FI62682C - TVAETTMEDELSKOMPOSITION - Google Patents

Description

6? 6 fi?

The present invention relates to a detergent composition capable of rapidly reducing the free polyvalent metal ion content of an aqueous solution and containing from 5 to 95% by weight of a water-soluble organic surfactant and from 5 to 95% by weight of a water-soluble organic surfactant. % of a water-insoluble aluminosilicate having a calcium ion exchange capacity of at least about 200 mg-eq / g, and, if desired, 5-50% by weight of a water-soluble booster salt.

The detergent preparation according to the invention is characterized in that the water-insoluble aluminosilicate is an aluminosilicate ion exchanger having the formula

NA6 (AlO2) 6 (SiO2) 10-15H2O

and having a calcium ion exchange rate of at least 34 mg / 1 / min / g.

It has long been known that laundry detergents work more effectively in soft water than in water containing significant amounts of hardening cations such as calcium ions, magnesium ions, etc. Laundry water can be softened prior to use by passing water through a zeolite column or other cation exchange columns. The use of zeolite or other cation exchangers to pre-soften the water requires a separate tank or device in which water can be slowly passed through the ion exchanger to remove unwanted cations. Such pre-softening procedures require additional costs from the user who has to acquire softening equipment. The second softening treatment is based on the use of water-soluble enhancer salts and / or chelators for the sequencing of undesired hardness-causing cations, i.e. to prevent their harmful effect. However, the use of such water-soluble enhancers necessarily brings certain substances into the wash water that may cause waste-water problems. Thus, a means of incorporating water-softening enhancer-5 agents into detergent compositions without the need for soluble enhancer additives is desirable.

Several different methods have been proposed to provide an effect or water softening effect simultaneously with the washing step of a household laundry operation, but without the use of water-soluble detergent additives. One such method uses a phosphorylated piece of fabric that can be added to a wash bath to sequester metal ions and that can be removed after washing, see U.S. Patent 3,424,545.

The use of certain alumina minerals for the adsorption of metal ions from wash baths has also been proposed; see, e.g., Rao, Soap, Vol. 3, Part 3, pages 3-13 (1950) and Schwartz et al., Surfage Active Agents and Detergents,

Vol. 2, page 297 et seq. (1966).

20 Zeolites, in particular naturally occurring aluminosilicate zeolites, have been proposed for use in detergents; see U.S. Patent Nos. 2,213,641 and 2,264,103.

Various aluminosilicates have been proposed for use as additives in detergent compositions; see, e.g., U.S. Patent Nos. 923,850 and 1,419,625 and GB Patent Publication Nos. 339,355, 461,103, 462,591 and 522,097.

From the above, it can be seen that various methods have hitherto been used to remove hardness-causing cations from aqueous washing systems simultaneously with the washing step of a household washing operation. However, these methods have not achieved overall success, primarily due to the inability of these agents to rapidly and effectively reduce the concentration of free polyvalent metal ions in the aqueous wash liquor to an acceptable level of hardness.

6 2 6 8 2

To be truly useful in laundry detergents, the ion exchanger must have sufficient cation exchange capacity to significantly reduce the hardness of the wash bath without requiring very large amounts of ion exchanger, and in addition, the ion-5 exchanger must act rapidly / so. it must reduce the cationic hardness in the aqueous wash bath to an acceptable level in a short time (about 10-12 minutes). Optimally, effective ion exchangers should be able to reduce calcium hardness to about 15-35 mg / L within the first 1-3 minutes of a wash cycle. Finally, cation exchangers should be water-insoluble inorganic substances so that they present little or no waste-water problems.

It has now been found that certain aluminosilicate materials have both a high ion exchange capacity and a high ion exchange rate, as well as other desirable properties.

Preferably, the preparations of this invention contain: a) about 5-95% by weight of a water-insoluble aluminosilicate ion exchanger having the formula: 20 Nag (A102) 6. (SiO2) 10.15H2O and an aluminosilicate ion exchanger having a grain size of about 0.1 -100 μm preferably about 0.2 to 10 μm, and the calcium ion exchange capacity is at least about 200 mg-eq / g and the calcium ion exchange rate is at least 34 mg / l / min / g, and b) about 5-95% by weight a water-soluble organic surfactant, namely an anionic, nonionic, ampholytic or zwitterionic surfactant, or a mixture thereof.

4,62682 In addition to the ion exchange agent and the organic detergent compound, the detergent compositions of the present invention may contain various other ingredients commonly used in detergent compositions. In particular, water-soluble excipients can be used. in preparations to help remove calcium hardness and sequester magnesium-10 cations in water where dissolved magnesium salts cause significant hardness problems.

In addition, the formulations disclosed herein may contain pH adjusting agents to maintain the pH of the wash liquor in the desired range.

The aluminosilicate ion exchangers disclosed herein are prepared by a process that results in the formation of materials that are particularly suitable for use as detergent builders and water softeners. In particular, the aluminosilicates 20a disclosed herein have both a higher calcium ion exchange capacity and a higher exchange rate than similar agents hitherto proposed as detergent builders. Such a high calcium ion exchange rate and capacity appear to be dependent on a number of interdependent factors resulting from the method of preparation of said aluminosilicate ion exchangers.

An essential feature of the ion exchange building materials disclosed herein is that they are in "sodium form".

In other words, it has surprisingly been found that, for example, the

The potassium and hydrogen forms of the 30 aluminosilicates do not have the optimum ion exchange rate or ion exchange capacity required for enhancer use.

Another essential feature of the ion exchange enhancers disclosed herein is that they are in hydrated form, i. contain 10-28% and preferably 10-22% by weight of water. The highly preferred alumino-5 62682 silicates disclosed herein contain about 18-22% by weight of water in their crystalline rice. For example, it has been found that less hydrated aluminosilicates, e.g., those with about 6% water, do not act effectively as ion exchangers when used in laundry detergents.

A third essential feature of the ion exchange enhancers disclosed herein is their particle size range. A suitable range of small particle sizes results in fast, highly effective effect materials.

The process for preparing the aluminosilicates disclosed herein takes into account all of the above essential factors. First, the method avoids contamination of the aluminosilicate product with non-sodium cations. For example, product washing steps involving acids or bases other than sodium hydroxide are avoided. Second, the process yields aluminosilicate in its most hydrated form. Thus, high temperature heating and drying is avoided. Third, the process yields aluminosilicate-20 materials in a finely divided state with a narrow range of small particle sizes. Of course, additional grindings can be used to further reduce the particle size. However, the need for such mechanical reduction steps is substantially reduced due to the new method.

