No. 2,882,243. The previously known synthetic zeolite Aluminosilicates are calcined to achieve optimal gas adsorption properties. You don't have the ones to be effective Water softeners and detergent builders required Cation exchange rate and capacity.

The German patent application filed on May 9, 1974 P 24 22 655.9 concerns complex crystalline aluminosilicates and their use as calcium hardness sequestering agents. Although these agents are suitable for the intended purpose, their use is limited by the fact that they only have calcium hardness sequester, but have practically no effect on the magnesium hardness. In the specified patent this is Difficulty is overcome by adding additional, water-soluble builders along with the aluminosilicates for the purpose of elimination the mixed hardness sets in.

From the above it can be seen that numerous methods for removing the hardness cations have hitherto been used were tested from water. Particular attention was paid to the removal of hardness cations from aqueous washing systems in the Washing process from household washing machines for free. In order to

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an ion exchange material in a detergent really If it is useful, it must have sufficient cation exchange capacity so that the hardness of the ash liquor is noticeably reduced without the need for excessive amounts of the ion exchanger. Furthermore, the ion exchange material must be quick act, i.e. the cation hardness of an aqueous wash liquor must be within the limited time. (approx. 10 to 12 minutes), that is available to a household washing machine during the washing process to an acceptable level. Optimally, effective ion exchange materials should be used be able to reduce calcium and magnesium hardness to about 0.96 to 1.92 dH within the first 1 to 3 minutes of the wash cycle to lower. Furthermore, useful cation exchange builders are suitably essentially water-insoluble, inorganic Materials that cause little or no ecological problems in wastewater.

It has now been found that certain amorphous and mixed amorphous / crystalline aluminosilicates both the high ion exchange capacity and the rapid ion exchange rate that are used for cation exchange builders in ashes are required. It was also found that the amorphous and mixed amorphous / crystalline aluminosilicates reduce both calcium and magnesium hardness without additional, water-soluble builders are required.

It is therefore an object of the present invention to provide Aluminosilicate ion exchangers that sequester both calcium and magnesium ions from aqueous solutions. Her Ion exchange capacity and ion exchange rate for calcium and magnesium ions should be so high that they are suitable as detergent builders.

Another aim of the invention is to provide detergents, which insoluble, amorphous, inorganic aluminosilicate

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contain ion exchangers that reduce the Ca ⁺⁺ and Mg ⁺ hardness without the need for additional G-builders. The detergents can optionally contain crystalline aluminosilicates.

The invention relates to aluminosilicate ion exchangers that reduce the calcium and magnesium ion content (mixed hardness) an aqueous solution rapidly reduce * The invention Aluminosilicates are of two types, both of which are useful as detergent builders. The first type is it is a water-insoluble, amorphous, hydrated Aluminosilicate ion exchange builder material of the empirical formula

Na (JtAlO _2. YSiO ₂ )

wherein χ is a number from 1 to 1.2 and y is 1, this continues through an Mg * ■ exchange capacity of approx 50 mg ÄcL. CaCO_ / g to about 150 mg-ÄcL. CaCO, / g (on anhydrous Base) is marked.

The second type of aluminosilicate builders according to the invention include mixed amorphous / crystalline aluminosilicate ion exchange builders containing

(a) a water-insoluble, crystalline aluminosilicate ion exchange material the formula

where χ is an integer from about 2o to about 3o (preferably 27) means wherein the crystalline aluminosilicate ion exchange material has a particle size of about 1 to about 100 microns in diameter (preferably 1 to about 10 microns Diameter), a calcium ion exchange capacity of at least about 2oo mg-eq ^. CaCO, -Härtt / g aluminosilicate, calculated on

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anhydrous basis, which is generally between about 500 mg-eq. / g and about 352 mg-eq. / g, and by a calcium ion exchange rate of at least about 1.92 ° dH Ga ⁺⁺ / minute / g aluminosilicate (anhydrous Basis), which is in the range from about 1.92 to 5 »85 ° dH- / minute / g, based on calcium ion hardness, is identified, and

(b) an amorphous, water-insoluble, hydrated aluminosilicate the formula

₂ . ySiO ₂ )

wherein χ is a number from 1 to 1.2 and y is 1, that continues by a Mg exchange capacity of about 50 mg-eq. GaCO_ / g to about 150 mg-eq. CaCO, / g (anhydrous Base) is marked,

wherein in the mixed amorphous / crystalline material a weight ratio from amorphous aluminosilicate to crystalline aluminosilicate from about 1: 4 to about 4 * 1 and preferably about 1: 1 is present.

The amorphous and mixed amorphous / crystalline aluminosilicate ion exchange builders are produced by a process that leads to the formation of products, especially as Detergent builders and water softeners are suitable. In particular, the aluminosilicates provided according to the invention have a higher caloium ion exchange capacity and a higher exchange rate than similar ones earlier materials proposed as detergent builders. In addition, the proposed aluminosilicates sequester Itoagneaiumcationen so sufficient that they act as builders are suitable in the detergent area.

The desired ion exchange properties of the invention Aluminosilicates appear to be a function of several interrelated factors that arise from the I) ar-

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positionally result. The amorphous aluminosilicates affect both Ga and Hg . The mixed amorphous / crystalline aluminosilicates also control both Oa ⁺⁺ and Mg ⁺⁺ , while the pure crystalline aluminosilicate only controls Oa. In order to eliminate mixed hardness, the ion exchanger materials provided according to the invention are therefore provided as essentially pure amorphous aluminosilicate and in the form of mixtures of substantial amounts of the amorphous aluminosilicate in combination with crystalline aluminosilicate.

From the above it is evident that the amorphous aluminosilicate according to the invention due to its Action against mixed hardness as an ion exchange builder is strongly preferred. The pure amorphous material noisy itself however, difficult to manufacture on an industrial scale. The mixed amorphous / crystalline aluminosilicate is easier to obtain, and allowed with a suitable proportion of amorphous to crystalline constituents an excellent removal of mixed hardness.

Am an essential feature of the amorphous as well as the mixed amorphous / crystalline ion exchange builders consists of that they are in "sodium form". Surprisingly, it was found, for example, that the potassium and hydrogen Fora of the described aluminosilicates neither the exchange rate still have the exchange capacity required for use as optimal framework materials.

A second essential feature of the present ion exchange builders They consist in the fact that they are in hydrated yeast, i.e., contain from about 10 to about 22% by weight of water. Particularly preferred aluminosilicates contain the theoretical maximum of about 18 to about 22% by weight v / water in the crystal matrix. For example, it has been found that less

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highly hydrated aluminosilicates, for example with about 6 % water, are not effective ion exchange builders for detergents.

The amorphous aluminosilicates provided according to the invention are among those commonly used in the manufacture of spray-dried Detergent used process conditions resistant. That is, that the amorphous aluminosilicates their ability to Maintain lowering of the mixed hardness even after heating to 50 to 100 G. This is unusual as others are amorphous Aluminosilicates lose their ion exchange properties when heated.

A third essential feature of the ion exchange builders of the invention is the range of particle size. It goes without saying that the envisaged amorphous aluminosilicates have peculiar to them - a small particle size (about 0.1 to 5 microns in diameter). The crystalline fraction of the mixed amorphous / crystalline substances have as small a particle size as possible in the specified range. The appropriate one Many small particle sizes lead to rapidly acting and highly effective builders. In addition, the small particle size The proposed aluminosilicates are believed to be the reason why there is no deposition on tissues from the aqueous Wash liquor takes place. This lack of deposit is a matter of course, desirable when using the aluminosilicates as detergent builders begins.

