DE3612701C2 - - Google Patents

Description

The invention relates to detergent in particulate form (detergent bars) for Hand wash or flow wash of textiles.

From GB-PS 21 27 426 detergents are in particulate form (detergent bars) containing 5 to 60% by weight of washing-active substances, 0 to 60% by weight detergency builder and acid-treated Bentonite to increase the hardness included. As detergent builder be water-soluble carbonates, organic Substances such. As sodium nitrilotriacetate, and especially water-soluble Phosphates used.

The known detergent in particulate form based on linear higher alkylbenzenesulfonates and pentasodium tripolyphosphate as a builder are so far because of their good washing effect recognized, wherein the linear higher alkylbenzenesulfonates are biodegradable and have an excellent washing effect while the polyphosphates are in principle considered good and safe builders are considered for the detergent. However, since the phosphates in recent years because of eutrophication of inland waters are less appreciated, one has  tries to use many other phosphate substitutes with builders To use properties. For example, it was assumed that carbonates, silicates, borax, the trisodium salt of nitrilotriacetic acid (NTA), organic sequestering agents, polyelectrolyte, Chelating agents and other products that Reinforce the cleaning effect of synthetic, organic detergents would. Most of these phosphate substitutes have however disadvantageous properties, although not so strong contribute to the eutrophication of inland waters, as is the case with the Attributes to phosphates. Some of these phosphate substitutes are toxic, others are thought to have carcinogenic properties, others are not storage stable or mediate the final product undesirable flow properties, give processing difficulties while others have a bad smell again or react with the other ingredients of the detergent. As a result, there is considerable uncertainty as to whether at all and if, what products as suitable phosphate substitutes to be considered.

It has recently been found that zeolites, in particular certain synthetic, crystalline molecular sieve Zeolites, preferably in at least partially hydrated Form suitable despite their water insolubility Ion exchangers for calcium ions are and therefore the Detergency of synthetic, organic detergents, in particular improve anionic detergents and also with non-ionic detergents can be used (US-PS 42 38 346).

It was therefore the task of a detergent in to produce lumpy form, the zeolite as Phosphate substitute contains and sufficient hardness exhibiting.

The invention relates to a detergent in lumpy form for use in hand washing or the River washing of textiles, characterized in that it has the following composition:

5 to 50% by weight of surface-active substances
5 to 60 wt .-% aluminum silicate
0 to 60% by weight of filler and wash alkalis
<1 wt .-% of additives
0 to 8% by weight of lubricant,

wherein the aluminum silicate is a synthetic produced, powdered zeolite type A with a calcium binding capacity in the range of 100 to 200 mg CaO / g of active substance and no primary or Secondary particles with diameters above 45 μm having.  

The aluminum silicates are synthetic manufactured, crystalline products. The preparation may, for. B. by reaction of water-soluble Silicates with water-soluble aluminates in the presence of Water done. For this purpose, aqueous solutions the starting materials mixed together or one in solid state present component with the other, as aqueous solution present component can be implemented. Also by mixing both, in a solid state present Components are obtained in the presence of water the desired Aluminum silicates. Also from Al (OH) ₃, Al₂O₃ or SiO.sub.2 can be converted by reaction with alkali metal silicate or Alkali aluminate solutions produce aluminum silicates. The Production can also be carried out by further known methods.

The preferred calcium binding capacity is about 100 to 180 mg CaO / g AS is found especially in compounds of the composition:  

0.7-1.1 Na₂O · Al₂O₃ · 1.3-2.4 SiO₂

The compounds have the X-ray diffraction pattern on the crystal structure of the zeolite A.

The crystalline aluminum silicate present in aqueous suspension can be separated by filtration from the remaining aqueous Separate solution and dry. Depending on the drying conditions the product contains more or less bound Water.

It is particularly advantageous to use aluminum silicates, at least 80% by weight of particles of 10 to 0.01 micrometer in particular from 8 to 0.1 microns.

The aluminum silicates contain no primary or secondary particles with diameters above 45 Micrometers. As secondary particles are particles by Agglomeration of the primary particles to larger structures emerged are designated.  

In a particularly preferred embodiment of the invention is aluminum silicate powdered type A zeolite used with a particularly defined particle spectrum.

Such zeolite powder can according to DE-AS 24 47 021, DE-AS 25 17 218, DE-OS 26 52 419, DE-OS 26 51 420, DE-OS 26 51 436, DE-OS 26 51 437, DE-OS 26 51 445 or DE-OS 26 51 485 produced become. They then show the particle distribution curves given there on.

In a particularly preferred embodiment, a pulververförmiger Type A zeolite can be used, which corresponds to the in DE-OS 26 51 485 described particle size distribution having.

The surface-active substances can anionic and / or be nonionic surfactants.

As anionic substances are used:

• Alkylbenzenesulfonate (ABS), preferably with linear alkyl Chain (LAS) with 8-22 C atoms, preferred
• Paraffinsulfonates with linear or branched C₁₀-C₂₀ chain, preferably C₁₃-C₁₇. Sulfonate group terminal or over the Chain distributed.
• - Sulfates of higher alcohols with C₈-C₂₂ chain, for example Lauryl, tallow and coconut fatty alcohol.
• - Ether sulfates of higher alcohols with C₈-C₂₂ chain, for example same alcohol radicals as in the aforementioned sulfates higher alcohols. The molar ratio of alkylene oxide - especially Ethylene oxide - to alcohol is 1: 1 to 5: 1.
• - α-Olefinsulfonate with C₈-C₂₀ chain, preferably in the range C₁₃-C₁₇.  
• Soaps are water-soluble salts of higher fatty acids
• - come as a cation for the aforementioned surfactants Sodium, potassium and ammonium or substituted ammonium ions such as mono-, di- and triethanol as well as tetramethylammonium in question.