The aluminosilicate disclosed herein is prepared according to the following procedure: a) adding sodium aluminate (NaA102) to water to form a homogeneous solution having a NaAlO2 content of about 16.5% by weight (recommended), b) adding sodium hydroxide from step a) sodium - to the aluminate solution in a weight ratio of NaOH: NaAlO 2 1: 1.8 (recommended) and maintaining the temperature of the solution at about 50 ° C until all the NaOH has dissolved to form a homogeneous solution, 35 c) sodium silicate (Na 2 SiO 3 with 6 62682

The weight ratio of SiO 2: Na 2 O is 3.2: 1) to the solution of step b) to obtain a solution in which the weight ratio of Na 2 O 2: NaOH is 1.4: 1 and the weight ratio of Na 2 SiO 2 is 0.63: 1, and d) is heated the mixture obtained in step c) to about 90-500 ° C and maintained at this temperature for about an hour.

In a preferred embodiment, the mixture obtained in step c) is cooled to a temperature below about 25 ° C, preferably between 17-23 ° C, and maintained at this temperature for about 25-500 hours and preferably about 75-200 hours.

The mixture obtained in step d) is cooled to a temperature of about 50 ° C and then filtered to recover the desired solid aluminosilicate. If a low temperature (^ 25 ° C) crystallization technique is used, the precipitate is filtered without further preparation steps. The filter cake can optionally be washed free of excess base (washing with deionized water is recommended to avoid cationic contamination). The filter cake is dried to a moisture content of 18-22% w / w. below about 150 ° C to prevent excessive dehydration. Preferably, the drying is performed at 100-105 ° C.

The following is a typical preparation of the aluminosilicate disclosed herein on a pilot plant scale.

7 6 2 6 8 2

Manufacture of aluminosilicate builder

Component Weight Dry weight Water content-% by weight of the mixture / kg / / kg / _ oral / kg / mixture____

NaAlO 2 26.0 22.3 3.7 16.40 (anhydrous) 5 Sodium silicate 37.1 13.9 23.2 10.26 Kate (3.2: 1 SiCl:

Na +)

NaCH 24.8 12.3 12.5 9.05 H 2 O (ionic 47.9 - - 64.29 exchanged)

Sodium aluminate was dissolved in water with stirring, and sodium hydroxide was added thereto. The temperature of the mixture was maintained at 50 ° C, and sodium silicate was added thereto with stirring. The temperature of the mixture was raised to 90-100 ° C and held between this for 1 hour with stirring to effect the formation of Na 2 O (Al 2 O 3 SiO 2) 2 O 2 27H 2 O. The mixture was cooled to 50 ° C, filtered and the filter cake was washed twice with 45.4 kg of deionized water. The cake was dried at a temperature of 100-105 ° C to a moisture content of 18-22% by weight to provide an aluminosilicate construction material.

Aluminosilicates prepared in the above manner are characterized by a cubic crystal structure.

Water-insoluble aluminosilicates with a molar ratio (A102) :( SiO2) of less than 1, i. between 1.0 and about 0.5, can be prepared in the same manner. These aluminosilicates (A102: SiC> 2 <1) are also capable of effectively reducing the concentration of free, polyvalent metal ions in the aqueous wash liquor in substantially the same manner as the aluminosilicate ion exchange material having a molar ratio of A102: SiC> 2 = 1 described above. An example of an aluminosilicate having a molar ratio of AlO 2: SiO 2 <1 is an aluminosilicate used in the invention having the formula: Na 6 (AlO 2) 6 (SiO 2) 10 15 H 2 O.

35 8 62682

Although fully hydrated aluminosilicate tion ion exchangers are preferred in this context, it is noted that partially dehydrated aluminosilicates of the general formula above are also excellent for rapidly and effectively reducing water hardness during the washing step. Naturally, variations in the reaction crystallization parameters in the manufacturing process of this aluminosilicate ion exchange agent can result in such partially hydrated materials. As indicated above, aluminosilicates with about 6% or less water do not work effectively for their intended purpose during washing. The suitability of the particular partially dehydrated, water-insoluble aluminosilicates in question for use in the preparations 15 of the present invention can be readily determined and includes only routine testing, such as the test described herein (cation exchange capacity; cation exchange rate).

The ion exchange properties of the aluminosilicates disclosed herein can be readily determined using calcium ion electrode. In this technique, the rate and capacity of Ca binding from an aqueous solution containing a known amount of Ca ++ ion is determined as a function of the amount of aluminosilicate ion exchange material added to the solution.

The water-Liu-25 non-water-resistant inorganic aluminosilicate ion exchange materials prepared in the above manner are characterized by a grain size between about 0.1 and 10 μm. Preferred ion exchange materials have a grain size of about 1-10. Other preferred water-insoluble aluminosilicates disclosed herein have a characteristic grain size between about 0.2 and 0.7. As used herein, the term "grain size" represents the average particle diameter of a particular ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscopy (SEM).

62682 9 The aluminosilicate ion exchangers disclosed herein are further characterized by a calcium ion exchange capacity of at least about 200 mg CaCO-j hardness / g aluminosilicate, calculated as the anhydrous substance, and generally between about 300 mg eq / g and 352 mg-eq / g.

The ion exchangers disclosed herein are further characterized by a calcium ion exchange rate of at least about 35 mg-Ca ++ / l / min / g aluminosilicate (calculated as anhydrous) and ranging from about 35-105 mg / l / min / g calculated as calcium ion hardness. The Ca ++ exchange rate of the optimum aluminosilicates intended for enhancer purposes is at least about 70 mg / l / min / g.

The above procedure for preparing the alumino-15 silicate ion exchangers disclosed herein can be modified in its various process steps as follows. Step a) can be modified using a solution concentration of NaA102 of between 5-22% by weight; the optimum concentration is 16-16.5%. Step b) can be modified by omitting NaOH. Sodium hydroxide is not required to form the aluminosilicates disclosed herein, but its use is recommended to initiate the reaction and maintain the reaction efficiency. Step b) can be further modified using temperatures between about 30 and 100 ° C; 50 ° C is recommended. Step 25 c) can be modified by varying the ratio of aluminate to silicate. In order to satisfy the stoichiometry requirements of the 1: 1 ratio of aluminosilicate A102: SiO2, which is particularly preferred, it is necessary in this particular case to ensure that the ratio of A102: SiO2 in the mixture is at least 3Q1 (calculated on the basis of NaA102 and Na2102). In the latter case, it is highly recommended to use an excess of NaAlO 2, as an excess of NaA102 has been found to promote the rate and efficiency of an aluminosilicate formation reaction with a molar ratio of A102: SiO2 of 1. Suitable 62682 10 water-insoluble aluminosilicate ion exchangers sSiCl 2 is less than about 1.0, i.e. between 1.0 and 0.5, can be prepared as described above, except that the molar amount of SiO 2 is increased. Appropriate determination of the excess silicate used in the formation reaction 5 can be easily optimized and requires only routine study.

Step d) can be modified using temperatures of 50-110 ° C at ambient pressures; 90-100 ° C is optimal. Naturally, higher temperatures can be used if high pressure equipment is used in the production of aluminosilicates. When using a high temperature (90-100 ° C) crystallization technique, step d) normally requires about 1-3 hours of formation reaction time. As discussed above, a further possibility for the preparation of ion exchangers is to modify step d) by cooling the mixture of step c) to a temperature below about 25 ° C and preferably between 17-23 ° C and to keep said mixture at this temperature for about 25-500 hours and preferably about 75- 200 hours.

