DE3640541A1 - Granular detergent - Google Patents

Abstract

Granular, phosphate-free detergents based on synthetic anionic surfactants, fine-particle, water-insoluble builder substances and fillers contain, to increase the fracture resistance and surface smoothness, 0.5 to 10 % by weight of an alkali metal silicate and 0.5 to 10 % by weight of a polyethylene glycol. Zeolite NaA is preferably employed as water-insoluble builder substance. The detergent granules can be produced by mixing the components, where appropriate with the addition of water, and extruding the mixture, chopping and, where appropriate, compressing to granules.

Description

The invention relates to a detergent in the form of a bar Based on synthetic anionic surfactants, fine-particle water-insoluble Builder substances and / or fillers, which for Increase in breaking strength and surface smoothness Addition of alkali silicate and polyethylene glycol.

Lump detergents based on synthetic surfactants, Builder substances and fillers have long been known and are used primarily for textile washing by hand and on the open Waters used. These so-called "built detergent bars" usually contain linear alkylbenzenesulfonate and / or as surfactants Alkyl sulfates, as fillers calcium carbonate, magnesium silicate (Talc) or clays and as builder substances are usually Phosphates, especially the pentasodium triphosphate used. GB-A 21 45 109 had also already proposed in addition to the water-soluble builder salts, water-insoluble Builder substances such as B. calcium ion exchanging Zeolites, e.g. B. zeolite A, X and Y, or layered silicates such as Use bentonite. In view of the need for Entry of phosphates in surface waters and the related to reduce associated entrophication technical need, the phosphates completely through ecological to replace safe builders. For this offer especially the synthetic zeolites with high calcium ion exchange capacity which has been in powder form for several years Detergents have already been used successfully as phosphate substitutes will.  

The phosphate builders have in the conventional, phosphate ones Recipes for detergent tablets by their ability to to bind water during hydration, a considerable Contribution to the formation of the required hardness and breaking strength of the detergent pieces. Your quantitative replacement due to synthetic zeolites leads to pieces of detergent plastic and brittle consistency. Another disadvantage of The replacement of phosphate with zeolites is a rough, sandy surface of the detergent strand produced by mixing and extruding or the detergent pieces made from it.

There was therefore the task of phosphate-free detergent tablets to develop with water-insoluble builder substances that sufficient hardness, breaking strength and surface smoothness exhibit. It has been found that this object is achieved by adding alkali silicate and polyethylene glycol.

The invention relates to a piece-like, phosphate-free Detergents containing synthetic anionic surfactants, fine particles water-insoluble builder substances and fillers characterized in that to increase the breaking strength and surface smoothness 0.5 to 10% by weight of an alkali silicate and 0.5 to 10 % By weight of a polyethylene glycol with an average molecular weight from 1000 to 35,000 is included.

Preferred synthetic anionic surfactants are those of the sulfonate and sulfate type. As sulfonate type surfactants come z. B. alkylbenzenesulfonates with 9 to 15 carbon atoms in the alkyl group, alpha olefin sulfonates and hydroxyalkane sulfonates and their mixtures, such as those obtained by sulfonation of alpha-olefins with 12 to 18 carbon atoms and subsequent ones Hydrolysis of the sulfonation products obtained are alkanesulfonates with 12 to 18 carbon atoms, alpha sulfofatty acid esters, e.g. B. the alpha-sulfonic acids of the methyl or ethyl esters hydrogenated  Coconut, palm kernel or tallow fatty acid. As surfactants from Sulfate type are the sulfuric acid monoesters with primary alcohols 10 to 18 carbon atoms, e.g. B. of coconut fatty alcohols, talc fatty alcohol or technical oleyl alcohol cuts. Also suitable the sulfuric acid monoesters of fatty acid alkanolamides, fatty acid monoglycerides or addition products of 1 to 4 moles Ethylene oxide to primary or secondary linear alcohols with 10 up to 18 carbon atoms or on alkylphenols with 8 to 15 carbon atoms in the alkyl group. The anionic surfactants can be in the form of their Sodium, potassium or ammonium salts are present. Particularly preferred becomes the sodium alkylbenzenesulfonate with a linear alkyl group with 9 to 15 carbon atoms. The anionic surfactants are in an amount of 10 to 35 wt .-% of the lump Detergent.

