AT396691B - Textile cleaning bath contg alumino silicates - as fine dispersion functioning as calcium sequestering agents - Google Patents

Abstract

The bath contains a fine water insol. suspension of crystalline particles able to fix >=50 (100-200) mg CaO/g of active anhydrous substances having formula:- (Cat2/nO)x, Me2O3, (SiO2)y, where Cat is a cation of valency n (Li, K, NH4, Mg or water sol. org. bases) exchangeable with Ca++, x is 0.7-1.5, Me is boron or aluminium, y is 0.8-6 pref. 1.3-4). Particle size of >=80% of the alumino silicates is 10-0.01 mu and no particles >40 mu. The bath contains 0.05-2 g/litre of calcium complexing agents e.g. polycarboxylic acid. The compsn. contains 5-30% surfactant, 5-70% alumino silicates, 2-45% complexing agents 0-50% detergents, 0-50% bleach and phosphates (pref. 3%P). This is a feasible industrial process for fixing cations during cleaning without the need to add large amts of e.g. phosphorylated cotton.

Description

AT396 691B

Master patent No. 368 185 relates to a process for washing or bleaching textiles by treating them with an aqueous liquor which contains suspended water-insoluble silicates. This process is characterized in that finely divided, crystalline, optionally bound water-containing synthetically produced silicates are used, the composition of which corresponds to the formula 0 ^ 2ΙτΡ) χ · ^ 2 ^ 3 · (Si02) y, in the cat a cation which is exchangeable with calcium Values n, x is a number from 0.7-1.5 and y is a number from 0.8-6, preferably from 0.9-4, and which have a calcium binding capacity of at least 50 mg CaO / g of anhydrous active substance (= AA ), determined by determining the reduction in the degree of hardness of 11 water of 30 ° dH and 22 ° C after 15 minutes of 1 g (based on AS) of the silicate defined above.

The calcium binding capacity can reach values of 200 mg CaO / g AS.

Sodium is preferred as the cation; but it can also be replaced by lithium, potassium, ammonium or magnesium and the cations of water-soluble organic bases, e.g. B. those of primary, secondary or tertiary amines or alkylolamines with at most 2 carbon atoms per alkyl radical or at most 3 carbon atoms per alkylol radical.

The cation-exchange compounds defined above to be used instead of the phosphates, in particular the tripolyphosphate, are hereinafter referred to as " aluminum silicates " designated. Sodium aluminum silicates are preferably used. All statements made for their manufacture and use apply mutatis mutandis to the other claimed compounds.

Compounds of the composition 0.7-1.1 N320 are of particular practical interest. AI203. U - 2.4 Si02.

The calcium binding capacity of these substances is approximately in the range of 100-200 mg CaO / g AS.

Various processes for producing the aluminum silicates are described in the parent patent; whose primary particle size can be in the range from 50 to 0.1 μm, depending on the production method and the state of crystallization. However, it is possible for the primary particles of the aluminum silicates to agglomerate as larger secondary particles when they are transferred from the crystallization slurry into a dry powder;

The design of the method is characterized in that at least 80% by mass of the silicates in the liquor as defined above consist of particles with a size of 10 to 0.01 μm, preferably 8 to 0.1 μm, and the aluminum silicates have practically no particles > Contain 40 μιη, but excluding the case that the aqueous liquor in a ratio of 1: 19 to 19: 1 an a) water-soluble, organic, surface-active agent from the group comprising anionic, nonionic, ampholytic and zwitterionic surface-active agents and mixtures thereof and b) a crystalline, water-insoluble, inorganic aluminosilicate ion exchange material of particle size from 1 pm to 10 pm and of the formula

Nai2 (AK) 2. Si02) j2 · ^ H20, with x an integer from 20 to 30, the aluminosilicate ion exchange material having a calcium ion exchange capacity of at least 200 mg equivalent calcium caibonate hardness / g aluminosilicate (calculated as anhydrous) and a calcium ion exchange rate of at least 0.034 g calcium carbonate / l / min / g aluminosilicate (calculated anhydrous).

The design of the agent of the parent patent is characterized in that at least 80% by mass of the aluminum silicates of the formula of the parent patent consist of particles with a size of 10 to 0.01 pm, preferably 8 to 0.1 pm, and the aluminum silicates contain practically no particles > 40 pm contain, but washing, bleaching and cleaning agents are excluded, which contain 5-95% by weight of the surface-active agent defined under a) and 5-95% by weight of the aluminosilicate defined under b).