2q After the formation of aluminosilicates by the above procedure, the materials are recovered and dried. When aluminosilicates are used as ion exchange enhancers, they must be in a highly hydrated form, i. contain 10-28% and preferably 2 ^ 10-22% by weight of water. Therefore, drying of the aluminosilicates is recommended under controlled temperature conditions. Dry temperatures of about 90-175 ° C can be used. However, drying at temperatures of about 150-175 ° C gives less hydrated substances (about 10% I 2 O). Thus, it is recommended to dry the aluminosilicates at 100-105 ° C to ensure optimum building materials contained in 18-22% by weight of water. At these latter temperatures, the stability of the preferred 27-hydrate form of aluminosilicate is independent of the drying time.

25 The ion exchange materials prepared in the above manner can be used in washing liquids in amounts of about 0.005 to 0.25% by weight based on the weight of the liquid and reduce the hardness level, 6 2 6 8? 11 in particular a calcium hardness of between about 17 and 52 mg / l in about 1-3 minutes. Naturally, the amount of use depends on the initial hardness of the water and the wishes of the user. The highly preferred detergent compositions 5 disclosed herein contain from about 20% to about 60% by weight of an aluminosilicate builder and from about 15% to about 50% by weight of a water-soluble organic detergent compound. In another highly preferred embodiment, the formulations disclosed herein contain from about 10% to about 50% by weight of an aluminosilicate enhancer.

Detergent Component The detergent compositions of this invention may contain all kinds of organic water-soluble detergent compounds as long as the aluminosilicate ion exchangers are compatible with all such materials. A typical list of classes and species of detergent compounds useful herein can be found in U.S. Patent No. 3,664,961.

Water-soluble salts of higher fatty acids, i. "soaps" are useful as a detergent component in the compositions disclosed herein. This class of detergents includes common alkali metal soaps, such as the sodium, potassium, ammonium, and alkylol ammonium salts of higher fatty acids, having from about 8 to 24 carbon atoms, and preferably from about 10 to 20 carbon atoms. Soaps can be prepared with soap-25 by directly adding fats and oils or by neutralizing free fatty acids. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, i. sodium or potassium tallow or coconut soap.

Another class of detergents includes water-soluble salts of organic sulfuric acid reaction products, especially alkali metal, ammonium and alkylol ammonium salts having an alkyl group having about 8 to 22 carbon atoms in the molecular structure and a sulfonic acid or sulfuric acid ester group and a sulfonic acid or sulfuric acid group.

35 (The term "alkyl" also includes the alkyl moiety of acyl groups).

12 62 68?

Examples of synthetic detergents in this group which form part of the detergent compositions of this invention include sodium and potassium alkyl sulfates, especially those obtained by sulfation of higher alcohols (C8-C10 carbon atoms) prepared by reduction of tallow or coconut oil glyceride. ; and sodium and potassium alkylberphenenesulfonates in which the alkyl group contains about 9 to 15 carbon atoms in a straight or branched chain structure, e.g., those described in U.S. Patent Nos. 2,220,099 and 2,477,383. Of particular value are linear, straight chain alkylated benzene sulfonates. alkyl groups contain on average about 13 carbon atoms and are abbreviated c13las.

Other anionic detergent compounds of this invention include sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow or coconut oil and monoglyceride disulfonates and sulfates of sodium coconut fatty acid; and sodium or potassium salts of an alkyl-phenol-ethylene oxide ether sulfate having about 1 to 10 ethylene oxide units per molecule and wherein the alkyl groups contain about 8 to 12 carbon atoms.

Water-soluble nonionic synthetic detergents 25 are also useful. as a detergent component of the preparation. Such nonionic detergent materials can be broadly defined as compounds prepared by condensing alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group condensed with a particular hydrophobic group can be readily adjusted to produce a water-soluble compound having the desired equilibrium between the hydrophilic and hydrophobic moieties.

13 6 2 6 8 2

For example, a well-known class of nonionic synthetic detergents is marketed under the tradename "Pluronic". These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by condensing propylene oxide with propylene glycol. Other suitable nonionic synthetic detergents include polyethylene oxide condensates of alkylphenols, e.g., condensation products of alkylphenols having an alkyl group of about 6 to 12 carbon atoms in either a straight or branched structure, ethylene oxide present in amounts corresponding to 5-25 per alkylphenol.

Water-soluble condensation products of aliphatic alcohols having 8 to 22 carbon atoms in either a straight-chain or branched structure with ethylene oxide, such as coconut alcohol-ethylene oxide condensate having 5 to 30 moles of ethylene oxide per mole of carbon and alcohols containing coconut alcohol useful nonionic detergents 20 in this context.

Semi-polar nonionic detergents include water-soluble amine oxides containing one alkyl moiety of about 10 to 29 carbon atoms and two moieties selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups; water-soluble phosphine oxide detergents having one alkyl group of about 10 to 28 carbon atoms and two alkyl or hydroxylalkyl groups of about 1 to 3 carbon atoms; and water-soluble sulfoxide detergents having one alkyl group of about 30 to 10 carbon atoms and one alkyl or hydroxylalkyl group of 1 to 3 carbon atoms.

Ampholytic detergents include derivatives of aliphatic, secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary or tertiary amines in which the aliphatic moiety may be straight-chain or branched and in which one of the aliphatic 62682 14 substituents contains at least one to 18 carbon atoms. the aliphatic substituent contains an anionic water-dissolving group.

Zwitterionic detergents are derivatives of aliphatic quaternary ammonium phosphonium and sulfonium compounds in which the aliphatic moieties may be straight-chain or branched and in which one of the aliphatic substituents contains about 8 to 18 carbon atoms and one contains an anionic water-soluble group.

Other detergent compounds useful herein include water-soluble salts of esters of sulfonated fatty acids having from about 6 to about 20 carbon atoms in the fatty acid group and from about 1 to about 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-1-sulfonic acids having about 2 to 9 carbon atoms in the acyl group and about 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing about 10 to 20 carbon atoms in the alkyl group and about 1 to 30 moles of ethylene rings; water-soluble salts of olefin-20 sulfonates having about 12 to 24 carbon atoms; and β-alkyloxyalkane sulfonates containing about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane moiety.

Preferred water-soluble organic detergent compounds disclosed herein are linear alkylbenzene sulfonates having from about 11 to about 14 carbon atoms in the alkyl group; tallow alkyl sulfates; kookosalkyyliglyseryy-sulfonates; alkyl ether sulfates; kookosalkyyligly-seryylisulfonaatit; alkyl ether sulfates having an alkyl moiety of about 14 to 18 carbon atoms and having an average degree of ethoxylation ranging from 1 to 6; sulfated condensation products of tallow alcohol with about 3-10 moles of ethylene oxide, olefin sulfonates containing about 14-16 carbon atoms; alkyldimethylamine oxides having an alkyl group of about 11 to 16 carbon atoms; alkyldi-35-methylammoniopropanesulfonates and alkyldimethylammoniohydroxypropanesulfonates, in both of which the alkyl group contains about 14-18 carbon atoms; soaps as defined above; a condensation product of tallow fatty alcohol with about 11 moles of ethylene oxide; and the condensation product of 5 secondary (average) alcohols with 9 moles of ethylene oxide.