Nonionic substances are used:

• - Condensation products of alkylene oxide (C₂-C₄) - preferred Ethylene oxide, propylene oxide and a hydrocarbon radical (Alkyl, alkylphenyl, higher fatty alcohols, higher fatty acids, higher fatty amines). As an example, tallow fatty alcohol (C₁₆-C₁₈) called with about 5-30 ethylene oxide units.
• Fatty acid amides formed from alkanolamine, preferably mono- and diethanolamine and isopropylamine, and a fatty acid. As an example, coconut fatty acid monoethanolamide may be mentioned here.

As fillers, the following substances in one Amount of 0 to 60 wt .-% are used:

As fillers are sulfates, carbonates and bicarbonates of sodium, potassium, calcium and magnesium, from the Literature are other substances such as bentonite and starch (Potato, rice and wheat) known.

As washing alkalis can sodium carbonate and / or sodium silicate be used.

Carboxymethylcellulose, optical brighteners, Color and / or fragrances are used. Preferably in an amount of 0.1 to 1.0 wt .-%.

As lubricant can be used in an amount of 0 to 8% by weight the following substances are used:  

Lubricants are process-related substances that are extruded the raw mass to obtain a good strand and a smooth, crack-free surface can be used. Suitable are high-melting fats, waxes and paraffins with Melting points greater than 40 ° C to about 60 ° C. Also can as Lubricants high melting nonionic surfactants used be like B. tallow alcohol with 25 ethylene oxide units or Coconut fatty acid monoethanolamide.

The detergent according to the invention in particulate form is on made known ways.

Preferably, the individual components are at a temperature from 30 to 60 ° C, especially at 40 to 50 ° C, with each other mixed, homogenized, preferably on one Three-roll chair, and pressed in a known manner.

The detergent according to the invention in particulate form advantageously contains no substances that eutrophicate the waters such as sodium tripolyphosphate.

However, it is also possible to use part of the aluminum silicate by the sodium and / or potassium salts of ortho-, pyro- and / or or replace triphosphate.

The washing effect as well as the handling and the dissolving speed of the detergent according to the invention in lumpy Shape is similar to the corresponding properties of the known Detergent in particulate form according to GB-PS 21 27 426.

Examples

The chemical constitution of those mentioned in the examples Fabrics is:

Texapon OT: lauryl sulfate Marlipal SU: Tallow alcohol with 25 moles of ethylene oxide Rewomid C 212: coconut fatty acid monoethanolamide Wessalith®: Zeolite A

Table I shows the composition of the samples used. Samples 1, 2, 3, 4, 5, 6, 7, 8 and 9 are detergents in lumpy shape according to the invention. The detergent in pieces Mold are made by adding Texapon OT and water in a kneader presents and while warming to 40 to Knead 50 ° C until the Texapon needles are dissolved.

Subsequently, Rewomid C 212 and Marlipal SU as 40% Added emulsion and then the remaining powder components added. The extrusion of the mass to detergent in lumpier Form takes place at 65 ° C.

The foam resistance and foaming are with determined the Reibschaumgerät.

The foam development becomes after 5 minutes and the foam resistance read after 30 minutes in milliliters. The Examinations are carried out in distilled water and in water performed at 15 ° dH.

The results are shown in Table II.

Table II

Foaming power and foam resistance of detergents in particulate form

table III Dissolution rate of detergents in particulate form

Method: "Abrasion in the drum"

The dissolution rate is carried out in a device according to FIG. 1 with normal tap water of about 12-14 ° C. and 4 ° German hardness.

The following conditions are met:
Weighing 1.0 ± 0.01 g
Water flow: 2 l / min
Speed: 35 rpm
Running time: 25 '

Fig. 1 describes the device for determining the dissolution rate. This device consists of the motor 1 , the axis 2 and the cylindrical cage. 3 The cylindrical cage 3 , which has an outer diameter of 200 mm, is covered with the mesh 4 with a mesh size of 1 mm. The interior of the cage 3 is divided into individual sections 5 by the partitions 6 , so that the different samples 7, 8, 9, 10 and 11 can be examined simultaneously. The partition walls 6 have an inner opening with an inner diameter of 100 mm. The partitions 6 are held together by 4 long screws with slid metal sleeves acting as spacers.

The cylindrical cage 3 is rotated about the axis 2 in horizonatal position by the motor 1 at 35 revolutions per minute about the longitudinal axis. A part of the cylindrical cage 3 is immersed in a pool of water 12 , which is so dimensioned that the inserted samples of detergent in particulate form are completely covered by the water 13 passing through. The water flows through the water tank 12 at a rate of 2 l / min, where it is added via the inlet 14 and discharged via the outlet 15 .

Table IV

Dissolution rate of detergents in particulate form

Method: "river washing" (data in%)

In this determination, a cotton towel is stretched on a firm base and then the detergent in chunky form under running cold Water (about 12 ° C) rubbed 400 times.

Claims (1)

Detergent in particulate form for use in hand washing or flow washing of textiles, characterized in that it has the following composition: 5 to 50 wt .-% of surface-active substances
5 to 60 wt .-% aluminum silicate
0 to 60% by weight of filler and wash alkalis
<1 wt .-% of additives
0 to 8 wt .-% lubricant, wherein the aluminum silicate is a synthetically produced, powdered type A zeolite having a calcium binding capacity in the range of 100 to 200 mg CaO / g of active substance and no primary or secondary particles having diameters above 45 microns ,