Precipitation conditions can already contribute to the formation of small particle sizes, whereby the mixed aluminate and silicate solutions - which can also be fed into the reaction vessel at the same time - are exposed to strong shear forces. In the production of crystallized aluminum silicates, the formation of large, possibly penetrating crystals is prevented by slowly stirring the crystallizing mass.

Nevertheless, undesirable agglomeration of crystallite particles can occur during drying, so that it is advisable to use these secondary particles in a suitable manner, e.g. B. to remove by air sifting. Aluminum silicates obtained in a coarser state, which have been ground to the desired grain size, can also be used. For this purpose, z. B. mills and / or air classifiers or combinations thereof. The latter are e.g. B. at Ullmann: " Encyclopedia of Industrial Chemistry " Volume 1.1951, pages 632 - 634 -2-

AT396691B.

For the rest, all the details of the parent patent also apply mutatis mutandis to this invention, the advantage of which lies first of all in the possibility of using microcrystalline aluminum silicates, which can be produced with reasonable technical effort and which can be washed out more easily and completely from washed laundry than products with the coarser parts contain. In addition, the aluminum silicates to be used according to the invention have a higher calcium binding rate than coarser products.

Examples:

The production of the aluminum silicates used is first described, for which no Schulz is sought. The silicate solution was added to the aluminate solution, which had been diluted with deionized water, in a vessel with a volume of 15 l and was mixed with a high-speed intensive stirrer (10,000 rpm; make "Ultraturrax") from Janke and Kunkel IKA-Werk, S taufen / Breisgan / Federal Republic Germany) treated, an X-ray amorphous sodium aluminum silicate formed as the primary precipitation product under an exothermic reaction. After vigorous stirring for 10 minutes, the suspension of the precipitate was transferred to a crystallization container, where it remained for some time with slow stirring at an elevated temperature for the purpose of crystallization. After the lye had been suctioned off from the crystal slurry and washed with deionized water until the wash water running off had a pH of about 10, the filter residue was dried, then ground in a ball mill and in a centrifugal classifier (Mikroplex wind classifier from Alpine, Augsburg, Federal Republic of Germany) into two fractions, the finer of which contained no portions above 10 pm. The grain size distribution was determined using a sedimentation balance

If one deviates from this general manufacturing regulation, this is expressly mentioned in the special section. The water contents were determined by heating the products to 800 ° C for one hour. All percentages are percentages by mass.

The aluminum silicates described here are correct in terms of precipitation conditions and analytical composition of the end product with the corresponding, ie. H. products from the parent patent largely correspond to the same Roman numeral; differ from the latter, however, by the particle size. For this reason, the products to be used according to the invention were identified by an “m” (= microcrystalline) after the Roman number

Manufacturers conditions for the aluminum silicate Im: Precipitation: 2.985 kg aluminate solution of the composition: 17.7% Na ^, 15.8% Al203.66.6% H20; 0.15 kg caustic soda; 9.420 kg of water, 2.445 kg of a 25.8% strength sodium silicate solution of the composition 1 Na20.6.0 SiO 2 freshly prepared from commercially available water glass and slightly alkali-soluble silica

Crystallization: 6 hours at 90 ° C Drying: 24 hours at 100 ° C

Composition: 0.9 Na20.1A1203.2.04 Si02.4.3 H20 (= 21.6% H20)

Degree of crystallization: fully crystalline, calcium binding capacity: 170 mg CaO / g AS

Production conditions for the aluminum silicate Ilm: precipitation: 2.115 kg aluminate solution of the composition: 17.7% Na20.15.8% A1203.66.5% H20; 0.585 kg caustic soda; 9.615 kg water; 2.685 kg of a 25.8% sodium silicate solution of the composition: 1 Na ^. 6 Si02 (manufactured as specified in Im)

Crystallization: 12 hours at 90 ° C Drying: 24 hours at 100 ° C and 27 mbar Composition: 0.8 Na20.1A1203.2.655 Si02.5.2 H20 Degree of crystallization: fully crystalline Calcium binding capacity: 145 mg CaO / g AS

Production conditions for the aluminum silicate Xllm: precipitation: 2.01 kg aluminate solution of the composition: 20.0% Na20.10.2% A1203, 69.8% H20; 1.395 kg caustic soda; 9.405 kg water; 2.19 kg of a 25.8% sodium silicate solution of the composition: 1 Na20.6 Si02 (prepared as given under Im);

Crystallization: 6 hours at 90 ° C

Drying: 24 hours at 100 ° C

Composition: 0.9 Na20.1A1203.2 Si02.3 H20 -3-

AT396691B

Degree of crystallization: fully crystalline Calcium binding capacity: 175 mg CaO / g AS

Production conditions for the aluminum silicate Xlllm: precipitation: 2.985 kg aluminate solution of the composition: 17.7% Na ^, 15.8% AljOß, 66.5% H20; 0.150 kg caustic soda; 9.420 kg water; 2.445 kg of a 25.8% sodium silicate solution of the composition: 1 Na20.6 Si02 (prepared as given under Im)

Crystallization: 6 hours at 90 ° C

To prepare the potassium aluminum silicate, the alkali was suctioned off, the residue was washed with water and slurried in an aqueous solution containing KCl. After heating for 30 minutes at 80-90 ° C., the mixture was filtered off and washed.