The process described below for preparing the aluminosilicates of the present invention is specific to the Production of the aluminosilicates in the amorphous state-oriented. The process works in particular with highly concentrated solutions, which cause the rapid formation of amorphous particles seem to favor. The solution concentrations are limited only to the extent that it must be possible to use the solutions pour and mix the "participants effectively"

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The procedure takes into account all essential factors those above for the preparation of an effective aluminosilicate builder material were called. The process thus avoids contamination of the aluminosilicate cations other than sodium. JTerner is the procedure on the production of the Aluininosilikata in as strong as possible hydrated jorm aligned. Therefore one avoids heating to high temperatures and drying. In addition, the process is based on the production of aluminosilicate materials aligned in a finely divided state with a narrow range of small particle sizes. Of course, additional Balding processes can be used to further reduce the particle size. The need for such a mechanical However, machining is significantly reduced using the following procedure.

In the preparation of the aluminosilicates according to the invention The chemical reactions that occur are complex because of the numerous possibilities that arise when mixing aluminate and silicate in an aqueous-basic medium. Under the applied reaction conditions, the reaction participants appear first to form an amorphous aluminosilicate, which seems to undergo a further transformation prior to conversion to the crystalline aluminosilicate. The amorphous / Crystalline transformation does not take place in stages, but rather through the process, to an extent, as itself the system of .league participants in a dynamic state is located. Theoretically, it should be possible for the Heaction participants to mix, to stop the reaction at a suitable time and only the desired amorphous aluminosilicate to isolate; however, this is not possible with technical approaches. In practice, the procedure is designed in such a way that that a mixture of amorphous and crystalline aluminosilicate is formed and the reaction is stopped at a point in time which a substantial amount (about $ 50 or more) of the amorphous

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Material has not yet been converted into the crystalline iOrm is. The use of highly concentrated mixtures of the reactants and careful control of the reaction time in the manner described below leads to this desirable result. After making the mixed amorphous / Crystalline products can be broken down by suspending them in water, the crystalline material settling out and the amorphous material remains suspended.

The aluminosilicate ion exchangers provided according to the invention are manufactured according to the following process:

(a) Mix sodium aluminate (NaAlOp) and sodium hydroxide in water to form a mixture with the following (preferred) Weight ratios of the components:

H ₂ 0 / NaA10 ₂ 5 , 9: 1 H ₂ O / NaOH 1 , 2: 1 NaAlO ₂ ZNaOH , 8: 1

When working at low temperatures, the mixture of aluminate and sodium hydroxide does not consist of a true solution and may contain small amounts of finely dispersed particulate materials. The temperature of the mixture we
set.

Mixture is adjusted to about 2o to 7o and preferably about 5o G

(b) To the mixture of step (a) a sodium silicate solution (about 37 wt .- ^ ₀ .Feststoffgehalt, SiO ^ ^ Na ratio 3.2: 1) is added rapidly. This mixing step can be carried out in a kettle with an effective stirrer, or the two mixtures at the desired temperature can be fed in measured quantities to a mixer located in a pipeline, which in turn is part of a main bath system, resulting in a continuous process. ' The ratio of NaAlO ₂ to sodium silicate (anhydrous basis) is

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carries about 1.6: 1.

(c) The mixture from step (b) is quickly heated to 75-95 ° C (preferably 8o to 85 ° C) and 10 to 60 minutes (preferably 10 to 20 minutes) held at this temperature.

(d) Then the slurry obtained in step (c) is made up cooled about 50 ° G and filtered. The resulting filter cake is washed in so much water that it becomes a vvaschwasser / ieststoff (anhydrous base) weight ratio

of about 2, o: 1 (preferred).

filtration and washing processes are repeated.

The filter cake obtained by the above process consists of a mixture of crystalline aluminosilicate and amorphous aluminosilicate in a weight ratio of about 1: 1. The material from the filter cake shows a rapid and effective uptake of both Ca and Mg ions. The filter cake can be used per se as an ion exchange material. For use in powder form! or granular detergents, it is preferred to dry the filter cake to a moisture content of about 1o to about 22 wt .- $, wherein applying a drying temperature below ⁰ Thus G, in order to avoid excessive dehydration. It is preferable to dry at 38 to 41 ° C

The amorphous aluminosilicate of the present invention can be used if desired from the amorphous / crystalline mixture obtained in the above manner, separated by simply suspended the filter cake in water. The crystalline portion of the mixture is deposited here (in the course of from about 1 to 6 hours)} while the amorphous material remains suspended in the aqueous medium. The amorphous material can be obtained by decanting or by other physical means

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be separated. Of course, you can also use less Centrifuged speed to separate amorphous and crystalline components more quickly.

On. There are aluminosilicates produced above from mixtures of amorphous and crystalline substances. Of the crystalline portion is characterized by a cubic crystal structure. The amorphous material naturally possesses an irregular structure that cannot be analyzed by X-ray diffraction.

Both the crystalline and the amorphous aluminosilicate ion exchanger are characterized by a ualcium ion exchange capacity that is at least about 2oo mg equivalent CaOÜ ^ hardness / g aluminosilicate, calculated on anhydrous Base, and which is generally between about 300 mg-eq. / G and about 352 mg-eq. / G.

The present ion exchangers are further characterized by their calcium ion exchange rate, which is at least about 1.92 ° dH (Ca ⁺⁺ ) / min./g aluminosilicate (anhydrous basis) and between about 1.92 and 5 »85 ° dH / minute / g, based on the calcium ion hardness. Aluminosilicates which are optimal as builders have a Ga 2 exchange rate of at least about 3.4 ° / minute / g.

The aluminosilicate ion exchangers according to the invention are further characterized by their magnesium exchange capacity, which is at least about 5o mg-eq. CaCO, hardness / g aluminosilicate calculated on an anhydrous basis, and is generally between about 50 mg-eq / g and 150 mg-eq / g.

The present ion exchangers are further characterized by their magnesium ion exchange rate, which is at least about ^{0.96 ° dH (Mg ++} ) / Liin / g aluminosilicate (anhydrous basis) and between 0.96 and about 2.88 °

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/ Minute / g, based on magnesium ions hardness. Optimal synthetic materials: aluminosilicates show a magnesium exchange rate of at least about 1.92 / minute / g. The ion exchange properties of the aluminosilicates are expediently determined by means of a calcium ion electrode and a divalent ion electrode. This method determines the rate and capacity of Oa and Mg ⁺⁺ uptake of an aqueous solution with a known amount of Oa and Mg ions as a function of the amount of aluminosilicate ion exchange material added to the solution. In particular, the ion exchange rates of the present amorphous and mixed amorphous / crystalline aluminosilicates are determined as follows:

The aluminosilicate produced in the above way is in the urodium form to 150 ml of an aqueous solution containing 4.5 ° dH Ca ⁺⁺ and 2.3 ° dH Mg ⁺⁺ (measured as OaUO ₅ ) at a concentration of 0.06 wt. -5 ^ and pH 1o, o, added with gentle stirring. The rate of calcium depletion is determined using the calcium electrode (commercially available: Orion) and the rate of total calcium and magnesium depletion is determined using the divalent cation electrode. The magnesium ion depletion is then determined as the difference in the readings. The rate of depletion is determined for each cation by taking measurements over time. The total impoverishment from the solution is calculated after 10 minutes, this period corresponding to the usual washing time for an aqueous washing process. The rate curves for calcium depletion, magnesium depletion and calcium and magnesium depletion mixed can be plotted in degrees of hardness versus time.