Suitable as a finely divided water-insoluble builder substance synthetic crystalline sodium aluminosilicates containing bound water, preferably zeolite NaA, in an amount of 10 up to 75% by weight of the detergent bar. It can also be used Zeolite NaX and its mixtures with Zeolite NaA. Suitable Zeolites have a calcium binding capacity, which according to the information is determined in DE 24 12 837 and that in the range of 100 up to 200 mg CaO / g. Preferably comes the one with the trade name Wessalith P available zeolite NaA with a content of approx. 20% by weight of bound water in an amount of 10 to 35 % By weight for use.

The detergent tablets according to the invention preferably contain also water-soluble builder salts such as B. alkali carbonate or alkali bicarbonate. Sodium carbonate in one is preferred Contain amount of 5 to 20 wt .-%.

Water-soluble and / or water-insoluble come as fillers Substances in question that have no or only one in the washing effect  have a minor share. As are water insoluble fillers e.g. B. sodium chloride or sodium sulfate. Prefers However, water-insoluble fillers in finely divided form added. As such, e.g. B. calcium carbonate (in the form of finely ground marble powder, calcite or chalk), dolomite, feldspar, Kaolin, magnesium silicate (talc) or bentonite in question. Calcium carbonate is preferred in the lumpy form according to the invention Detergents contained in an amount of 20 to 65 wt .-%.

Sodium and potassium silicates are also suitable as alkali silicates a molar ratio of Na₂O (or K₂O): SiO₂ = 1: 2:  4, preferably 1: 3 to 1: 3.5. The alkali silicates can be used as solid, anhydrous crystal powder or in the form of aqueous Water glass solutions are used. A is preferably suitable Sodium silicate with a molar ratio of Na₂O: SiO₂ of 1:  3.4 to 3.5.

Polyethylene glycols are understood to mean addition polymers of ethylene oxide with ethylene glycol or water. The products are homolog mixtures of the general formula HO (CH₂-CH₂-O) _n -H, in which n is the average degree of polymerization. Polyethylene glycols which have a soft to wax-like consistency at room temperature, ie the polyethylene glycols with an average molecular weight of 1000 to 35,000 (ie n = 22.7 to 795), are particularly suitable for the detergent tablets according to the invention. Polyethylene glycols with an average molecular weight of 1000 to 10,000 are particularly preferred.

In addition to the components mentioned, the inventive piece-like detergents further, in such detergent pieces usual additives and auxiliaries in an amount up to contain a total of about 5 wt .-%. Such suitable additives and  Tools are e.g. B.

• - dirt-bearing and dispersing, water-soluble polymers such as B. carboxymethyl cellulose or hydroxyethyl cellulose, water-soluble starch or synthetic carboxyl-containing Polymers,
• - Foam boosters such as B. fatty acid (C₁₂-C₁₈) monoethanolamides, Fatty alcohols with 12 to 18 carbon atoms, fatty acid partial glycerides, Sorbitan fatty acid esters,
• - Water-soluble complexing agents such as. B. nitrilotriacetic acid Sodium salt, ethylenediaminetetraacetic acid sodium salt, Salt of hydroxycarboxylic acids such as. B. sodium citrate, sodium tartrate, Sodium salt of polyoxycarboxylic acids,
• - Pigments such as B. titanium dioxide,
• - water-soluble dyes,
• - fragrances,
• - antioxidants,
• - antimicrobial agents.

Particularly preferred application properties as well good breaking strength, hardness and surface smoothness has an inventive lumpy, phosphate-free detergent with a Salary of

10-35% by weight of a linear C₉-C₁₅ alkylbenzenesulfonate Sodium salt 10-35 wt% zeolite NaA 5-20% by weight sodium carbonate 30-50% by weight calcium carbonate (marble powder) 0.5-10% by weight sodium silicate 0.5-10 wt .-% polyethylene glycol with a medium Molecular weight from 1000 to 10,000 3-10 wt% water

The production of the detergent in the form of bars according to the invention can be done in a very simple way: the powdery components are mixed using conventional powder mixers, such as the Lödige mixer type. The mixture becomes the polyethylene glycol in the molten state e.g. B. at a temperature of 100 ° C, best in shape of a spray mist. However, it is also the addition of solid polyethylene glycol possible if for a homogeneous distribution is taken care of. After all, so much water - too ideally in the form of a spray - added to the mixture, that a total water content of about 5 to 15 wt .-% in the mixture results. The water can also be mixed into the way be introduced that one of the components completely or partially added in water-containing form. So z. B. the anionic surfactant partly in the form of an aqueous surfactant solution, the sodium silicate in the form of a water glass solution or the zeolite NaA can be added in the form of an aqueous zeolite suspension. After extrusion and curing, the total water content should be are between 3 and 10% by weight.