Drying: 24 hours at 100 ° C

Composition: 0.28 N ^ O. 0.62 K20.1 A12C > 3.2.04 Si02.43 H20 Degree of crystallization: fully crystalline Calcium binding capacity: 180 mg CaO / g AS

Manufacturing conditions for aluminum silicate XVm:

Precipitation: 8.450 kg of aluminate solution of the composition: 11.3% Na20.18.7% Al2O3.70.0% H20; 6350 kg of a »34.9% sodium silicate solution of the composition: 1 Na20.3.46 Si02 crystallization: 24 hours at 80 ° C

Drying: The filter cake was not dried, but slurried in water after washing and used in this form for the application studies. Composition: 0.9 Na20.1Α120 ^. 2 Si02. x H20

Degree of crystallization: fully crystalline, calcium binding capacity: 170 mg CaO / g AS

Manufacturing conditions for aluminum silicate XVIIIm:

Precipitation: as with aluminum silicate XVm crystallization: 6 hours at 90 ° C drying: 24 hours at 100 ° C composition: 0.9 Na2Ü. 1 A12C > 3.2 Si02.4.4 H20 Degree of crystallization: fully crystalline Calcium binding capacity: 172 mg CaO / g AS

The particle size distribution of the above-described microcrystalline products Im-Xlllm and XVIIIm determined by sedimentation analysis was in the following range: > 40 pm=0% < 10 pm=100% < 8 pm = 50 - 95%

Maximum of the particle size distribution curve = 3 - 6 pm

The particle size distribution of the product XVm was in the following range: &gt; 40 pm=0% &lt; 10 pm = 100% <8 pm=99%

Maximum of the particle size distribution curve = 1 - 3 pm

The salt-like constituents contained in the washing or washing aids of the examples — salt-like surfactants, other organic salts and inorganic salts — were present as sodium salts, unless expressly stated otherwise. This also applies to the precipitation retarders, which for the sake of simplicity are labeled with the names of the corresponding acids. The related terms or abbreviations mean: &quot; ABS &quot; the salt of an alkylbenzenesulfonic acid with 10-15, preferably 11-13 carbon atoms in the alkyl chain obtained by condensing straight-chain olefins with benzene and sulfonating the resulting alkylbenzene, "HPK &quot; sulfonate" a sulfonate obtained from hydrogenated palm kernel fatty acid by sulfonating with SO3, ΌΑ + x ÄO &quot; or &quot; TA + x ÄO &quot; the addition products of ethylene oxide (ÄO) on technical -4-

AT 396 691B

Oleyl alcohol (OA) or tallow fatty alcohol (TA) (JZ = 0.5), the numerical values for x denoting the molar amount of ethylene oxide attached to 1 mol of alcohol, &quot; NTA &quot; or &quot; EDTA &quot; the salts of nitrilotriacetic acid or ethylenediaminetetraacetic acid, &quot; HEDP &quot; the salt of l-hydroxyethane-l, l-diphosphonic acid, 5 &quot; DMDP &quot; the salt of dimethylaminomethane diphosphonic acid, "CMC" the salt of carboxymethyl cellulose.

The washing tests described in the parent patent were also carried out with the microcrystalline aluminum silicates to be used according to the invention. This showed at least equally good, often better washing results.

Example 1:

This example demonstrates the washing effect of various aluminum silicates to be used according to the invention without the addition of further washing-active constituents. 15 working conditions: untreated cotton, 10 g / 1 aluminum silicate; Liquor ratio: 1: 12, 30 min at 90 ° C in a launderometer.

In a parallel test, the dirt removal was determined with water without any further addition or with the addition of 10 g / 1 tripolyphosphate.

When testing the aluminum silicates Im, Ilm and IYm, mostly better values were obtained than with the 20 attempts of the parent patent.

Example 2:

To demonstrate the improvement in the washing action of a detergent 25 containing aluminum silicate - produced by mixing the dry aluminum silicate with perborate, a precipitation delay »and a detergent powder obtained by hot atomization and not containing the three components mentioned above - by adding complexing agents or precipitants for calcium detergents as follows Composition: 30

45.0% Al-Silicate Xllm 22.1% Perborate 2.5% Na20.33 Si02 13% CMC I, 7% MgSiOg 2, l% Na2S04 II, 1 %% 0 53% ABS.