Typical detergents suitable for use herein include: linear sodium C 1-6 alkyl benzene sulfonate; triethanolamine C 1-6 C 1-6 alkylbenzene sulfonate; natriumtalialkyylisulfaatti; sodium coconut alkyl glyceryl ether sulfonate; the sodium salt of the sulfated condensation product of tallow alcohol and about 3-10 moles of ethylene oxide; a condensation product of coconut fatty alcohol and about 6 moles of ethylene oxide; the condensation product of tallow fatty alcohol with about 11 moles of ethylene oxide; 3- (N, N-dimethyl-N-kookosalkyyliammonio) -2-hydroxypropane-l-sulfonate; 3- (Ν, Ν-dimethyl-N-kookosalkyyliammoni) prop-ane-l-sulfonate; 6- (N-dodekyylibentsyyli-N, N-dimethyl ammonio) hexanoate; dodekyylidimetyyliamiinioksidi; koo-20 cosalkyldimethylamine oxide; and water-soluble sodium and potassium salts of higher fatty acids having 8 to 24 carbon atoms.

It should be noted that any of the above detergents can be used alone or in mixtures. Examples of 25 detergent compositions recommended in this context are as follows.

A particularly preferred alkyl ether sulfate detergent component for these compositions is a mixture of alkyl ether sulfates having an average (arithmetic mean) carbon chain length of between about 12-15 carbon atoms and preferably about 14-15 carbon atoms and an average (arithmetic mean) degree of ethoxylation of about 1 to 4 carbon atoms. ethylene oxide and preferably about 2-3 moles of ethylene oxide.

62682 16

More particularly, such Preferred Compositions contain from about 0.05 to about 5% by weight of a mixture of C 1-4 compounds, from about 55 to about 70% by weight of a mixture of C 1-4 compounds; about 25-40% by weight of a mixture of C16-8-g compounds and about 0.1-5% by weight of a mixture of C2-6- g compounds. Further, such Preferred alkyl ether sulfate mixtures contain from about 15 to 25% by weight of the mixture of compounds having a degree of ethoxylation of 0, from about 50 to 65% by weight of the mixture of compounds having a degree of ethoxylation from 1 to 4, from about 12 to 22% by weight of the mixture. the degree of ethoxylation is 5-8 and about 0.5-10% by weight of the mixture of compounds with a degree of ethoxylation greater than 8.

Examples of alkyl ether sulfate mixtures that fall within the limits defined above are shown in Table I.

17 62682

C/O

CO rt * tfP rt> ¢ 0 o rt »rt * rt * rt» n r 'co n .. m in (M in <0 mm n h m n 55

B

a o ® <*> rt * o VO ΙΛ α> r- {

Ta! ^ TO <*> *> «#» <#> cm · rt * rt »· rt t ^ h-» inmi-H »cn m cm o z

aj H ^ voen M in io H

«E ^

"B

B

2 (0 --— --—- _

•B

M

© + »f» co m OHND rt »rt * rt * .rt * OJ rt> rt» rt »rt * m rf" SS "„ · 5S5 "* s .u rt -4 --—---

B

o

> 1 CO

M 00 rt »e *» rt * rt »ON rt» rt »rt» rt »5 M ^ m CD in v in m iH r-ι« a m en «h · η vd cm

S M

£ <.

Φ -f »<-s _ e -¾ -S p, 8 * *

Is 3 ~

? | = · 3 S

S2 v „rt->» a

s 2 3 k B e Τίί -S

5 SH v * 1 · *

* rt fl c) Sfl 5 B

g-do-H eHö

• »i S α o αΉ S

rj «o 4» gJ3 J2 Ö Ö * »« 1 a T * * 3 * ** -rt ö 4>

Gail Hccc κβΦΦ O rt CJ »4 o2 | rt g'- 's 3-2 ώ | S§ S £ ET 3 - 13¾ c !. Λ vi> <£ SS 0 T? + § COMP, H rt H H WC-OrrtmON 5 - * ---- 1 62682 18

Preferred "olefin sulfonate H" detergent compositions useful herein include olefin sulfonates having from about 10 to about 24 carbon atoms. Such materials can be prepared by sulfonating N-ol-5 fines with uncomplexed sulfur dioxide and then neutralizing the sulfones present to hydrolyze any sulfonates present. The starting β-olefins preferably have 14 to 16 carbon atoms, said preferred O-olefin sulfonates are described in U.S. Patent 3,332,880.

In this context, the preferred C 1-6 olefin sulfonate mixtures consist essentially of about 30-70% by weight of component A, about 20-70% by weight of component B and about 2-15% by weight of component C, wherein component a) A is a mixture of double bond site isomers of water-soluble salts of alkene-1-sulfonic acids having from about 10 to 24 carbon atoms, which mixture of site isomers contains about 10-25%, β-unsaturated isomer, about 30-70% β-unsaturated isomer, about 5-25% b) component B is a mixture of water-soluble salts of bifunctionally substituted sulfur-containing saturated aliphatic compounds having from about 10 to about 24 carbon atoms, the functional units being hydroxy, γ-, Δ-unsaturated isomer and about 5-10% .00-unsaturated isomer, and sulfonate groups, the sulfonate groups always being on the main carbon and the hydroxyl group attached to a carbon atom at least two carbon atoms away from the terminal carbon of at least 90 % of hydroxy group substitution at the 3-, 4-, and 5-positions; and c) component C is a mixture of about 30-95 * water-soluble salts of alkene disulfonates having from about 10 to 24 carbon atoms and about 5-70% water-soluble salts of hydroxide sulfonates having from about 10 to 24 carbon atoms, the 19 62682 alkene disulfonates having a terminally attached second sulfonate group a sulfonate group attached to an internal carbon atom up to about 6 carbon atoms away from the terminal carbon atom, the alkene-5 double bond being split between the terminal carbon atom and about 7 carbon atoms, said hydroxide sulfonate group attached to the other a carbon-10 atom from said terminal carbon atom to an internal carbon atom and the hydroxy group is attached to a carbon atom up to 4 carbon atoms from the point of attachment of said second sulfonate group.

Additional Enhancers As set forth above, the formulations of this invention may contain, in addition to aluminosilicate ion exchange enhancers, parallel water-soluble enhancers, such as those advised for use in detergent compositions. Such co-enhancers can be used in the sequestration of metal ions from the earth and are particularly useful in combination with aluminosilicate ion exchange enhancers in cases where magnesium ions contribute significantly to water hardness. Such excipients may be used in concentrations of about 5 to 50% by weight and more preferably about 10 to 35% by weight, based on the detergent compositions disclosed herein, to provide their adjuvant builder activity. Additional enhancers of this invention include all conventional inorganic and organic water-soluble enhancer salts.