The components were then mixed intensively. This moist, slightly crumbly or lumpy premix will then in an extruder, preferably in a screw extruder, transferred in which a further intimate mixing of the components he follows. To plasticize the premix, the Extruder are heated so that a product temperature of 90 to 120 ° C. The mixture is passed through the extrusion nozzle extruded in the form of a strand, the strand of detergent formed is shaped so that it is cut into uniform Sections in the bar-shaped detergent according to the invention can be transferred. To achieve a smooth, shiny The surface of the extrusion die should be 95 to 130 ° C.  H. heated to 5 to 10 ° C above product temperature. Alternatively  the detergent strand can also be closed in a unit press Detergent pieces of any shape can be processed. The so Bar detergent produced take off while cooling to room temperature, about within 1 to 2 hours final hardness and breaking strength. The hardness of the invention lumpy detergent should be above 80 shore A (DIN 53 505), preferably 80 to 100 Shore A.

The following examples are intended to illustrate the subject matter of the invention explain without restricting him to this.  

Examples Manufacture of detergent in the form of bars production method

The powdered components were in a Lödige mixer mixed, the polyethylene glycol melted at 80 ° C and the Water and, in Approach 1.2, the sodium silicate solution were added in succession sprayed on the powder mixture. A came into being 20 ° C free-flowing, slightly lumpy powder. The powder was via a screw conveyor into a twin-screw extruder (type Continua A from Werner & Pfleiderer), whose jacket on approx. Was heated to 120 ° C, metered. With a throughput of 15 kg / h at 30 rpm and a product temperature at the nozzle outlet of about 95 ° C was a detergent strand of about 6 cm wide and 2.5 cm high extruded and cut into 8 cm long pieces, which completely cooled and hardened within approx. 3 hours were.

There were pieces of detergent with a smooth surface and good Obtained breaking strength. After storage for 24 hours at room temperature  (23 ° C) the Shore hardness was determined according to DIN 53 505. The following values were obtained:

Recipe 1.1 Shore A hardness 94
Recipe 1.2 Shore A hardness 85

A determination of the needle penetration according to DIN 52 010 at 25 ° C with 100 g load and a sink time of 8 seconds following values:

Recipe 1.1 penetration value 14 mm
Recipe 1.2 penetration value 15 mm

Claims (7)

1. Lumpy, phosphate-free detergent, containing synthetic anionic surfactants, finely divided water-insoluble builder substances and fillers, characterized in that to increase the breaking strength and surface smoothness 0.5 to 10 wt .-% of an alkali silicate and 0.5 to 10 wt .-% of one Polyethylene glycol with an average molecular weight of 1000 to 35,000 is included. 2. Lumpy, phosphate-free detergent according to claim 1, characterized in that as finely divided water-insoluble Builder substance zeolite NaA and possibly NaX in one Amount of 10 to 75 wt .-% is included. 3. Lumpy, phosphate-free detergent according to the claims 1 or 2, characterized in that as a synthetic anionic surfactant with a sodium alkylbenzolysulfonate preferably linear alkyl group with 9 to 15 carbon atoms in an amount of 10 to 35 wt .-% is included. 4. Lumpy, phosphate-free detergent according to the claims 1 to 3, characterized in that in addition 5 up to 20% by weight sodium carbonate as a water-soluble builder substance is included. 5. Lumpy, phosphate-free detergent according to the claims 1 to 5, characterized in that an additional 20th up to 65% by weight calcium carbonate as a water-insoluble filler are included. 6. lumpy, phosphate-free detergent according to claim 1, characterized in that  10-35% by weight of a linear C₉-C₁₅ alkylbenzenesulfonate Sodium salt 10-35 wt% zeolite NaA 5-20% by weight sodium carbonate 30-50% by weight calcium carbonate (marble powder) 0.5-10% by weight sodium silicate 0.5-10 wt .-% polyethylene glycol with a medium Molecular weight from 1000 to 10,000 3-10 wt .-% water are contained. 7. Process for producing a lumpy, phosphate-free Detergent according to claims 1 to 6, characterized characterized in that the components are optionally mixed intensively with the addition of water, at 90 to Plasticized 120 ° C and the mixture over to 95 ° C to 130 ° C heated extrusion die extruded and the strand by cutting and pressing if necessary Pieces processed.