EP1275709A1 - Process for the production of bleach activator granules - Google Patents

Abstract

Process for the preparation of bleach activator granules, characterized in that a mixture of bleach activator, anionic or nonionic surfactant and polyalkylene glycol is extruded at temperatures from 60 to 80 ° C and a pressure from 10 to 30 bar and the extrudates obtained, at a temperature of Granulated at 60 to 80 ° C on a rounder.

Description

The present invention relates to a method for producing cylindrical ones to spherical extrudates containing bleach activators with defined Particle sizes and narrow particle size distribution, which have a low abrasion behavior and show good flow behavior.

Methods for the production of extruded washing and Detergent known. EP 486 592 describes the production of extruded Shaped bodies described, taking a solid and free-flowing premix Use of a plasticizer and / or lubricant when using relatively high pressures between about 25 and 200 bar is extruded. The strand has one such consistency that it emerges from the hole shape by means of a Cutting device can be cut directly to predetermined granule dimensions can. Aqueous and / or lubricants in particular are used as plasticizers Anionic surfactant pastes, aqueous polymer solutions and / or at room temperature called liquid nonionic surfactants. The extruded so producible Moldings generally have a size of up to 2 cm, preferably up to 0.8 cm on, the length-diameter ratio advantageously between 1: 1 and 3: 1 lies.

As described in WO 99/27061, bleach activators are advantageously packaged in the form of cylindrical extrudates in order to ensure compatibility with other detergent constituents and adequate storage stability. It is assumed that the highly reactive bleach activator is predominantly embedded in the interior of the cylindrical granulate and that the surface consists mainly of binding materials and plasticizers.
In order to avoid segregation of the different particles in the detergent formulation during transport and storage, the particle diameter should be between 0.2 mm and 2 mm, preferably between 0.5 mm and 0.8 mm, the particle length in the range from 0.5 mm to 3.5 mm, ideally between 0.9 mm and 2.5 mm.
All of the previously described processes for the production of extrudates either provide moldings with a relatively broad particle size distribution and / or a comparatively high dust content. The particles have sharp corners and edges at the interfaces, which cause high abrasion with dust formation and an unfavorable flow behavior. If the extrudates are produced under high compression forces, the dissolving behavior of the particles is significantly impaired.

The object of the invention was now cylindrical to spherical Extrudates containing bleach activators for use in washing or To produce cleaning agents which have a very narrow particle size distribution have and at the same time a low tendency to abrasion, low dust formation favorable flow behavior, as well as good dissolving behavior during washing and Show cleaning process.

The invention relates to a process for the production of bleach activator granules, characterized in that a mixture of bleach activator, anionic or nonionic surfactant and polyalkylene glycol at temperatures from 40 to 90 ° C, preferably 60 to 80 ° C and a pressure of 10 to 30 bar extruded and the extrudates obtained at a temperature of 40 to 90 ° C, preferably granulated at 60 to 80 ° C on a rounder.

Possible bleach activators are, for example, N, N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), Sodium 4-benzoyloxybenzenesulfonate (SBOBS), Sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglycoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxim (ADMG), 1-phenyl-3-acetylhydantoin (PAH), nonanoylcaprolactamphenylsulfonate ester (APES), nitrilotriacetate (NTA), preferably the sodium salt of Nonanoyloxybenzenesulphonate (NOBS), the sodium salt of 3,5,5-trimethylhexanoyloxyphenyl sulfonate (iso-NOBS) or the sodium salt of Acetoxyphenyl sulfonate (ABS).

Preferred anionic surfactants are alkali metal salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkyl sulfates, alkyl ether sulfates, alkyl amide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonate sulfates, alkyl amide sulfonates, alkyl aryl sulfonate sulfates, α-olefin sulfonates, α-olefin sulfates Alkyl polyglycerol carboxylates, alkyl phosphates, alkyl ether phosphates, alkyl sarcosinates, alkyl polypeptidates, alkyl amido polypeptidates, alkyl isethionates, alkyl taurates, alkyl polyglycol ether carboxylic acids or fatty acids such as oleic acid, ricinoleic acid, palmitic acid; Stearic acid, copra oleic acid salt or hydrogenated copra oleic acid salts. The alkyl radical of all these compounds normally contains 8-32, preferably 8-22, carbon atoms. Linear straight-chain alkylbenzenesulfonates are particularly preferred, in particular with a C ₈ -C ₂₀ -, particularly preferably with a C _11-13 -alkyl group.

As nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerolated fatty acid esters, polyethoxylated esters of fatty acids and of Sorbitol, polyethoxylated or polyglycerolated fatty amides are preferred.