The oalcium exchange capacity of the aluminosilicates loud can be determined by simple titration. In the practical implementation, the uni-inosilicate is coated with a well-known

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shot at üa ^{++ brought} into balance. After the calcium ions have been absorbed, the excess calcium ion remaining in solution is determined by a standard titration with ethylenediaminetetraacetic acid using the standard indicator Eriochrome black Ϊ. The magnesium ion capacity is determined titrimetrically in a similar way.

As mentioned above, both the crystalline and amorphous components of the present aluminosilicates exhibit excellent exchange rates and exchange capacities for calcium ions. The amorphous material also absorbs magnesium ions quickly and efficiently. The mixture of crystalline and amorphous material therefore makes it possible to lower the mixed (Ja ⁺⁺ / Mg ⁺ hardness.

The following example illustrates the production of the mixed amorphous / crystalline aluminosilicate ion exchanger on a pilot plant scale. As already mentioned, the amorphous aluminosilicate can easily be separated from the crystalline aluminosilicate by suspending the filter cake in water. The crystalline fraction of the Gemiacha settles (about 1 to 6 hours are) while the amorphous I ¹ remains suspended eil in water. The separation can be done by decantation or other mechanical means.

example 1

The following loading was carried out in a semi-technical test facility used:

filled amount (

Weight $ (anhydrous)

• teaser 95.8 64.29

Sodium aluminate 52.2 x 16.4o

Sodium hydroxide (50 $ aq.) 49.9'9.05

Sodium silicate (SiO _p : Na _? O ratio 3.2: 1, approx. 5%

watery Solution) 74.8 1o, 26

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The device used consisted of an insulated reaction vessel with a capacity of 2o3 l and provided with baffle plates a propeller mixer and a heat exchanger designed as a side arm, which was designed for recirculation and was fed by a gear pump. The pump had a capacity of 19 liters per minute. The discharge stream off the heating vessel -based another heat exchanger, in which cooling took place, whereupon the stream was fed to a rotary vacuum filter. The filter cake fell from the filter into a tank equipped with a propeller mixer, in which he was slurried with washing water. The slurry was fed to a rotary vacuum filter and the filter cake was removed or washed again as desired. A measuring pump was part of the auxiliary equipment to which the silicate solution was supplied in a desired amount.

The reaction vessel was filled with water, then with sodium aluminate and sodium hydroxide charged. The mixture was agitated until the aluminate "dissolved". The temperature was on 5o ° Ü set, then the sodium silicate with 5o ° 0 in the

introduced at a rate of about 15.9 kg / minute. Maximum agitation is required in this part of the process to prevent solidification of the slurry. The slurry is agitated for about 15 minutes to break up clumps and ensure complete contact between the reactants. It is then passed through the heat exchanger designed as a side arm and the temperature is increased to about 80 to 100 ° C. and held there for about 1 hour. The slurry then passes through a heat exchanger, vff! Ftf cooled to about 37 ⁰ O and filtered "1. The filter cake is washed several times with water.

The aluminosilicate produced in this way consists approximately

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in a weight ratio of 5o: 5o from a crystalline hydrated aluminosilicate of the formula

Na ₁₂ (SiO ₂ .AlOg) ₁₂ .27H ₂ O

with a particle diameter of 1 to 2o microns, one Oa exchange rate of about 4.80 / minute / g and a Ca exchange capacity of about 300 mg-eq. / G, and an amorphous aluminosilicate of the general formula

Na (a1Ü _2. ^ IO ₂ )

This amorphous aluminosilicate is also characterized by a magnesium ion exchange capacity of about 125 mg-eq_. CaGU., / G aluminosilicate characterized.

The amorphous aluminosilicate is separated from the crystalline aluminosilicate by the filter cake in about 6 hours suspended in water and then the supernatant liquid containing the amorphous material is drawn off and dried.

The detergents according to the invention can contain all types of organic water-soluble detergent compounds, provided the aluminosilicate ion exchangers are compatible with them. A typical listing of the classes and types of useful detergent compounds is found in U.S. Patent 3,664,961. The following list of detergent compounds and their mixtures is representative of these materials but not limiting of the present invention.

"Water-soluble salts are suitable as detergent components higher fatty acids, i.e. "soaps". This class of substances includes the usual alkali metal soaps such as sodium, Potassium, ammonium and alkylolammonium salts of higher fatty acids with from about 3 to about 24, and preferably from about 10 to about 20 carbon atoms. Soaps can be

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soaping of fats and oils or by neutralizing free fatty acids are produced. The sodium and potassium salts of the fatty acid mixtures are particularly advantageous, obtained from coconut oil and tallow, i.e. the sodium or potassium day and coconut soaps.

Another class of detergents includes those which are water-soluble, in particular the alkali metal, ammonium and alkylolammonium salts of organic sulfuric acid reaction products, which are im Molecule is an alkyl radical containing from about 3 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester group (the term "alkyl" also includes the alkyl radical of Acyl groups) »Examples of this group of synthetic detergents, which form part of the detergents according to the invention are the sodium and potassium alkyl sulfates, in particular those obtained by sulfating higher alcohols (3 to 13 carbon atoms), which one in turn, by reducing the glycerides of tallow or coconut oil, wins the sodium and potassium alkylbenzenesulfonates with straight or branched chain alkyl groups of from about 9 to about 15 carbon atoms, e.g. US-PSS 2,220,099 and 2,477,383. Particularly Straight-chain alkylbenzenesulfonates with an average of about 13 carbon atoms in the alkyl radical are valuable, which are also abbreviated as C ^ LAS.

Other possible anionic detergent compounds are the sodium alkyl glyceryl ether sulfonates, in particular the ethers of higher alcohols from tallow or coconut oil, the sodium coconut oil fatty acid monoglyceride sulfonates and sulfates and the sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to 10 ethylene oxide units per molecule and with alkyl groups of about S to 12 carbon atoms.

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Also water-soluble, non-ionic synthetic detergents can serve as a detergent component of the agents according to the invention. These non-ionic detergents can generally to be defined as compounds produced by condensation of alkylene oxide groups (hydrophilic) with an organic hydrophobic compound can be obtained, the latter. can be aliphatic or alkyl chromatic. The length of the Polyoxyalkylene group, which is condensed with the respective hydrophobic group, can easily be adjusted so that you get a water soluble compound with the desired balance between hydrophilic and hydrophobic elements receives.

For example, one known class of nonionic synthetic detergents is under the trade name "Pluronics" on the market. These connections are made by condensing ethylene oxide with a hydrophobic base, which in turn by condensation of propylene oxide with propylene glycol. Other suitable nonionic synthetic detergents are the polyethylene oxide condensates of alkylphenols, e.g. the condensation products of alkylphenols with alkyl radicals with about 6 bia 12 carbon atoms in a straight or branched chain ^ and Ethylene oxide, the ethylene oxide being present in amounts of 5 to 25 moles per mole of alkylphenol.

Also water-soluble condensation products of aliphatic alcohols with 8 to 22 carbon atoms in straight or branched ones Chain and ethylene oxide can be used as non-ionic detergents in the present case, e.g. a coconut alcohol / Ethylene oxide condensate with 5 to 3o moles of ethylene oxide per mole Coconut alcohol, with the coconut alcohol traction 1o to Has 14 carbon atoms.