Such additional enhancers may be, for example, water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, phosphonates, carbonates, polyhydroxysulfonates, silicates, polyacetates, carboxylates, polycargoxylates and succinates. Typical examples of inorganic phosphate enhancers are sodium and potassium tripolyphosphates, pyrophosphates, phosphates and hexametaphosphates. Polyphosphonates include, in particular, the sodium and potassium salts of ethylenediphosphonic acid, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid, and the sodium and potassium salts of ethane-1,1,2-tri-5-phosphonic acid. Examples of these and other phosphorus-containing builders are disclosed in U.S. Patent Nos. 3,159,581, 3,213,030, 3,422,021, 3,422,137, 3,400,176, and 3,400,148.

Phosphorus-free sequestrants can also be selected for use as additional builders in this context.

Typical examples of phosphorus-free inorganic detergent builders are water-soluble inorganic carbonate, bicarbonate and silicate salts. Alkali metal salts, i.e. sodium and potassium carbonates, bicarbonates and silicates, are particularly useful in this context.

Water-soluble organic adjuvants are also useful in this context. For example, alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates are useful adjuvants. preparations. Typical examples of polyacetate and polycarbonate tentane salts are the sodium, potassium, lithium and ammonium substituents of ethylenediaminetetraacetic acid, nitrilotriacetic acid, succinic acid, mellitic acid, benzene polycarboxylic acid and citric acid.

Highly preferred non-phosphorus enhancers in this context are sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodium oxysuccinate, sodium mellinate, sodium nitrilotriacetate and sodium ethylenediamine tetraacetate, and mixtures thereof.

Other highly preferred additional enhancers in this connection are the polycarboxylate enhancers disclosed in U.S. Patent No. 3,308,067, which is incorporated herein by reference. Examples of such substances are dihydric acid of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, methylenemalonic acid, 1,1,2,2-ethanetetracarboxylic acid and homoacetic acid. water-soluble salts of.

Other additional adjuvants recommended in this context are the water-soluble salts of carboxylmethyloximalonate, carboxylmethyloxysuccinate, cis-cyclohexane hexacarboxylate, cis-cyclopentane tetracarboxylate and phloroglucinol trisulfonate, especially sodium salts.

Examples of highly preferred phosphorus-containing adjuvant salts for use herein include alkali pyrophosphates having a weight ratio of ion exchange material to pyrophosphate of from about 20 1: 2 to 2: 1, other preferred adjuvants such as sodium tripolyphosphate acid and nitrile phosphate with an equally excellent potency of the ion exchanger and the auxiliary structural salt in a weight ratio of about 1: 1 to 1: 3, the ion exchange aluminosilicates together with the citrate-25 booster salts provide complete removal of free metal ions in the wash liquor when the molar ratio of zeolites used is AlCl 2 SiCl 2. . It is to be understood that in the above-mentioned preferred ranges between the additional enhancer and the aluminosilicate, the enhancer component may be represented by mixtures of said enhancers.

The detergent compositions disclosed herein containing an aluminosilicate ion exchange enhancer and a water-soluble additive enhancer are useful because the aluminosilicate primarily adsorbs calcium-35 ion in the presence of an additional enhancer. Thus, aluminosilicate primarily removes calcium hardness from solution, 62682 while the additional enhancer remains free to sequester other polyvalent hardness ions such as magnesium and iron ions.

The detergent compositions disclosed herein may contain all kinds of additives commonly found in detergent-5 and cleaning compositions. For example, such preparations may contain thickeners and stain suspending agents such as carboxymethylcellulose, etc. Enzymes, especially proteolytic and lipolytic enzymes commonly used in laundry preparations, may also be present in these preparations. Various perfumes, optical brighteners, fillers, anti-caking agents, textile plasticizers, etc. may be present in these preparations to provide the usual benefits of using such agents in detergents. It will be appreciated that all such excipients are useful in this context insofar as they are compatible and stable in the presence of aluminosilicate ion exchange enhancers.

The granular detergent compositions disclosed herein may also preferably contain from about 3 to about 40% by weight of the peroxygen bleach component, and more preferably from about 8 to about 33% by weight. Examples of peroxygen bleach components suitable for use herein include perborates, persulfates, persilicates, perphosphates, percarbonates, and most commonly all inorganic and organic peroxygen bleaches known to be suitable for use herein. preparations.

The detergent compositions of this invention can be prepared by any of a number of methods well known in the art of preparing commercial detergent compositions. For example, they can be prepared simply by mixing together an aluminosilicate ion exchange material and a water-soluble organic detergent compound. The adjuvant and optional ingredients may simply be added to the set if desired. Alternatively, an aqueous solution of alumino-35 silicate ion exchange enhancer containing 23 62 68? containing dissolved water-soluble organic detergent compound and optional and other additives, can be spray-dried in a tower to provide a granular preparation. Granules 5 of such spray-dried detergent preparations contain an aluminosilicate ion exchange enhancer, an organic detergent compound and optional and additives.

Alternatively, the aluminosilicate ion exchange materials disclosed herein can be used separately in aqueous wash and / or rinse baths to reduce hardness-causing cations. When used in this way, the user can simply add an effective amount, i. sufficient to reduce the hardness to about 15-35 mg / L in a water bath and then add one of the commercial detergent compositions of its choice. Generally, when aluminosil 15 is used in this manner, it is added to about 0.005 to 0.25% by weight of the water bath.

The detergent compositions disclosed herein are used in aqueous liquids to clean surfaces, particularly textile surfaces, using any standard washing and cleaning technique. For example, the formulations disclosed herein are particularly suitable for use in standard automatic washing machines at concentrations of about 0.01 to 0.50% by weight. Optimal results are obtained when the preparations disclosed herein are used in a wash bath in an amount of at least about 0.10% by weight.

As with most commercial laundry detergents, the dry formulations described herein are usually added to a conventional wash solution in an amount of about 100 ml / 30 L of wash water.

Although the aluminosilicate ion exchange enhancers disclosed herein act to remove calcium ions over a wide pH range, it is recommended that detergent formulations containing such materials have a pH between about 8.0-11 and preferably about 9.5-10.2. As with other standard detergent formulations, the formulations disclosed herein perform optimally in the alkaline pH range, removing stains and triglyceride stains and dirt. Although the regional 24 6 2 6 8? the minosilicates naturally provide an alkaline solution, detergent preparations containing an aluminosilicate and an organic detergent compound may additionally contain about 5-25% by weight of a pH adjusting agent. Such preparations may, of course, contain the additional building blocks and optional ingredients described above. The pH adjusting agents used in such preparations are selected such that the pH of a 0.05% by weight aqueous solution of said preparation is between about 9.5 and 10.2.