Polyalkylene glycols are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include in particular sulfates and / or disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12000 and in particular between 1000 and 4000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights between 600 and 6000, preferably between 1000 and 4000. Furthermore, ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.
The preferably used polyethylene glycols can have a linear or branched structure, linear polyethylene glycols being preferred in particular. The particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000 especially in combination with polyethylene glycols with a relative molecular weight around 4000 can be used and such combinations advantageously to more than 50% by weight, based on the total amount of the polyethylene glycols, have polyethylene glycols with a relative molecular weight between 3500 and 5000.
The modified polyethylene glycols also include polyethylene glycols which are end group-capped on one or more sides, the end groups preferably being C ₁ -C ₁₂ -alkyl chains, preferably C ₁ -C ₆ , which may be linear or branched. Polyethylene glycol derivatives capped at one end may also correspond to the formula Cx (EO) y (PO) z, where Cx can be an alkyl chain with a C chain length of 1 to 20, y 50 to 500 and z 0 to 20.
Low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000 are also suitable. Relative molecular weight ranges between 3,000 and 30,000 are preferred here. Polyvinyl alcohols are preferably used in combination with polyethylene glycols.

To improve the plasticizing and sliding properties, but also the Abrasion resistance of the Bieichaktivator granules can additionally or added several components that are liquid at room temperature or below the processing conditions as a melt, for example linear or branched fatty acids, especially nonanoic acid or ethoxylated fatty acids 2 to 100 EO.

The mixture of all components described above can additionally be low Contain amounts of a solvent, preferably less than 15% by weight, preferably less than 10% by weight, particularly preferably less than 7% by weight. The preferred solvent is water.

Other suitable additives are substances that adjust the pH during storage and Affect application. These include organic carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, Succinic acid, maleic acid or lactic acid. In addition, additions are possible that influence the bleaching capacity, such as complexing agents and Transition metal complexes, e.g. Contains iron, cobalt and manganese Metal complexes as described in EP-A-0 458 397 and EP-A-0 458 398.

Particularly advantageous embodiments of the invention contain the sodium salt of nonanoyloxyphenylsulphonate (NOBS) as bleach activator, linear straight-chain alkylbenzenesulfonates as solubilizers, in particular with a C ₈ -C ₂₀ -, particularly preferably with a C11-13-alkyl group (LAS), as well as nonanoic acid and polyethylene glycol ( PEG) 4000 as a consistency agent and plasticizer, the proportion of NOBS being 70% by weight to 90% by weight, preferably 80% by weight to 87% by weight, particularly preferably 81% by weight to 85% by weight %, of LAS 2% by weight to 10% by weight, preferably 3% by weight to 5% by weight, particularly preferably 3.7% by weight to 4.5% by weight, of nonanoic acid 0 , 1% by weight to 6% by weight, preferably 1% by weight to 4% by weight, particularly preferably 2.5% by weight to 3.5% by weight, of PEG 4000 1% by weight. % to 15% by weight, preferably 5% to 10% by weight, particularly preferably 7% to 8% by weight.

Bleach activators, for example, are advantageously used Nonanoyloxyphenylsulphonate (NOBS) and anionic or nonionic surfactant, for example alkylbenzenesulfonate (LAS) mixed in powder form, plasticizers, for example nonanoic acid and PEG 4000 at 50 to 70 ° C, preferably 60 to 65 ° C entered and at a temperature in the range of 60 to 70 ° C and a pressure extruded from 14 bar to 22 bar. In a preferred embodiment the mixture is continuously a 1-shaft extruder, 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guide supplied, its housing and Extruder pelletizing head must be heated to the predetermined extrusion temperature can. Under the shear of the extruder screws, the mixture is under Compressed, plasticized, in the form of strands through the perforated nozzle plate in the Extruder head extruded, if necessary with fine-grained antibacking agent, for example, TiO2, silica, zeolite, powdered by yourself, in rough straw pieces crushed and on a to 40 to 90 ° C, preferably 60 to 80 ° C, in particular 60 to 65 ° C heated rounder transferred.