The semi-polar non-ionic detergents include

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water-soluble amine oxides with an alkyl radical of about 1o up to 28 carbon atoms and 2 alkylreates or hydroxyalkylreates with 1 to about 3 carbon atoms, the water-soluble phosphine oxide detergents with an alkyl radical with about 1o up to 23 carbon atoms and 2 alkyl or hydroxyalkyl radicals with about 1 to 3 carbon atoms and the water-soluble sulfoxide detergents with an alkyl radical with about 1o to 28 carbon atoms and one alkyl- ^ or hydroxyalkyl radical with 1 to 3 carbon atoms.

The ampholytic detergents include the derivatives of aliphatic or the aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic The remainder can be straight-chain or branched and one of the aliphatic substituents is about 8 to 18 carbon has atoms, while at least one aliphatic substituent has an anionic water-solubilizing group owns.

The zwitterionic detergents include the derivatives of aliphatic quaternary ammonium, phosphonium and Sulfonium compounds, in which the aliphatic .Reste straight chain dder can be branched and one of the aliphatic Substituents about 8 to 18 carbon atoms, another an anionic water-solubilizing group contains. -

Further detergent compounds which can be used according to the invention are the water-soluble salts of esters 0 (. sulfonated. fatty acids with about 6 to 2o carbon atoms in .Fett acidic st and about 1 to 10 "carbon atoms in the ester group, the water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids with about 2 to 9 carbon atoms in the acyl radical and about 9 to Carbon atoms in the alkane radical, the alkyl ether sulfates with

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about 1o to 2o carbon atoms in the alkyl radical and with about 1 to 3o moles of ethylene oxide, the water-soluble salts of olefinsulfonates with about 12 to 24 carbon atoms, and the ß-alkoxyalkane sulfonates with about 1 to 3 carbon atoms in the alkyl radical and about 8 to 20 carbon atoms in the alkane residue.

Preferred water-soluble organic detergent compounds are the linear alkyl benzene sulfonates at about 11-14 Carbon atoms in the alkyl radical, the alkyl sulfates with alkyl radicals from the tallow range, the coconut alkyl glyceryl sulfonates, the alkyl ether sulfates with alkyl radicals with about 14 up to 18 carbon atoms and an average degree of ethoxylation between 1 and 6, the sulfated condensation products of tallow alcohol with about 3 to 1o moles of ethylene oxide, the ülefinsulfonate with about 14 to 16 carbon atoms, the Alkyldimethylamine oxides with alkyl radicals with about 11 to carbon atoms, the alkyldimethyl-ammonio-rpropane sulfonates and alkyl dimethyl ammonio hydroxypropane sulfonates with Alkyl radicals of about 14 to 18 carbon atoms each, the soaps as defined above, the condensation products of tallow fatty alcohol and about 11 EoI of ethylene oxide and the Condensation products of a secondary alcohol with an average of 13 carbon atoms with 9 toöl ethylene oxide.

Particularly preferred detergents include: Sodium Linear-C. -U.g-alkylbenzenesulfonates, triethanolamine-C. O.Q-alkylbenzenesulfonates, Sodium tallow alkyl sulfate, sodium coconut alkyl glyceryl ether sulfonate, the sodium salt of a sulfated condensation product of a tallow alcohol with about 3 to about 1o tool ethylene oxide, the condensation product of a coconut fatty alcohol with about 6 LoI ethylene oxide, the Condensation product of tallow fatty alcohol with about 11 moles of ethylene oxide, 3- (N, N-Din: ethyl-N-coconut alkylainmonio) -2-hydroxypropane-1-sulfonate, 3- (N, N-dimethyl-N-coconut alkylammonio) -propane-1-sulfonate, 6- (N-dodecylbenzyl-N, N-dimethylacimonio) -hexanoate, "Dodocyl dimethyl amine oxide, coconut alkyl dimethyl amine oxide and the water-soluble sodium and potassium

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salts of higher fatty acids with 8 to 24 carbon atoms.

Of course, all of the above detergents can be used can be used alone or as mixtures. Examples of preferred detergent mixtures are as follows:

A particularly preferred alkyl ether sulfate detergent for the agents according to the invention consists of a mixture of Alkyl ether sulfates, which have a mean (arithmetic Medium) carbon chain length from about 12 to 16 and preferably from about 14 to 15 and an average (arithmetic mean) degree of ethoxylation of about 1 to 4 and preferably has about 2 to 3 mol of ethylene oxide (see BE-PS 8o7 262).

Such preferred mixtures contain a total of about o, o5 to 5 wt i <> 0 _{1? 1} ^ compounds, about 55 to 70 wt .- ^ C. .. ^ - compounds, about 25 to 40 wt .- ^C , b C ₁₆ "compounds and about 0.1 to 5 wt .- ^ CLg ^ q -Links. Such preferred Alkyläthersulfat mixtures further contain about 15 to 25 wt -.? ° ß> to compounds of the degree of ethoxylation O, approximately 5o to 65 wt .- $ of compounds from the degree of ethoxylation 1-4f about 12 to 22 wt .- ö to compounds Degree of ethoxylation 5 to 8 and about 0.5 to 10 wt .- ^ of compounds with a degree of ethoxylation more than 8.

Examples of alkyl ether sulfate mixtures within the above ranges can be seen from Table I.

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Table I.

ο co co co ο

Disability properties Alkyl ether sulfate. mixture

Average Chain length I II III IV 14.86 '14.68 14.86 14.88

12-13 C atoms (wt .- /)

14-15 carbon atoms (")

16-17 carbon atoms (»)

18-19 carbon atoms (")

4 / 1/ 1/ 3 / 55 # 65 / 65 / C ^Γ 7 Gt
^ JI / O 36 / 33 / 33 / 3Qf ° 5 / 1/ 1/ 2 /

through. Degree of ethoxylation (mol EO) 1.98

2.25 2.25

0 mol of ethylene oxide (wt .- /) 1-4 mol of ethylene oxide (") 5-8 mol of ethylene oxide (") more than 8 moles of ethylene oxide (")

3 *

salt

3., ο

22.9 / 18 /

65/55 /

12 /. 22 /

0.1 / 5 /

N / A

Preferred "olefin sulfonate" detergent mixtures which can be used in the detergents of the present invention contain olefin sulfonates having from about 10 to 24 carbon atoms. You can X.-olefins obtained with uncomplexed sulfur dioxide and subsequent neutralization under conditions such that possibly existing S ultorte be hydrolyzed to the corresponding hydroxyalkane by sulfonating ". The oil olefins used as starting material preferably contain 14 to 16 carbon atoms. These preferred olefin sulfonates are described in U.S. Patent 3,332,380.

BevorzugteV-Olefinsulfonatgemische consist essentially of about 3o to about 7o percent by weight of a component A, about 2O to about 7o wt. -Fo a component B, and about 2 to about 15 wt .-% of a component C, whereby

(a) Component A from a mixture of double bond position isomers water-soluble salts of alkene-1-sulfonic acids with about 10 to about 24 carbon atoms, the mixture of the isomers of about 10 to about 25? » of an δ, ß- unsaturated isomer, about 3 ° to about 70 $ of a ^, ^ "unsaturated isomer, about 5 to about 2 a) f, b -unsaturated isomer and about 5 to about 1 contains a ^, 8 -unsaturated isomer,

(b) component B from a mixture of water-soluble salts of bifunctionally substituted, sulfur-containing saturated salts of aliphatic compounds with about 10 to about carbon atoms, the functional groups Are hydroxyl or sulfonate groups and the sulfonate groups are always on terminal carbon atoms and the hydroxyl groups on carbon atoms are at least 2 carbon atoms away from the terminal carbon atom are, with at least 90 $ of the hydroxyl substituents in 3-,

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4- and 5-position are available, and

(c) the component u of a mixture of about 3o to 95> i water-soluble salts of alkene disulfonates of about 1o to about 24 carbon atoms and about 5 to about 7o ° / o water-soluble salts of Hydroxydisulfonaten with about 1o consists to about 24 carbon atoms, wherein the alkene disulfonates have a sulfonate group on the terminal carbon atom and a second sulfonate group on an internal carbon atom which is not more than "about 6 carbon atoms away from the terminal carbon atom, furthermore the Alkeri double bond extends to the carbon atoms between the terminal carbon atom and about the 7th carbon atom Carbon atom distributed, wherein the hydroxydisulfonates are also saturated aliphatic compounds having a sulfonate group on a terminal carbon atom and a second sulfonate group on an internal carbon atom, which is not more than about 6 carbon atoms from the terminal carbon atom, u nd a hydroxyl group is attached to a carbon atom which is no more than about 4 carbon atoms from the point of attachment of the second sulfonate group.