10 Optional pH adjusting agents useful in this context are all water-soluble bases commonly used in detergent compositions. Typical examples of such water-soluble substances are sodium phosphates, sodium silicates, especially those having a weight ratio of silica to sodium oxide of about 1: 1 to 1: 3.2, and preferably about 1: 1.7 to 1: 2.3; sodium hydroxide; of potassium-hydroxide; triethanolamine; diethanolamine; ammonium hydroxide, etc. Preferred pH adjusting agents in this connection include sodium hydroxide, triethanolamine and sodium silicate.

The following examples illustrate the detergent compositions of this invention.

25 6 2 6 8 2

Example I

Prepare a detergent base granulate having the following composition by conventional spray drying 5 Ingredient Weight TAE3S 14.5

Sodium tallow alkyl sulphate 2.5

Silicate solid 13.0 (Na 2 O / SiO 2 ratio = 2.0) 10 Sodium sulphate 15.0

Other ingredients such as sodium toluene sulphonate, trisodium sulphosuccinate, moisture, etc. 5.0

Sodium salt of ethoxylated tallow alkyl sulfate having an average of about 3 ethylene oxide units per molecule. A mixture is then prepared containing the above detergent base granules and the builder component listed below. The mixture thus obtained is used to clean polyester bags soiled with a clay stain mixture. The patches are then washed for 10 minutes in 40 ° C wash water containing 0.12% by weight of the above detergent mixture. The hardness and the calcium-2g magnesium ratio are varied as shown. After washing, the patches are rinsed, removed from the washing machine and dried. The washing performance is expressed as the sum of Hunter whiteness readings at hardness values of 0, 34, 68, 100, 130, 170 and 200 mg / l (Ca / Mg = 2/1) so that Hunter whiteness is 0 when 0.06 to 30% by weight of sodium sulphate is used instead of the builder mixture, and 100 when 0.06% by weight of sodium tripolyphosphate is used as the builder component. The replacement level of 0.06% by weight is related to the amount of said ingredients in the washing liquid.

The enhancer component is represented by a mixture of alu-22 minosilicate of the formula: 6 2 6 8 2 26

Nag (AlO2) 6 (SiO2) 10.15H2O

prepared as described above and having an average diameter of 3 μm, and additional enhancing agents, namely sodium pyrophosphate, sodium tripolyphosphate, sodium nitrilotriacetate and sodium citrate.

The detergent base granulate represents 0.06% by weight of the washing liquid; the remaining 0.06% by weight constitutes the indicated enhancer component. The whiteness results are:

Aminosilicate ^ Sodium pyrophosphate ^ Hunter white 0.014 0.046 117 0.023 0.037 102 0.033 0.027 94 15% by weight of the washing liquid.

Sodium citrate is evaluated as an additional enhancer instead of sodium pyrophosphate using the experimental conditions shown. In addition, the Ca / Mg hardness level of the gear Haan, as indicated. Hunter whiteness readings are as follows:

Ca: Mg Aluminosilium Sodium citrate ^ Hunterate 1) whiteness 25 1: 1 0.033 0.027 35 0.023 0.037 61 0.0.14 0.046 51 2: 1 0.033 0.027 38 0.023 0.037 52 3Q 0.0.14 0.046 53 3: 1 0.033 0.027 37 0.023 0.037 54 0.014 0.046 50 35% by weight of the washing liquid.

6268? 27

The sodium salt of nitrilotriacetic acid and sodium tripolyphosphate are also evaluated as additional enhancers as substitutes for the sodium pyrophosphate enhancer using the experimental conditions described above. The Ca: Mg ratio is 2: 1.

5 Hunter whiteness readings are as follows:

Alumino- .. Sodium nitrile- Sodium tri- Hunter silicate 'triacetate 1) polyphosphate whiteness 1) 0.014 0.046 to 108 10 0.023 0.037 to 82 0.033 0.027 to 64 0.014 to 0.046 95 0.023 to 0.037 91 0.033 to 0.027 79% by weight of washing liquid .

The above experimental results show the superior washing performance obtained by using special combinations of aluminosilicates and booster salts in connection with the detergent.

Preparations capable of providing substantially similar potency are obtained when the ethoxylated tallow alkyl sulfate is replaced with a substantially equivalent amount of sodium trialkyl sulfate, sodium coconut alkyl sulfate, and sodium decyl benzene sulfonate.

28 62682

Example II

Prepare a spray-dried detergent preparation having the following composition:

Component Amount ^ (% by weight)

A surfactant system containing: 18% sodium thalylalkyl) 30.6 sulfate) 4% condensation product formed from one mole of a secondary fat containing about 15 carbon atoms anicni. l va-alcohol and about 9 moles- 'r3? ~ it ethylene oxide '

Nag (A102) 6. (SiO2) 1Q.15H2O X) 63.9

Water 5.5 x)

Prepared as described above; average diameter 5 .mu.m 20 The above preparation gives an excellent fabric washing performance when used under normal household washing conditions in a washing liquid having a hardness of 120 mg / l, the concentration of the preparation in the washing liquid being about 0.12% by weight. Under such conditions, the foaming and cleaning performance of the formulation of Example II 25 can be advantageously compared to the performance of conventional, fully filled high foaming anionic detergent compositions. Such a preparation is free-flowing and prepared by a conventional spray dryer.

30 The performance quality for a substantially identical Val preparations obtained by the preparation example shown in the above-II natriumtalialkyylisulfaatti replaced by the equivalent amount of kaliumtalialkyylisulfaattia, kaliumkookosalkyyli sulfate, natriumdekyylibentseenisulfonaattia, sodium-35 undekyylibeniseenisulfonaattia, natriumtridekyylibentseeni- 29 62 682 sulfonate, natriumtetradekyylibeitsyylisulfonaattia, sodium tr apropyleenibertseenisulf onate, kaliumdekyyli-bertseenisulfonaattia, kaliumundekyylibertseenisulfonaattia, kaliumtridekyylibertseenisulfonaattia , potassium tetrade-5 kylbercenesulfonate or potassium tetrapropylene benzenesulfonate.

Preparations substantially similar in performance, physical properties and manufacturability are obtained when, in the preparation of Example II described above, the condensation product of a secondary alcohol having 15 carbon atoms and 9 moles of ethylene oxide is replaced by an equivalent amount of tridentecyl alcohol and about 6 ethylene oxide a condensation product of coconut fatty alcohol and about 6 moles of ethylene oxide (HLB = 12.0); Neodol 23-6.5 (HLB = 12); Neodol 25-9 (HLB = 13.1); and Tergi-tol 15-S-9 (HLB = 12); Neodol 25-9 (HLB = 13.1); and Tergitol 15-S-9 (HLB = 13.3).

