FI63057C - TEXTILUPPMJUKARE - Google Patents

Description

1 63057

Tekstiilipehmennin

The present invention relates to a textile plasticizer, characterized in that it contains a) 5-95% by weight of a water-insoluble aluminosilicate tion ion exchanger having the formula: Na (AlO 2) · (SiO ,) * XH, 0, where z and y are integers of at least 6, the molar ratio of z: y is between 1.0 and about 0.5, and x is an integer between about 15 and about 264, wherein The aluminosilicate ion exchanger has a grain size of between about 0.1 and about 100 microns, a calcium ion exchange capacity of at least about 200 mg-eq / g, a calcium ion exchange rate of at least about 34 mg / l / min / g, and a moisture content of between 10 and 28% by weight, and 15 b) about 1 to about 35% by weight of a cationic textile softener.

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 the softening equipment. The second softening treatment is based on the use of water-soluble enhancing salts and / or chelators to sequester the undesired hardness-causing cations, i.e. to prevent their adverse effect. However, the use of such water-soluble enhancers necessarily brings certain substances into the wash water that may cause wastewater problems. Thus, a means of incorporating water softening enhancers into detergent compositions without the need for soluble enhancer additives is desirable.

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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., 10 Rao, Soap, Vol. 3, Part 3, pages 3-13 (1950) and Schwartx et al., Surfage Active Agents and Detergents, Vol. 2, page 297 et seq. (1966).

Zeolites, especially naturally occurring aluminosilicates, have been proposed for use in detergents; see 15 U.S. Patents 2,213,641 and 2,264,103.

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

20 It can be seen from the above 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 hardness level. To be truly useful in laundry detergents, the ion exchange zone 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 exchanger must act rapidly, i. it must reduce the cationic hardness in the aqueous wash bath to an acceptable level in a short time (about 10-12 minutes).

35 Optimally, effective ion exchangers should be able to reduce calcium hardness to about 15-35 mg / L during the first 1-3 minutes of a wash cycle. Finally, cation exchangers should be water-insoluble inorganic substances that present little or no wastewater problems.

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

In a preferred embodiment of the present invention, the water-insoluble aluminosilicate ion exchanger has the formula: Na 2 (AlCl 2, SiO 2) 13 * x 2 O, where x is an integer of about 20-30 (preferably about 27).

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 disclosed herein have both a higher calcium ion exchange capacity and a higher exchange rate than similar substances hitherto proposed as detergent builders. Such a high rate and capacity of calcium ion-20 exchange turns out to be dependent on several interdependent factors resulting from the process of preparation of said aluminosilicate ion exchangers.

An essential feature of the ion exchange components 25 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 aluminosilicate do not have the ion exchange rate or ion exchange capacity required for optimal 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 aluminosilicates disclosed herein contain about 18-22% by weight of water in their crystal matrix. For example, it has been found that less hydrated aluminosilicates, for example those with about 6% water, do not act effectively as ion exchangers when used in laundry detergents.

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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 described below for the preparation of 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 provides aluminosilicate in its most hydrated form. Thus, high temperature heating and drying is avoided. Third, the process yields aluminosilicate 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 NaAlCl2 content of about 16.5% by weight (recommended), b) adding sodium hydroxide from step a) sodium aluminum NaOH: NaAlO 2> 1 1: 1.3 (recommended) and maintaining the temperature of the solution at about 50 ° C until all NaOH is dissolved to form a homogeneous solution, c) sodium silicate (Na 2 O 2 with SiO 2: The Na 2 O weight ratio is 3.2: 1) to the solution of step b) to provide a solution in which the Na 2 O 2: NaOH weight ratio is 1.4: 1 and the Na 2 SiO 2 weight ratio is 0.63: 1, and d) is heated. the mixture obtained in step c) is about 90-100 ° 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 more preferably about 75-200 hours.

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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 filtrate is filtered without further preparation. 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% by weight using a temperature 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.

Manufacture of aluminosilicate builder

Component Weight Dry weight- Water content- Weight% of oral size ^ kg / LH1 of the mixture

NaAlO- 26.0 22.3 3.7 16.40 (anhydrous *)

Sodium silicate 37.1 13.9 23.2 10.26 "(3.2: 1 SiO 2: Na 2 O) 20 NaOH 24.8 12.3 12.5 9.05" Η ~ 0 (ion-exchanged) 47.9 - - 64.29

Sodium aluminate was dissolved in water with stirring, and sodium hydroxide was added thereto. The temperature of the mixture was maintained at 50 ° C. Sodium silicate was added thereto with stirring. The temperature of the mixture was raised to 90-100 ° C and maintained for 1 hour with stirring to effect the formation of Na 2 O (Al 2 O * SiO 2) 12 * 27H 2 O. The mixture was cooled to 50 °, 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.

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

35 Water-insoluble aluminosilicates with a molar ratio (A102) :( SiO2) of less than 1, i. between 1.0 β 63057 and about 0.5, can be prepared in the same manner. These aluminosilicates (AlC> 2: SiO 2 <1) are also able to effectively reduce the concentration of free, polyvalent metal ions in the aqueous wash liquor in substantially the same manner as the alu-5 minosilicate ion exchange material with a molar ratio of A102:

SiO 2 = 1 and described above. Examples of aluminosilicates having a molar ratio of A102: SiO2 <1 and suitable for use in this preparations are: Nagg / (AlC> 2) gg (SiO2) 10G _ / * 264 H2O and Na6 </ “(A102) 6 (SiO2) 10_7 * 15 H2O.

Although fully hydrated aluminosilicate 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 15. Naturally, in the manufacturing process of this aluminosilicate ion exchanger, variations in the reaction crystallization parameters 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 compositions of this invention can be readily determined and includes only routine testing, such as Test 25 (cation exchange capacity; cation exchange rate) described herein.