The detergents according to the invention can also contain an aluminosilicate ion exchange builder contain additional water-soluble builders, as they are usually used for detergents can be specified. These additional builders can be used to sequester the hardness ions to support and to contribute to the adjustment of the pH of the washing liquid. The additional builders can in concentrations of about 5 to about 5o wt .- ^ and preferably from about 10 to about 35 weight percent on the detergent, can be used to support the builder and pH-controlling function.

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Suitable additional builders include conventional inorganic and organic water-soluble framework salts.

These framework salts can e.g. water-soluble phosphates, pyrophosphates, orthophosphates, polyphosphates, phosphonates, Carbonates, polyhydroxysulfonates, silicates, polyacetates, Be carboxylates, polycarboxylgites or ouccinates. Specific Examples of inorganic phosphate builders are sodium-- and potassium ffcripolyphosphates, phosphates and hexametaphosphates. The polyphosphonates specifically include the sodium and potassium salts of ethylene diphosphonic acid, the Sodium and potassium salts of ethane-i-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Examples of this and other phosphorus-containing framework blockages are US-PSS 3,159,581, 3,213,030, 3 422 o21, 3 422 137, 3 4oo 176 and 3 4oo 148.

Non-phosphorus-containing chelating agents can also be used as additional builders can be used.

Specific examples of phosphorus-free, inorganic additional Detergent builders are the water-soluble inorganic carbonates, bicarbonates, and silicates. In particular the alkali metal, e.g., sodium and potassium carbonates, bicarbonates, and silicates are useful.

Water-soluble organic builders can also be used, such as the alkali metal, ammonium and substituted ones Ammonium polyacetates, -carboxylates, -polycaroxylates and polyhydroxysulfonates. Specific examples of polyacetate and polycarboxylate framework salts are the sodium, potassium, lithium, ammonium and substituted ammonium salts of the Ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, cellitic acid, the benzene polycarboxylic acids and citric acid.

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- 35 -

Particularly preferred, phosphorus-free additional fuels are sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodium oxi / disuccinate, sodium mellitate, Sodium nitrilotriacetate and sodium ethylenediamine tetraacetate and mixtures thereof.

further particularly preferred additional builders are the polycarboxylates described in U.S. Patent 3,380,067. Examples of this are the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, Itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Another preferred additional builder is the water-soluble Salts, in particular the sodium and potassium salts of oxymethyloxymalonic acid, carboxymethyloxysuccinic acid, cis -cyclohexane hexacarboxylic acid, cis -cyclopentane tetracarboxylic acid and phloroglucinetrisulfonic acid.

The detergents according to the invention can contain all additives that are commonly used in detergents and cleaning agents. For example, they can be thickeners and soil suspending agents such as carboxymethyl cellulose and the like. Also enzymes, in particular proteolytic and lipolytic enzymes commonly used in Vila Schmitt an may be present. Perner you can use different odorous substances, optical bleaching agents, Contain fillers, anti-caking agents, fabric softeners and the like. Of course For example, all of these additives are useful in that they are compatible and in the presence of the aluminosilicate ion exchange builder are persistent.

The detergents according to the invention can according to various known process for the production of commercially available V / a schmitt el

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getting produced. For example, the detergents can be made by simply using the aluminosilicate ion exchanger mixed with the water-soluble organic detergent. The builder to be used, if any, and the other auxiliaries can simply be mixed with it if desired. It can also be an aqueous slurry of the aluminosilicate ion exchange builder, the dissolved water-soluble organic detergents and any auxiliaries present contains, spray-dried in a tower and converted into granular form. The granules - one such spray-dried Detergents contain the aluminosilicate ion exchange builder, the organic detergent and other desired substances.

The aluminosilicate ion exchange materials can also be used separately in aqueous washing or rinsing baths in order to reduce the cations which cause hardness. You can then simply add an effective amount (ie sufficient to reduce it to about 1 to 2 ° dH) to the bath and then add any commercially available detergent. In this application, the mixed amorphous-crystalline aluminosilicate is in an amount of from about 0.005 to about 0.25 weight - added to the aqueous bath.%.

The aluminosilicates in question here can also be used in Combination with common cationic fabric softeners can be used in fabric baths. Remove at this application the aluminosilicates remove the hardening cations and produce softer and softer-feeling tissues. Typical cationic Fabric softeners, which are suitable for a combination with the aluminosilicate ion exchangers Tallowtrimethylammonium bromide, tallowtrimethylammonium chloride, ditallowdimethylammoni, can be used, for example umbromide and ditallowdimethylammonium chloride,

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-.27 -

Aqueous fabric softeners containing an aluminosilicate ion exchanger contain about 5 to 95 percent by weight of the amorphous aluminosilicate of the present invention and about 1 to about 35% by weight of the cationic fabric softener.

The detergents according to the invention are in aqueous Liquids for cleaning surfaces, in particular fabric surface η, used, using the usual washing and apply cleaning procedures. The means are suitable in particular for use in conventional automatic washing machines in concentrations of about 0.01 to about 0.50 percent by weight. Optimal results are achieved when used in an aqueous wash liquor in a concentration of at least about 0.1o As with most commercial laundry detergents, the dry mix of the present invention will usually be a conventional one aqueous wash solution in an amount of about one cup per 64 liters of wash water.

Although the aluminosilicate ion exchange framework materials according to the invention eliminate calcium and magnesium hardness ions within a wide pH range, they are preferably used in detergents which in a solution ^{have a concentration of about 1.2 c} / o in a pH range of about 8. o to about 11, and preferably 9 »5 to about 10.5. Like other standard detergents, the detergents according to the invention are also the best way to remove dirt and triglyceride soiling and staining in the basic pH range. Although. the "aluminosilicates give a basic solution per se, the aluminosilicate, and organic detergent compound-containing detergent may additionally contain about 5 to about 25 wt -. contain ^c / o of a pH adjusting agent The detergent may, of course, the optional water-soluble builders described above, and. The pH-adjusting agents are chosen so that the pH of an 0.05% strength by weight aqueous mixture is in the range between about 9.5 and about 10.5.

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-the

To any pH-Y / ert adjusting agents to be used include all water-soluble, basic substances that are commonly used in toasting agents. Typical examples are sodium phosphate, sodium silicate, sodium hydroxide, Potassium hydroxide, triethanolamine, diethanolamine, ammonium hydroxide and the like. Preferred pH adjusting agents are Sodium hydroxide, triethanolamine and sodium silicate.