6 2 6 8 2 30

Example III

Prepare a spray-dried detergent preparation useful in water containing both Ca and Mg ++ hardness and having the following composition: ^ Kanponent Amount (% by weight)

Surfactant system containing: 20% linear sodium alkylbenzene) 27.3 sulphanate with an average alkyl group length of 11.8) weight ratio of 10 carbon atoms) anionic / 4.7% condensation product obtained from 4 ° 26 one mole of coconut fatty alcohol and about 6 moles of ethylene oxide

Na6 (A102) 6. (SiO2) 1q.15H2O x) 17.2 15 Sodium silicate (weight ratio Na2O / SiO2 = 1: 2.4) 16.6

Sodium citrate 22.1

Sodium acetate 5.5

Sodium toluene sulphonate 2.2

Water 4.4 20 Other ingredients 4.7 x)

Prepared as described above; average diameter 7.5 yUm.

The preparation according to Example saa provides excellent Textile cleaning performance when used under normal household washing conditions in a washing liquid + + with a hardness of 120 mg / l Ca / Mg, the concentration of the preparation in said washing liquid being about 0.12% by weight.

The pH of the solution is then about 10.2. Under such conditions, the foaming performance of the preparation of Example III can be advantageously compared to the performance of conventional highly foaming anionic detergent compositions rich in enhancer salts. The preparation is a free-flowing and storage stable 35 and is manufactured by conventional spray drying equipment.

31 62 682

Performance In terms of quality, physical characteristics and manufacturability substantially similar preparations obtained by the above-mentioned preparation, sodium citrate is replaced by the equivalent amount of NAT 5 riumtripolyfosfaattia, sodium carbonate, solution of sodium carbonate, sodium silicate, natriumoksidisukkinaattia, natriummellitaattia, natriumnitrilotriasetaattia, sodium ethylenediaminetetraacetate, natriumpolymaleaattia, natriumpolyitakonaattia, natriumpolymesakonaattia, sodium 10 polyfumarate, sodium polyaconitate, sodium polyseraconate or sodium polymethylene malonate, or a mixture of these substances.

A preparation substantially similar in performance quality, physical properties and manufacturability is obtained when about 3% by weight of sodium perborate is added to the preparation of Example III while all other components remain relatively the same in relative amounts. Such perborate-containing preparations are particularly suitable for use in the washing conditions commonly found in Europe.

When the entire surface-active system in the preparation according to Example III is replaced by an equivalent amount of the alkyl ether sulphate mixtures I, II, III or IV present in Table I, a preparation with excellent washing performance is also obtained.

6 2 6 8 2 32

Example IV

Prepare a phosphorus-free detergent preparation having the following composition:

Component Weight% 5 Surfactant System 40.3

Triethanolamine (pH adjuster) 8.1

NaOH (pH adjuster) 0.6

Nag (A102) 6. (SiO2) 10.15H2O Xx) 25.1

Sodium citrate 17.3

Water and Other Ingredients 8.6 xx ^ The surfactant system contains a mixture of β-olefin sulfonates consisting essentially of about 30-70% by weight of component A, about 20-70% by weight of component A. B and about 2-15% of component C, wherein: a) component A is a mixture of double bond site isomers of water-soluble salts of alkene-1-sulfonic acids having about 10-24 carbon atoms containing about 10-25 β-unsaturated isomers, about 30 -70 'h β, fr 2 -unsaturated isomer, about 5-25% V *, Δ-unsaturated isomer and about 5-10% Δ. -unsaturated isomer; b) component B is a mixture of water-soluble salts of bifunctionally substituted sulfur-containing saturated aliphatic compounds having about 10 to 24 carbon atoms, the functional units being hydroxy and sulfonate groups, the sulfonate groups being always terminal and the hydroxyl groups at least 2 carbon atoms away from the terminal carbon atoms with at least 90% of the hydroxy group substitution at the 3-, 4- and 5-positions; and c) component C is a mixture of 30-95% water-soluble salts of alkene disulfonates having from about 10 to 24 carbon atoms and about 5-70% water-soluble salts of hydroxide sulfonates having from about 30 to 24 carbon atoms, 33 6? 6 H? said alkene disulfonates containing one sulfonate group attached to the terminal carbon atom and another sulfonate group attached to an internal carbon atom up to about 6 hi-5 liatoms from the terminal carbon atom, the alkene double bond having a carbon atom bonded to the terminal carbon of about 7 said hydroxide sulfonates being saturated aliphatic compounds in which one sulfonate group is attached to the terminal carbon, another sulfonate group is attached to an internal carbon atom up to about 6 carbon atoms from said terminal carbon atom, and a hydroxy group attached to the carbon atom at most, 4 carbon atoms away from the point of attachment of said second sulfonate group.

15 XX)

Prepared as described above; average diameter 12 μm.

The preparation according to Example IV is added to a water bath at 43 ° C: 20% by weight and used for washing oily textiles. Excellent washing 2+ 2+ results are obtained when the Ca / Mg hardness is 120-200 mg / l.

When, in the preparation of Example IV, the surfactant system is replaced with an equivalent amount of linear sodium C 1-6 alkyl benzene sulfonate, sodium thallalkyl sulfate, sodium coconut alkyl glycosyl ether enoxysole condensate, talc alcohol and about 3-10 ethyliminoate sulfate and about 6 ethyleneoxy-30-dimol condensation products, tallow fatty alcohol and about 11 ethylene oxide-molar condensation products, 3- (N, N-dimethyl-N-cocoalkylammonio) -2-hydroxypropane-1-sulfonate, 3- (N, N -dimethyl-N-cocoalkylammonio) -propane-1-sulfonate, 6- (N-dodecylbenzyl-N, N-dimethylamino-35-nio) -hexanoate, dodecyldimethylamine oxide, coconut 34 6 2 6 ft 2 alkyldimethylamine oxides or 8-24 carbon atoms water-soluble sodium and potassium salts of fatty acids, or a mixture thereof, give similar results.

When the surfactant system in the preparation of Example IV is replaced with an equivalent amount of a mixture of alkyl ether sulfate compounds containing from about 0.05% to about 5% by weight of a mixture of C 1 -C 2 compounds, from about 55 to about 70% by weight of C is a mixture of C26-17 ~ 20% by weight, a mixture of about 0.1-5% by weight of a mixture of C the degree of ethoxylation is 0, about 50-65% by weight of a mixture of compounds having a degree of ethoxylation of 1-4, about 12-22% by weight of a mixture of compounds having a degree of ethoxylation of 5-8 and about 0.5-10% by weight a mixture of compounds with a degree of ethoxylation greater than 8 gives similar results.

When sodium citrate in the preparation of Example IV is replaced by an equivalent amount of sodium carbonate, sodium bicarbonate, sodium silicate, sodium oxide succinate, sodium melitanate, sodium nitrile triacetate or a mixture of the same as described in U.S. Pat. No. 3,308,067,

Substitution of sodium citrate in the preparation of Example IV with an equivalent amount of carboxymethyloximalonate, carboxymethyloxysuccinate, cis-cyclohexane hexacarboxylate, cis-cyclopentanetetracarboxylate and phloroglucinol trisulfonate gives sodium or the same potassium as potassium.