The subsequent rounding process gives cylindrical to spherical granules with defined particle sizes and a very narrow particle size distribution, the particle diameter between 0.2 mm and 2 mm, preferably between 0.5 mm and 0.8 mm, the particle length in the range of 0.5 mm to 3.5 mm, ideally between 0.9 mm and 2.5 mm. The extrudates are placed directly on the rounder or, if necessary, roughly comminuted. In a preferred embodiment, the shaping process according to the invention is carried out continuously in cascade operation, but batch-wise work is also possible.
The size and shape of the particles can be influenced and brought about in the rounding process by means of several parameters. The shaping process is determined by the filling quantity, the temperature of the mixture, the residence time of the mixture in the rounder, by the speed of rotation of the rounding wheel, and by the plastic deformability of the mixture.
As the filling quantity in the rounder decreases, shorter cylinder granules and a narrower distribution of particle sizes are obtained. With decreasing temperature and thus decreasing plasticity, longer granules are obtained, with further cooling the dust content increases significantly.
The residence time of the mixture in the rounder depends not only on the plasticity but also on the filling quantity and is preferably 10 seconds to 120 seconds, particularly preferably 20 seconds to 60 seconds, and the peripheral speed is 10 m / sec. up to 30 m / sec., preferably 12 m / sec. up to 20 m / sec.

In a particular embodiment, the temperature in the rounder is controlled by air or gas flow (N2), preferably via the splitting device. The temperature of the air or gas streams is 50 to 120 ° C., preferably 60 to 90 ° C., so that, depending on the design of the rounder, the desired working temperature can be maintained in the rounder.
After the molding process, the cylindrically shaped and rounded particles are cooled to temperatures below 40 ° C. in a downstream apparatus, preferably in a fluid bed cooler in a cold air or gas stream, in order to avoid the granules from sticking together.

The granules obtained in this way are characterized by favorable flow behavior, low dust content and high abrasion resistance.
The bulk density is in the range from 300 g / l to 2000 g / l, preferably in the range from 400 g / l to 1500 g / l and particularly preferably in the range from 500 to 800 g / l.

The granules obtained according to the invention can be used directly in washing and Suitable detergents. You can, if necessary, with a coating sleeve be provided.

Other possible additives are substances in the wash liquor with the from the Activator released peroxycarboxylic acid with formation of reactive intermediates, such as dioxiranes or oxaziridines, react and in this way the reactivity can increase. Corresponding compounds are ketones and sulfonimines corresponding to US-A-3 822 114 and EP-A-0 446 982.

The amount of the additive depends in particular on its type. For example, acidifying additives and organic catalysts for increasing the performance of the peracid are used in amounts of 0 to 20% by weight, in particular in amounts of 1 to 10% by weight, based on the total weight. added, however, metal complexes in concentrations in the ppm range.
The granules obtained are characterized by very good abrasion resistance and storage stability in powder detergent, cleaning and disinfectant formulations. They are ideal for use in heavy-duty detergents, stain salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.

In these formulations, the granules according to the invention are mostly in Combination with a hydrogen peroxide source used. examples for this are Perborate monohydrate, perborate tetrahydrate, percarbonates as well Hydrogen peroxide adducts with urea or amine oxides. In addition, the Further state-of-the-art formulation Have detergent ingredients such as organic and inorganic builders and Co-builders, surfactants, enzymes, brighteners and perfume.

The following examples are intended to explain the invention in more detail without restricting it. Example 1: Production of a NOBS granulate, active ingredient content: 84.4% by weight Granule diameter d 0.7 mm Granule length I 1.4 mm

844 g of the sodium salt of nonanoyloxybenzenesulphonate (NOBS), 50 g of linear C _11-13 -alkylbenzenesulfonate, Na salt, 31 g of nonanoic acid and 75 g of polyethylene glycol 4000 are added to the ploughshare mixer (manufacturer Lödige) at room temperature at a speed of 120 per minute and switched on Cutter head mixed homogeneously over a period of 150 seconds, heated to 65 to 71 ° C, transferred to a single-shaft dome extruder (manufacturer Fitzpatrick) with a hole diameter of 0.7 mm in the punch die and at an extruder screw speed of 45 per minute, a throughput of 287 g / min. extruded. Then 500 g of extrudates at a temperature of 65 to 69 ° C in a batch rounder (manufacturer Schlüter) with a diameter of 0.3 m at a speed of 1000 per minute, a peripheral speed of 15.71 m / sec and a dwell time from 40 seconds to the previously specified particle shape. After the molding process, the cylindrically shaped and rounded particles are cooled in a downstream apparatus, preferably in a fluid bed cooler, in a cold air stream in order to prevent the granules from sticking together. 94.9% of the granules obtained correspond to the target size of d = 0.7 mm and an average length of I ₅₀ = 1.37 mm. The width of the length distribution is in the range from I ₁₀ = 1.03 mm to I ₉₀ = 1.66 mm. 5.05% fine fraction and 0.05% coarse fraction are sieved off, the sieved target fraction has a bulk density of 692 g / l. Example 2: Production of a NOBS granulate, active ingredient content: 85.8% by weight Granule diameter d 0.7 mm Granule length I 1.4 mm