2.0% TA +14 ÄO 2.8% soap'C12-C22 0 or 4.2% complexing agent 35 or precipitant for calcium

Here, too, there was an improvement in washing success through the simultaneous presence of the following 40 complexing agents or precipitants for calcium: 45

Oxalic acid tartaric acid citric acid O-carboxymethyl-tartronic acid O-carboxymethyl-methyltartronic acid

Na5P3 ° 10 alanine glutamic acid nitrilotriacetic acid ethylenediamine tetraacetic acid N, N-dimethylamino methane diphosphonic acid polyacrylic acid polyhydroxy polycarboxylic acid +) 50 +) This substance pattern was prepared by polymerizing acrolein and treating the polymer according to Canizzaro in the presence of formaldehyde. 55 Example 3:

This example demonstrates the gradual replacement of the triphosphate contained in a detergent with aluminum silicate. The composition of the detergents was within the scope of the following recipe -5- 60

AT 396 691B 53% ABS 2.0% TA + 14ÄO2.8% soap 43-33.4% Na5P3O10 45 - 0.0% aluminum silicate Im 22.1% NaB02. . 3 H20 23% Na20.33Si02 13% CMC 1.7% MgSiOg 2.1% N ^ S04 rest H20% detergent content of Ν ^ Ρ ^ Οβ aluminum silicate 43 45.0 83 39.4 123 33.8 16. 7 28.1 20.8 223 25.0 16.9 293 113 33.4 0

All of these detergents have practically the same detergency. ggispigie4_aad.2i

These examples demonstrate the replacement of the tripolyphosphate by aluminum silicate on two detergents, the detergent according to the invention being added by the addition "e", the comparative detergent by the addition "v". is marked

Part of the mass% of detergent

Detergent 4v 4e 5v 5e ABS 8.0 8.0 TA + 14ÄO 3.0 3.0 - - OA + IOÄO - - 15.0 15.0 Soap C18-C22 33 33 3.0 3.0 Na5P3 ° 10 33 , 4 23 10.0 3.0 aluminum silicate XHIm - 45.0 * 27.0 NaBOo - H0Oo. 3 H0O 22.1 22.1 24.0 24.0 Na20.33Si02 23 23 10.0 10.0 CMC U 13 - MgSiOj 1.7 1.7 - - Na2S04 19.0 2.1 30.0 10, 0 h2o 5j6 8.4 8.0 8.0

The washing results on native cotton, finished cotton and cotton-polyester blended fabrics were at least identical to those specified in the parent patent, in general somewhat better. -6-

AT 396 691B

Example 6: Detergents of the following recipes 6a and 6b are suitable for use in commercial laundries:

component

Content in% for detergent 6a 6b ABS 1.4 1.4 OA + IOÄO 7.6 73 Na2C03 183 183 NajSiOß 5.4 5.4 aluminum silicate XVIIIm 183 33.4 Na5P3 ° 10 16.73 53 CMC 03 03 brightener, Na2S04 10.0 10.0 h2o 213 173

The NagPßO ^ o can be in detergent 6a by a phosphorus-free organic complexing agent for calcium, in detergent 6b by HEDP or another calcium complex-binding phosphonate, by a phosphorus-free complexing agent for calcium or by a non-complexing calcium precipitant (e.g. oxalic acid, Set adipic acid or sebacic acid in the form of their water-soluble salts) ».

Example · ?: A detergent intended for washing heavily soiled work clothing has the following composition: 18.0% ÖÄ + 10ÄO 60.0% Na ^ Oj 12.0% aluminum silicate Ilm 5.5% O-carboxymethyl-tartronic acid (Na salt) 13¾ CMC 03% brightener 2.9% H20

Example 8: Bleaching detergents, of which product a is suitable as an additive for washing liquors in commercial laundries and product b as an additive for the rinse water which is effective in the cold, have the following composition:

Component mass% component in the composition according to Example 8a 8b

NajBOj. H2O2.3 H2O 36.0 18.0 tetraacetylglycoluril - 18.0 MgSiOß 3.6 3.6 aluminum silicate in 313 313 Na citrate 73 73 Na2C03 15j0 15.0 brightener 03 03 h2o 6.4 6.4 -7 -

AT396691B

Examples 9 to 16

The following are the recipes for some other detergents containing aluminum silicate:

Detergent component mass% component in the detergent according to Example 9 10 11 12 TA + 14ÄO 7.0 103 10.7 6.8 aluminum silicate Xllm 52.1 473 513 643 Na5P3 ° 10 - 5.1 33. 63 Sodium citrate 73 - 2.1 - EDTA 03 03 0.1 03 Na20.33Si02 1.7 63 3.1 33 NaB09.H909.3H90 24.9 24.9 203 - CMC 0.8 1.6 1.1 2 , Na2S04 + H20 6.0 4.4 83 17.0

Detergent component mass% component in the detergent according to Example 13 14 15 16 HPK sulfonate 1.0 2.6 1.6 ABS 43 4.7 7.1 - TA + 14ÄO 23 13 6.4 OA + IOÄO - - - 4, 1 soap 2.0 1.6 33 aluminum silicate XVIIIm 45.0 473 48.1 493 Na5P3 ° 10 5.0 63 8.0 73.EDTA 03 03 03 03 Na ^ .33 Si02 63 3.7 2.6 3, 4 NaB09. H909.3 H90 25.1 263 223 22.1 CMC U 03 13 1.6 Na2S04 + H20 7.1 3.8 7.0 4.1 50 The better rinsability of the microcrystalline aluminum silicates to be used according to the invention is particularly evident on edges and Corners of bed or pillow cases as well as on the collar and cuffs of shirts. -8- 55

Claims (9)

AT396691B PATENT CLAIMS 1. Process for washing or bleaching textiles by treating them with an aqueous liquor which contains suspended water-insoluble silicates, using finely divided crystalline synthetically produced silicates which optionally contain bound water and whose composition is of the formula (K ^ / h ^ x A12 ° 3, in which Kat is a cation exchangeable with calcium of the valence n, x is a number from 0.7 to 1.5 and y is a number from 0.8 to 6, preferably from 0.9 to 4, and which has a calcium binding capacity of at least 50 mg CaO / g of anhydrous active substance (= AS), determined by determining the reduction in the degree of hardness of 11 water of 30 ° dH and 22 ° C after 15 minutes of 1 g (based on AS) of the Silicates defined above, according to Patent No. 368 185, characterized in that at least 80% by mass of the silicates as defined above from particles having a size of 10 to 0.01 μ ιη, preferably from 8 to 0.1 μιη and the aluminum silicates practically no particles &gt; Contain 40 μιη, but excluding the case that the aqueous liquor in a ratio of 1:19 to 19: 1 an a) water-soluble, organic, surface-active agent from the group comprising anionic, nonionic, ampholytic and zwitterionic surface-active agents and mixtures thereof and b) contains a crystalline, water-insoluble, inorganic aluminosilicate ion exchange material with a particle size of 1 μm to 10 μm and the formula Nai2 (AlC> 2. SiO ^) ^ H ^ O, with x an integer from 20 to 30, the aluminosilicate ion exchange material containing one Calcium ion exchange capacity of at least 200 mg equivalent calcium carbonate hardness / g aluminosilicate (calculated as anhydrous) and a calcium ion exchange rate of at least 0.034 g calcium carbonate / l / ml / g aluminosilicate (calculated anhydrous). 2. The method according to claim 1, characterized in that the treatment liquors contain substances which are able to complex and / or precipitate calcium. 3. The method according to claim 1 or 2, characterized in that the rotting contains surfactants in amounts up to 2.5 g / 1 4. The method according to any one of claims 1 to 3, characterized in that the rotting contains inorganic or organic framework substances in amounts up to 6 g / 1. 5. The method according to claim 3 or 4, characterized in that the rotting contains pervey bonds in amounts of up to 0.4 g / 1 of active oxygen and optionally stabilizers and / or activators for the per-compounds. 6. The method according to claim 3 or 4, characterized in that the rotting contains active chlorine compounds in amounts which are equivalent to up to 0.4 g / 1 of active oxygen. 7. To carry out the method according to one of claims 1 to 6 certain washing, bleaching and cleaning agents containing substances which are capable of binding the hardness formers of water, characterized in that they are capable of binding the hardness formers of the water Substances containing finely divided silicates as claimed in claim 1, and at least one further compound having a washing, bleaching or cleaning action, but excluding washing, bleaching and cleaning agents which contain 5 to 95% by weight of the content of the disclaimer in claim 1 under a) defined surface active agent and 5 to 95 wt .-% of the aluminosilicate defined there under b). Process for the preparation of compositions according to claim 7, characterized in that the powdered silicates according to claim 1 are incorporated into an aqueous mixture of the water- and heat-stable constituents of the composition, dried in a manner known per se and optionally the dried product is heated with or moisture-unstable components of the agent. -9-