35 6 2 6 8 2

Example V

Prepare a soap-based detergent granulate having the following composition:

Component Weight% 5 Sodium soap ^ 42.6

Potassium soap ^ 11.2 tae3s 2) 10.7 C11.8LAS 3) 8.8

Sodium silicate 8.9

Sodium citrate 11.9

Brightness 0.57

Scent 0.17

Water 3.4

Miscellaneous rest 15

Soap mixes containing 90% tallow and 10% coconut soap 2)

Sodium salt of ethoxylated tallow alkyl sulphate with an average of about 3 ethylene oxide units per 20 molecules 3)

The sodium salt of a linear alkyl benzene sulfonate having an average alkyl chain length of about 12 carbon atoms.

25 parts by weight of the soap-based granules prepared above are mixed with 17 parts by weight of Na 2 O (AlCl 2) 6 · (SiO 2) 2 O · 15H 2 O (prepared as described above), size 25 μm. The mixture is used in an amount of 0.12% by weight based on the weight of the washing liquid, and an excellent fabric washing performance of 170 mg / l is obtained.

The preparation of Example V is modified by the addition of 3 parts by weight of sodium perborate to give an excellent washing performance in hot water (50-80 ° C).

As can be seen from the above, the 35 aluminosilicate ion exchange enhancers disclosed herein can be used for 36 h? 6 8? in all kinds of detergent preparations. In addition, aluminosilicate builders in combination with water-soluble additive builders that sequester magnesium, iron and other polyvalent water hardness cations can also be used in conjunction with all kinds of detergent preparations. Depending on the user's wishes, it is of course possible to add aluminosilicate builders or a mixture of aluminosilicate builders and additional builders to the washing or rinsing liquid separately from the detergent preparations. Such separate use provides flexibility while providing the desired benefits of the enhancers disclosed herein.

Since most hard waters contain polyvalent metal ions other than calcium ions, the use of aluminosil-15 coating enhancers requires the presence of additional enhancers of the type described above. Such additional enhancers may be any phosphorus-containing enhancers, or, if such enhancers are not acceptable, any of the phosphorus-tower enhancers described above. Aluminosilicate builders and additional builders can, of course, be added separately to water to provide their softening effect. However, it is easier to add such substances to the water being treated at the same time. Thus, the user is provided with formulations containing about 5-95% by weight of the aluminosilicate enhancer disclosed herein and about 5-95% by weight of additional enhancers of the type described above. Preferably, such preparations contain an aluminosilicate builder and an adjuvant in a weight ratio of about 5: Ι to ΒΟ 1: 5. Such formulations may be provided to the user in any form suitable for use as detergent builders, such as dry powders, tablets, pre-packaged packages, or water-soluble, which may simply be added to the aqueous solution to be plasticized.

37

Various excipients such as bleaches, bleaches, textile plasticizers, foam modifiers, perfumes and sanitary agents, etc. may optionally be included in such preparations to provide the desired additional benefits.

The rate of action and ion exchange capacity of the aluminosilicate materials disclosed herein are easy to determine when such agents are used to pre-soften washing liquids. In order to be suitable for such use, the substances 10 must not be so slow that they require too long a waiting time before adding the laundry detergent to the washing liquid. Moreover, it is also not desirable to require the user to use substances with such a low ion exchange capacity that an unreasonably large amount is required for efficient sequencing of hardness ions. For these reasons, the aluminosilicates disclosed herein are particularly suitable for such enhancer and water softener purposes.

The following is an example of the booster-20 substance preparation of the present invention suitable for use in water containing all kinds of polyvalent hardness cations.

Example VI

Component Weight% 25 Nag (A102) 6. (SiO2) 10.15H2O X) 62

Sodium citrate 38 V)

Made as described herein; diameter 100 μm. 30

The above preparation is prepared as a granular powder. Add 57 g of the powder to 56 l of washing water and stir for 1/2 hour. During this time, the hardness cations decrease substantially to a level of about 15-35 mg / l (starting from a hardness of 120 mg / l). The commercial laundry detergent is then added to the 38 62 6ft 2 5 water bath. Textiles that can be washed in such pre-softened water are cleaned very effectively.

In the above preparation, sodium citrate is replaced by the equivalent amount of sodium polyphosphate, sodium carbonate, sodium bicarbonate, sodium silicate-10-acetate, natriumoksidisukkinaattia, natriummellitaattia, sodium nitrilotriacetate, natriumetyleenidiamiinitetra gun-acetate, natriumpolymaleaattia, natriumpolyitakonaattia, natriumpolymasakonaattia, natriumpolyfumaraattia, sodium polyakonitaattia, natriumpolyistrakonaattia, natriumpoly-15 methylene malonate, sodium carboxymethyloximalonate, sodium carboxymethyloxysuccinate, cis-cyclohexane hexacarboxylate, cis-cyclopentane tetracarboxylate or fluoroglycinol trisulfonate, or a mixture thereof, provides an effective hard water washing power.

The above preparations are used in concentrations of 0.005 to 0.25% by weight and effectively soften water containing polyvalent cations.

The aluminosilicate builders and mixtures of aluminosilicate builders and additional builders disclosed herein are useful in all types of cleaning preparations. In addition to the above, they can also be effectively used in other detergent compositions, such as floor cleaning compositions and abrasives, where water hardness also causes cleaning performance problems. Typical abrasive cleaning compositions may contain, for example, about 25-95% by weight of an abrasive (e.g., silica), about 10-35% by weight of the aluminosilicate enhancer disclosed herein, about 0.20% by weight of the additional enhancer disclosed herein, and about 0.2-10% by weight. % by weight of organic detergent compound.

39 (: '?. F> 8' /

Example VII

Prepare a granular detergent mixture having the following composition: 5 Ingredients Weight parts RAE3S 15 15.3

Sodium tallow alkyl sulphate 2.2

Sodium tripolyphosphate 25.5

Nag (A102) 6. (SiO2) 1Q.15H2O 2) 11.9 10 Sodium sulphate 38.9

Clear 1/0

Moisture 5.3 ^ Sodium salt of ethoxylated tallow alkyl sulfate with an average of about 3 ethylene oxide units per molecule 2)

Prepared as described herein; average diameter 3-5 [mu] m 20 This preparation provides excellent stain removal and cleaning performance during normal washing, even in water with a high initial hardness, e.g. 120-240 mg / l.

Claims (2)

A detergent preparation capable of rapidly reducing the content of free polyvalent metal ion 5 in an aqueous solution and containing 5-95% by weight of a water-soluble organic surfactant and 5-95% by weight of a water-insoluble aluminosilicate having a calcium ion exchange capacity of at least about 200 mg-eq / g, and if desired 5-50% by weight of a water-soluble booster-10 salt, characterized in that the water-insoluble aluminosilicate is an aluminosilicate ion exchanger having the formula: Na6 (AlO2> 6- <Sio2) i0-15H2o 15 and having a calcium ion exchange rate of at least 34 mg / l / min / g. Detergent preparation according to Claim 1, characterized in that the aluminosilicate ion exchanger has a grain size of between about 0.2 and 10 μm.