I) ie the use of the aluminosilicates according to the invention as Water softener and detergent builder is made by the following examples are illustrated:

Example 2

One insensitive to water hardness, the present one Laundry soap containing aluminosilicates can be composed as follows:

component

Tallow soap (Na-SaIz) 7o

Aluminosilicate 2o sodium chloride 3

Water and low Additions reads

5o: 5o mixture of amorphous and crystalline aluminosilicate obtained by the procedure of Example 1.

This soap mixture shows excellent cleaning and foaming behavior in hard water with up to 11.5 ° mixed Ga and Mg hardness. In an aqueous liquor containing o, 15 wt .- / scaffold-containing soap washed laundry has no deposits, such as those caused by insoluble Ca ⁺ and Mg ⁺ -Seifenniederschläge.

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If you replace the mixed amorphous / crystalline in the above mixture Aluminosilicate by an equivalent amount of the amorphous aluminosilicate according to Example 1, so are equally good results achieved.

in the above mean the 50:50 mixture of amorphous and crystalline aluminosilicate is replaced by 8o: 2o, 7o: 3o, 6o: 4o, 4o: 6o, 3o: 7o, 2o: 8o or 1o: 9o mixtures replaced, so you get good 'detergency in hard water.

The following example illustrates the use of the invention Aluminosilicates in Synthetic Detergents

containing detergents:

Example 3

Component - weight

Alkylbenzenesulfonate, sodium salt

(linear O ₁₂ average alkyl group) 3o

Aluminosilicate ⁺ 25

Sodium sulfate 2o

Sodium citrate 1o

Water and low Additives Heat

5o: 5o mixture obtained by the procedure of Example 1 made of amorphous and crystalline aluminosilicate.

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- 3ο -

Example 4

Ea is a spray-dried detergent with the following formulation manufactured:

Part wt ° / o

surface act. System off -. . ■

Sodium tallow alkyl sulfate

le «al £ hols ^ it A»

15 carbon atoms and about \

9 moles of ethylene oxide

Weight ratio anionic /

= 4.5: 1

Amorphous aluminosilicate $ 74

Water 4%

Manufactured according to the procedure of Example 1.

The above mixture shows excellent washing behavior under normal household conditions in a washing liquid of 6.7 ° mixed Mg / Ga hardness with a Concentration in the washing liquid of about 0.12 wt .- ^. Under these conditions, the agent according to Example 4 compares favorably with regard to foaming and cleaning behavior conventional, high-foaming anionic builders Detergent formulations. The agent is pourable and is produced in a conventional spray dryer.

Detergents with essentially similar usage behavior are obtained if, in the formulation of Example 4 the sodium tallow alkyl sulfate by an equivalent amount Potassium tallow alkyl sulfate, sodium coconut alkyl sulfate, potassium coconut alkyl sulfate, Sodium decylbenzenesulfonate, sodium

409886/1266

dec ^ lbenzenesulfonate, sodium tridecylbenzenesulfonate, Sodium tetradecylbenzenesulfonate, sodium tetrapropylenebenzenesulfonate, Potassium decylbenzenesulphonate, potassium undecylbenzenesulonate, Potassium tridecylbenzenesulfonate, potassium tetradecylbenzenesulfonate or potassium tetrapropylene benzene sulfonate.

Detergents obtained from essentially the same physical properties and processability are achieved if one in the formulation of Example 4 the condensation product of secondary alcohol with 15 carbon atoms and 9 I «ol ethylene oxide by an equivalent Amount of the condensation product from tridecyl alcohol and about 6 Liol ethylene oxide (HLB = 11.4), the condensation product & from coconut fatty alcohol and about 6 moles of ethylene oxide (HLB = 12, o), "Neodol 23-6.5" (HLB = 12); "Neodol 25-9 "(HLB = 13.1) or" '^ ergitol 15-3-9 "(HLB = 13.3) replaced.

Example 5

A spray-dried laundry detergent that comes with water Ua and Mg hardness can be used as follows

formulated:

Ingredient wt .- ^

surface act. System from: '$ 24.7

Sodium linear alkyl benzene sulfonate with alkyl groups with avg. about 11.8 carbon atoms chain length

Weight ratio

anionic /

Condensation product of 1 non-ionic

Moles of coconut fatty alcohol and " ⁼ 4, <^: i about 6 moles of ethylene oxide

Amorphous aluminosilicate 25, o $

Sodium silicate (Na ₉ O / SiO "weight ratio =

1: 2.4) ^d * ■ 15, o / _o

Sodium sulfate 2o, o%

Sodium acetate

Sodium toluenesulfonate 2, ο

Water 4, O ^

minor additions rest

Prepared according to the procedure of Example 1.

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The V / a schmitt el of Example 5 shows excellent cleaning behavior when used under normal household conditions in a washing liquid with 6.7 mixed Ua and Mg hardness at a concentration in the washing liquid of about 0.12 wt .-? O. The mixture pH in Solution at this concentration is about 1o.2. Under these conditions, the detergent according to Example 5 cuts favorable compared to in terms of foaming behavior conventional, built-up, high-foaming anionic detergent formulations. The mean is easily pourable and storable and is produced with conventional spray drying.

Means are obtained with essentially the same performance properties, physical properties and "processing properties" when one uses the sodium silicate in the above mixture by an equivalent amount of sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium oxidisuccinate, sodium mellitate, Sodium nitrilotriacetate, sodium ethylenediamine tetraacetate, sodium polymaleate, sodium polyitaconate, sodium polymesaconate, Sodium polyfumarate, sodium polyaconitate, Sodium polycitraconate, sodium polymethylene malonate or mixtures replaced by it.

In means with essentially the same usage behavior, physical properties and processability one obtains, if the mixture of Example 5 is about 3 wt .- ^ sodium perborate in the solid state, with all other components retained in the same relative amounts will. Such perborate-containing mixtures are suitable in particular for use under the washing conditions customary in Europe.

If the entire surface-active system in the above mixture is replaced by an equivalent amount of the

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visible alkyl ether sulfate mixtures I, II, III or IV, in this way detergents with excellent washing behavior are also achieved.

Example 6

A phosphorus-free detergent with the following composition is formulated:

Component weight - ° ß>

surface act. System $ 35

i'riethanolamine (pH-adjusting agent) 7 $ NaOH (pH adjusting agent) 0.5 $

Amorphous aluminosilicate 35%

Sodium Sulphate $ 15

Water and minor additives remainder

⁺ The surface-active system comprises a mixture of od-olefin sulfonates, which consists essentially of about 3o to about 7o wt .-% of a component A ^ about 20 to about 70 wt .-% of a component B and about 2 to about 15 ^a / ° one Component G consists, where

(a) Component A consists of a mixture of double bonds of positionally isomeric water-soluble salts of alkene-1-sulfonic acids with about 10 to about 24 carbon atoms, the mixture of positional isomers about 10 to about 25% of a ^, ^ - unsaturated isomer, about 3o up to about 70% of an H ₁ 2T "" ^uri S ^e saturated isomer, about 5 to about 25% of a> T, t? contains -unsaturated isomers and about 5 to about 10 $ of a &, £ -unsaturated isomer,

(b) component B from a mixture of water-soluble salts of bifunctionally substituted, sulfur-containing

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Saturated aliphatic compounds with about "Io to about 24 carbon atoms, the functional groups are hydroxyl or sulfonate groups and the sulfonate groups are always on terminal carbon atoms and the hydroxyl groups on carbon atoms that are at least 2 carbon atoms away from the terminal carbon atom, wherein at least 9o ^c / o of the hydroxyl substituents are in 3-, 4- and 5-part division, and

(c) the component U from a u-emic. from about 3o to 95; j water-soluble salts of alkene disulfonates with about 10 to about 24 carbon atoms and about 5 to about To ^L / _o water-soluble salts of hydroxydisulfonates with about 10 to about 24 carbon atoms, the alkene disulfonates having a sulfonate group on the terminal carbon atom and a have second sulfonate group on an internal carbon atom which is not more than about 6 carbon atoms away from the terminal carbon atom, furthermore the alkene double bond being distributed over the carbon atoms between the terminal carbon atom and about the 7th carbon atom, furthermore the Hydroxydisulfonate saturated aliphatic compounds having a sulfonate group attached to a terminal carbon atom and a second SuIfonatgruppe to Einein internal olefins carbon atom, which by no more than about 6 carbon atoms from the terminal carbon s ± ^v fatom is removed and a hydroxyl group at a Koh is bonded fuel atom which is removed by no more than about 4 carbon atoms from the bond portion of the second sulfonate group.