858 g of the sodium salt of nonanoyloxybenzenesulphonate (NOBS), 42 g of linear C _11-13 -alkylbenzenesulfonate, Na salt, 29 g of nonanoic acid and 71 g of polyethylene glycol 4000 are mixed in the ploughshare mixer (manufacturer Lödige) at room temperature at a speed of 120 per minute and switched on Cutter head mixed homogeneously over a period of 150 seconds, heated to 62 to 65 ° C, transferred to a single-shaft dome extruder (manufacturer Fitzpatrick) with a hole diameter of 0.7 mm in the punch die and at an extruder screw speed of 45 per minute, a throughput of 199 g / min. extruded. Then 1 kg of extrudates at a temperature of 60 to 62 ° C in a batch rounder (manufacturer Schlüter) with a diameter of 0.3 m at a speed of 1000 per minute, a peripheral speed of 15.71 m / sec and a dwell time from 40 seconds to the previously specified particle shape. After the molding process, the cylindrically shaped and rounded particles are cooled in a downstream apparatus, preferably in a fluid bed cooler, in a cold air stream in order to prevent the granules from sticking together. 97.37% of the granules obtained correspond to the target size of d = 0.7 mm and I ₅₀ = 1.45 mm. The width of the length distribution is in the range from I ₁₀ = 1.03 mm to I ₉₀ = 1.93 mm. 2.46% fine fraction and 0.17% coarse fraction are sieved off, the sieved target fraction has a bulk density of 686 g / l. Example 3: Production of an APES granulate, Granule diameter d 0.7 mm Granule length I 1.4 mm

675 g nonanoylcaprolactamphenylsulfonate ester (APES), 14.3 g linear C _11-13 alkylbenzenesulfonate, Na salt, 10.7 g sodium citrate and 7.5 g water are in the ploughshare mixer (manufacturer Lödige) at room temperature at a speed of 120 per minute and connected cutter head mixed homogeneously over a period of 150 seconds, transferred to a single-shaft dome extruder (manufacturer Fitzpatrick) with a hole diameter of 0.7 mm in the perforated die and at an extruder screw speed of 45 per minute, a throughput of 199 g / minute extruded. The extrudates are then at room temperature in a batch rounder (manufacturer Schlüter) with a diameter of 0.3 m at a speed of 1000 per minute, a peripheral speed of 22.3 m / sec and a dwell time of 40 seconds to the previously specified particle shape brought. After the shaping process, the cylindrically shaped and rounded particles are dried and cooled in a downstream apparatus, preferably in a fluid bed dryer.

Claims (13)

Process for the production of bleach activator granules, characterized in that a mixture of bleach activator, anionic or nonionic surfactant and polyalkylene glycol is extruded at temperatures of 40 to 90 ° C, preferably 60 to 80 ° C and a pressure of 10 to 30 bar, and the extrudates obtained, granulated at a temperature of 40 to 90 ° C, preferably 60 to 80 ° C on a rounder. A method according to claim 1, characterized in that additionally linear or branched fatty acids or ethoxylated fatty acids with 2 to 100 EO are used. A method according to claim 1, characterized in that an alkylarylsulfonate is used as the anionic surfactant. A method according to claim 1, characterized in that polyethylene glycol is used as the polyalkylene glycol. A method according to claim 1, characterized in that Na nonanoyloxybenzenesulfonate is used as the bleach activator. A method according to claim 1, characterized in that a granulate is prepared which consists of 70 to 90 wt .-% Na nonanoyloxybenzenesulfonate, 2 to 10 wt .-% alkylbenzenesulfonate, 0.1 to 6 wt .-% nonanoic acid and 1 to 15 % By weight of polyethylene glycol 4000. Method according to claim 1, characterized in that the extrudates are fed directly onto the rounder or are roughly comminuted. A method according to claim 1, characterized in that the temperature in the rounder is controlled by supplying air or gas. A method according to claim 1, characterized in that one works at a circumferential speed in the rounder of 10 to 30 m / sec. A method according to claim 1, characterized in that one works with a dwell time of 10 to 120 sec in the rounder. A method according to claim 1, characterized in that the rounding process is carried out batchwise or continuously in cascade mode. A method according to claim 1, characterized in that the extrudates are powdered with an anti-caking agent. Bleach activator granules, produced by the process according to one or several of claims 1 to 12.