The ion exchange properties of the aluminosilicates disclosed herein can be easily determined by means of a 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-insoluble inorganic aluminosilicate ion exchange materials prepared in the above manner are characterized by a grain size between about 0.1 and 100. Preferred ion exchange materials have a grain size of about 1 to 10 microns. Other preferred water-insoluble aluminosilicates disclosed herein are characterized by a grain size between about 7,63057 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 5 microscopy (SEM).

The aluminosilicate ion exchangers disclosed herein are further characterized by a calcium ion exchange capacity of at least about 200 mg CaCO 3 hardness / g aluminosilicate calculated as anhydrous material, 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 optimum aluminosilicates intended for enhancer purposes is at least about 70 mg / l / min / g.

The above procedure for preparing the aluminosilicate ion exchangers disclosed herein can be modified in its various process steps as follows. Step a) can be modified using a solution concentration of NaAlCl 3 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 preferred. Step c) can be modified by varying the ratio of aluminate to silicate. In order to satisfy the stoichiometric requirements of 2: 1 aluminosilicate AIO: SiO2 in a particularly preferred ratio, it is necessary in this particular case to ensure that the molar ratio of AlO2: SiO2 in the mixture is at least 1 (calculated on the basis of NaAlO2 and ^ 28102). In the latter case, it is highly recommended to use an excess of 35 NaAlO 2, as an excess of NaA10 2 ”has been found to enhance the rate and efficiency of the aluminosilicate formation reaction with a molar ratio of AlO 2: SiO 2 of 1. Suitable water-insoluble aluminosilicate ion exchangers, water-insoluble aluminum having a molar ratio of AlCl 2 SiO 2 of less than about 1.0, i.e. between 1.0 and 0.5, can be prepared as described above, except that a molar amount of SiO 2 sn is added. Appropriate determination of the excess amount of silicate-5 used in the formation reaction can be easily optimized and requires only routine investigation.

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 to make the aluminosilicates. When using the 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 15 d) by cooling the mixture of step c) below a temperature below about 25 ° C and preferably between 17-23 ° C and keeping said mixture at this temperature for about 25-500 hours and preferably about 75 -200 hours.

After the formation of aluminosil-20 cats 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 10-22% by weight of water.

Therefore, drying of the aluminosilicates is recommended under controlled temperature conditions. Drying temperatures of about 90-175 ° C can be used. However, at drying temperatures of about 150-175 ° C, less hydrated substances are obtained (about 10% H 2 O). Thus, it is recommended to dry the aluminosilicates at 100-105 ° C to ensure optimum building materials containing 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.

The ion exchange aluminosilicates disclosed herein can also be used in conjunction with standard cationic textile-35 plasticizers in fabric rinsing. When used in this way, aluminosilicates remove hardening cations and provide a softer feel to the softened textiles. Typical cationic textile plasticizers useful in conjunction with aluminosilicate ion exchangers include thallitrimethylammonium bromide, thallitrimethyl-ammonium chloride, ditalidimethylammonium bromide, and ditalidomethylammonium chloride. Aqueous textile plasticizers containing aluminosilicate ion exchangers contain from about 5 to 95% by weight of aluminosilicate and from about 1 to 35% by weight of a cationic textile plasticizer.

10 The following examples in tabular form illustrate the invention. The column on the left lists the components of the textile softener, and the column on the right lists the amounts of the ingredients.

Example I II III

15 Zeolite A (1) 10

Zeolite X (2) 7

Zeolite P (B) (3) 28

Ditalidimethylammonium chloride 13 6 20

Glycerol monostearate 2 3 20 Branched C ^ g-C22 “alkane mixture 10

Thallamine + 5 ethylene oxide 1

Condensation product obtained from 1 molar tallow alcohol and II molar ethylene oxide 2

Dithalimidazolinium methosulphate 10 5 25 Sodium sulphate 38

Sodium perborate 4

Remaining water and additives total 100% (1) Na ^ 2 (AlC ^ 'SiOj) ^ 2 * 27Η2θ: grain size 1-3 ^ um (2) Nagg (Al O2) 86 (SiOj) iq6 * 264 grain size 0.5- 2yUm 30 (3) Na6 (AlOj) g (SiO2) ^ · ^ H2Of grain size 1-2 .mu.m.

♦

Claims (4)

10 63057 A textile softener, characterized in that it contains 5 a) 5-95% by weight of a water-insoluble aluminosilicate ion exchanger having the formula: Na (A10 „). (SiO-) .xH-0 zzzzy 2 10 where z and y are integers of at least 6, the molar ratio of z: y is from about 1.0 to about 0.5, and x is an integer from about 15 to about 264, wherein the aluminosilicate ion exchanger has a grain size of between about 0.1 and about 100, has a calcium ion exchange capacity of at least about 200 mg-eq / g, a calcium ion exchange rate of at least about 34 mg / l / min / g, and a moisture content of between 10 and 28% by weight, and b) about 1- about 35% by weight of a cationic textile softener. Textile plasticizer according to Claim 1, characterized in that the aluminosilicate ion exchanger has the formula: Na 12 (AlO 2 .SiO 2) 12.xH 2 O 25 where x is an integer between 20 and 30. Textile plasticizer according to Claim 1, characterized in that the aluminosilicate ion exchanger has the formula: Na 12 (AlO 2 .SiO 2) 12.27H 2 O. Textile plasticizer according to Claim 1, characterized in that the cationic textile plasticizer is tallow trimethylammonium bromide, tallow trimethylammonium chloride, ditalidimethylammonium bromide or ditalidimethylammonium chloride.