^{++ Manufactured} according to the procedure of Example 1.

The agent according to Example 6 is an aqueous bath of 43 ° C in an amount of 0.15 & ew.-5 & added and for washing Oily (woven fabric used, tan achieved excellent

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Cleansing effect under the conditions of an initial mixed water hardness from 6.7 to 11.5 dH.

In the above formulation, the surface-active system by an equivalent amount of sodium-linear-C. -Cjo-alkylbenzenesulfonate, Sodium tallow alkyl sulfate, sodium coconut alkyl glycerol ether sulfonate, Sodium salt of a sulfated condensation product of a tallow alcohol and about 3 to about 1o mole of ethylene oxide, condensation product of a fatty alcohol with about 6 ΙνΊοΙ ethylene oxide, condensation product from Tallow fatty alcohol and about 11 moles of ethylene oxide, 3- (N, N-dimethyl-N-coconut oil-alkylammonio) -2-hydroxypropane-1-sulfonate, 3- (N, N-J) imethyl-N ~ coconut oil-alkylammonio) -propane-1-sulf onate, 6- (N-i) odeeylbenzyl-M, N-dimeth ^ lanimonio) -hexanoate, dodecyldimethylamine oxide, Coconut alkyl dimethylamine oxide or the water-soluble sodium and potassium salts of higher fatty acids replaced with 8 to 24 carbon atoms or mixtures thereof, equivalent results are obtained with the resulting mixtures.

In addition, equivalent results are obtained if the surface-active system in the above mixture is replaced by an equivalent amount of a mixture of the following alkyl ether sulfate compounds: about 0.05 to 5% by weight of C., compounds, about 55 to 70% by weight. - ^c / o ü. - compounds, about 25 to 4-0 wt .- $ Cg "compounds, such as o 1 to 5 wt .- ^ .Q C. _q compounds, wherein about 15 to 25 wt .. - ⁰ Jo of Gemiacta.3 a degree of ethoxylation O, approximately 5o to 65 wt .- ^ S a degree of ethoxylation of 1 to 4, about 12 to 22 parts by weight jS -fo a degree of ethoxylation of 5 bis 8 and about o, 5 to 1o percent. a Have a degree of ethoxylation greater than 8.

Good detergents in hard water are also obtained by replacing the sodium sulfate with an equivalent in the above solution Amount of sodium carbonate, sodium bicarbonate, sodium

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silicate, sodium oxidisuccinate, sodium mellitate, sodium nitrilotriacetate or polymeric carboxylates according to US Pat. No. 3,380,067 replaced.

Example 7

A granular soap-based detergent contains the following setting is made:

Ingredient wt .- ^ o

Sodium ^ ¹ ^ -Olves 42.6

Potassium Soap ^ 11.2

1o, 7

11.8 ⁸ ' ⁸

Sodium silicate 8.9

. Sodium citrate 11.9

Brightener o, 57

Perfume o, 17

Water 3.4

Various rest

(1) Soap mix of $ 9o tallow and $ 1o coconut soaps.

(2) Sodium salt of ethoxylated algae alkyl sulfate with an average of about 3 ethylene oxide units per molecule

(3) the sodium salt of a linear alkylbenzenesulfonate with average alkyl chain length of about 12 carbon atoms.

75 parts by weight of the soap-based granules are included 25 parts by weight of the amorphous aluminosilicate according to Example 1 mixed. The mixture is in a ^ concentration of 0.12 wt .- ^ o used in a washing liquid and with a mixed hardness of 9 »6 ° results in excellent

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No refinement and foaming behavior.

The mixture of Example 7 was modified by adding 3 parts by weight of sodium perborate. Receives a detergent with excellent cleaning properties in healthy water (49 to 82 ° above sea level).

In addition, it has been found that the use of polyethylene glycols in the molecular weight range from about 4,000 to about 8,000 and preferably about 6,000 in the washing agents according to the invention achieves the effect of remaining white. The use of polyethylene glycols in detergents is known from US Pat. No. 2,806,001. When used in an amount of o, 1 to about 3 and preferably from o.5 to 1.5 wt. ~ ° / o in the above VVA schmitt eleven ormulierungen will result in desirable white laundry. The following example illustrates a preferred laundry detergent which contains polyethyleneglycol:

Example 8

Ingredient "wt .-? O

surface act. System from: 24 »7 / &

Sodium linear alkyl benzenesulfonate with alkyl groups with through. 11.3 G-

Gev / .verh.

anionic /

non-ionic

Atoms chain length 2o% _x . _{oc Λ}

° j | = 4 »* - b: 1

Condensation product of 1 mole of coconut fatty alcohol and about 6 moles of ethylene oxide 4.7 $;

⁺ Aluminosilicate 42, o $

Sodium silicate (Na _p 0 / 3i0 _p weight ratio =

1: 2.4) · 15.00 $

Polyethylene glycol (mole weight 6,000) $ 1.5

Sodium Sulphate 1o, o $

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Component . · (Each .-> o

Sodium toluenesulfonate 2, o ^ 1

Itest water and minor additives

According to .Example 1 prepared.

The above mixture is used for washing 'textiles applied at a concentration of one cup to 64 liters of water. A good cleaning effect is achieved and improved laundry whiteness in water of 6.7 ° mixed hardness.

As can be seen from the above, the amorphous aluminosilicate ion exchange agents according to the invention in all kinds of detergents and detergents be used. The fact that the aluminosilicates inorganic "nature, probably contributes to their stability and compatibility with all components such detergents. Depending on the consumer's views, it is of course appropriate to add the present aluminosilicate builders to a washing or rinsing liquid separately from the detergent. The separate addition increases the flexibility in the choice of the »detergent by the consumer, although the advantages of the invention Scaffolding materials can be applied. The inventive AluminoSilicates can also be used as water softeners for Wäacfc ^ vaschwasser can be used. Even the separated ones Use of the aluminosilicate builders according to the invention for the preliminary softening of washing water falls within the scope of the present invention.

The favorable exchange speed and ion exchange capacity of the amorphous aluminosilicates according to the invention can be seen well when used for the preliminary softening of washing liquids. To for this purpose

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2433A85

to be suitable, the aluminosilicates must not be so react slowly that you have to wait a long time before the ' "Addition of the 'detergent to the washing liquid is required. It is also undesirable if the consumer has to use substances that are so low in exchange capacity that it requires an excessively large diameter for the effective sequestration of the hard ions. Finally, the fabrics should mixed polyvalent hardness cations such as Ga, Mg, Fe and sequester Fe.

The aluminosilicate builders of the invention can can be used for all purposes. In addition to the above-mentioned purposes, they can also be used in detergent-containing substances Use floor cleaning agents, abrasive cleaning agents and the like, which also have the hardness of the water presents a difficulty. Typical abrasive cleaning agents contain, for example, from about 25 to about 95% by weight of an abrasive (e.g., silica), from about 10 to about 35% by weight an amorphous aluminosilicate builder of the invention and about 0 to about 2o 5'ό by weight of an additional Gatiststoffs of the type described above and about 0.2 to about 10 wt .- 'j of an organic detergent compound.

You get excellent cleaning behavior if you the amorphous aluminosilicate of Examples 4 to 8 through replaced mixed amorphous / crystalline aluminosilicates.

The mixed amorphous / crystalline aluminosilicates are produced according to the procedure of Example 1. The typical average crystal particle size is 5 to iviikrons. Preferred proportions between amorphous and crystalline aluminosilicate are between 1: 4 and 4: 1.

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Claims (1)

Claims Q) Amorphous, water-insoluble, hydrated aluminosilicate ion exchange compound the empirical formula Na (XAlO _2. YSiO ₂ ) where x is a number from 1 to 1.2 and y is 1, with a Mg exchange capacity of about 50 mg-eq. CaCuVg to about 150 mg-Ä'c ^. CaCO ^ / g. 2. alumino-silicate builder according to claim 1, characterized by a Mg exchange rate of 0.96 / minute / g up to about 2.88 ° / kinute / g. 3 · Mixed amorphous / crystalline aluminum inosilicate ion exchanger substance containing (a) a water-insoluble, crystalline aluminosilicate ion exchange material the ^ 'ormel where χ is an integer from about 20 to about J> 0, with a particle diameter of about 1 to about 100 liqueurs and a calcium ion exchange capacity of at least about 200 mg-eq. CaCU, / g and a calcium ion exchange rate of at least about 1.92 / Iv'.inute / g, and (b) an amorphous, water-insoluble, hydrated aluminosilicate ion exchange G-framework material the formula wherein χ is a number from 1 to 1.2 and y is 1, with one fcg exchange capacity of about 10 mg eq. CaOO ^ / g to about 409886/1266 150 mg-eq. UaC! 0, / g and a Mg exchange rate from 0.96 ° / minute / g to about 2.88 ° / l'itiute / g, with the mixed amorphous / crystalline material has a weight ratio of amorphous aluminosilicate to crystalline aluminosilicate from about 1: 4 to about 4: 1. 4 · Mixture according to claim 3> characterized in that them as crystalline aluminosilicate contains. 5. Mixture according to claim 4, characterized in that the The weight ratio of crystalline to amorphous aluminosilicate is 1: 1. 6. Process for the production of an aluminosilicate ion exchange material, which is capable of rapidly reducing the hardness of an aqueous solution, characterized in that, daij man (a) Sodium aluminate and sodium hydroxide in Viasser of 2o Mixed up to 7o C to form a mixture with the following weight ratios:
H ₂ 0 / NaAl0 ₂ = 2.9: 1
H ₂ 0 / Na0H = 5.2: 1
NaA10 ₂ / NaOH = 1.3: 1 (b) rapidly adding a concentrated sodium silicate ^{solution to mixture 1} of step (a) to form a mixture having a sodium aluminate to sodium silicate ratio of about 1.6: 1; and (c) The mixture from step (b) is rapidly heated to 75-95 ° U and keeps for 10 to 60 minutes at this temperature, whereupon 409886/1266 man the mixed amorphous / crystalline aluminosilicate solids isolated. Y. The method according to claim 6, characterized in that daü the mixed amorphous / crystalline solids 1 to 6 Hours suspended in water and the amorphous aluminosilicate isolated. 8. To quickly control the content of an aqueous solution detergent capable of free polyvalent metal ions, containing (a) about 5 to about 95 wt .- ^ u of an amorphous, water-insoluble, hydrate aluminosilicate ion exchange builder the empirical i'ormel · '- wherein, χ is a number from 1 to 1.2 and y is 1, with one Mg exchange capacity of at least about 50 mg Aq. OaCÜ ^ / g and a Ca exchange capacity of at least about 2oo mg-eq. UaCÜ ^ / g and (b) about 5 to about 95 weight percent of a water soluble organic anionic, non-ionic, ampholytic and / or zwitterionic detergent compound. 9. detergent according to claim 8, characterized in that it further about 5 to about 50 wt .-% of an additional Contains water-soluble detergent builder. 10. Detergent according to claim 9j, characterized in that it as an additional builder sodium tripolyphosphate or Contains potassium tripolyphosphate. 409886/1266 11. Detergent according to claim 9> characterized in that it is a phosphorus-free Geraststoff as additional Geriiststoff contains. 12. Detergent according to claim 11, characterized in that it is a water-soluble inorganic as an additional Geriiststoff Contains urarbonate, carbonate or silicate. 13. Detergent according to claim 11, characterized in that it is water-soluble organic as an additional Geriiststoff Contains polyacetates, carboxylates, polycarboxylates or polyhydroxysulfonates. 14 V / Detergents, according to claim 11 characterized it dan as additional Geriiststoff sodium carbonate, sodium bicarbonate, Natriums.ilikat, sodium citrate, Natriumoxydisuccinat, Natriummellitat, sodium nitrilotriacetate, disodium ethylenediaminetetraacetate, sodium polymaleate, Natriumpolyitaconat, Natriumpolymesaconat, Natriumpolyfumarat, Natriumpolyaconitat, Natriumpolycitraconat, Natriumpolymethylenmalonat, Watriumcarboxymethylmalonat , Sodium carboxymethyl succinate, sodium cis-cyclohexane hexacarboxylate, sodium cis-cyclopentane tetracarboxylate, or sodium pKLoroglucintrisulfonat contains. 15 · detergent according to claim 8, characterized in that it as an additional component about 0.1 to 3 percent by weight of a polyethylene glycol of molecular weight in the range contains from 4oo to 8,000. 16. Detergent according to claim 15, characterized in that that it is o, 5 to 1, 5> ^> Contains polyethylene glycol with a molecular weight of 6,000. 409886/1266 17 · 2 for the rapid lowering of the content of an aqueous solution capable of free polyvalent metal ions Containing detergents (1) a mixed amorphous crystalline aluminosilicate ion exchange builder consisting essentially of (a) a water-insoluble, crystalline aluminosilicate ion exchange material the -e'oriael Na ₁₂ (AlO ₂ .UiO ₂ ) ₁₂ .XH ₂ O wherein χ is an integer from about 2o to about 3o, with a particle size of about 1 to about 100 Kikron .Durchmesser, a calcium ion exchange capacity of at least about 2oo mg-eq. GaCO hardness / g aluminosilicate and. an calcium ion exchange rate of at least about 1.92 Ca / minute / g of aluminosilicate, and (b) an amorphous, water-insoluble hydrating alumino- Silicate ion exchange G-fuel of the formula Na (xAlO ₂ .ySiO ₂ ) wherein χ is a number from 1 to 1.2 and y is 1, with a Mg exchange capacity of about 50 mg-Aq. CaCü "/ g up to about 150 mg-eq CaOOy'g ^ with mixed amorphous / Crystalline G-e rust st off mate rial an u-weight ratio from amorphous uluminosilicate to crystalline aluminosilicate from about 1: 4 to about 4: 1, and (2) about 5 to about 95 ü-ew.-jo of a water-soluble anionic, non-ionic, ampholytic and / or zwitterionic detergent compound. .B ¹ Ur: The Procter & Gamble Company Cincinnati, Ohio, Y.üt.A. r. H. J. WoIH (i-lawyer) 409886/1266