JP2005514467A - Method for producing coated bleach activator granule - Google Patents

Abstract

The present invention relates to methods for coating bleach activator-containing granules by treatment with an acidic aqueous consolidating solution, comprising polymeric polycarboxylate and/or alkali metal phosphonate as coating and consolidation active ingredient, with simultaneous drying in a fluidized-bed apparatus.

Description

  The present invention provides bleach activation by treating with an acidic consolidated aqueous solution comprising a polymeric polycarboxylate and / or an alkali metal phosphonate as a coating and consolidation active component while simultaneously drying in a fluid bed apparatus. The present invention relates to a method for coating granules containing an agent.

In addition to components essential to the cleaning process (e.g., surfactants and builder substances), cleaning agents and cleaning agents can be summarized in terms of `` cleaning aids '' and include various groups of active ingredients (e.g., foam control agents). It is usual to contain further constituents, including, for example, graying inhibitors, bleaches and color migration inhibitors. Such auxiliaries also include substances that aid the performance of the surfactant as a result of oxidative degradation of soil on the fabric or soil in the liquid. The same is true for the cleansing agent for hard surfaces. For example, inorganic peroxygen compounds (especially hydrogen peroxide) and solid peroxygen compounds that dissolve in water to release hydrogen peroxide (e.g. sodium perborate and sodium carbonate perhydrate) are intended for disinfection and bleaching purposes. It has been used for a long time as an oxidizing agent. The oxidation action of these substances is highly dependent on the temperature of the diluted solution. That is, for example, when H ₂ O ₂ or sodium perborate is used in an alkaline bleaching solution, sufficiently rapid bleaching of the soiled fabric occurs only at temperatures above about 60 ° C. At lower temperatures, the so-called bleach activator can be added to improve the oxidative action of the inorganic peroxygen compound, and the bleach activator is mainly composed of N- or O-acyl compounds. Many proposals from are known from the literature. These include, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, And carboxylic anhydrides, especially phthalic anhydride, carboxylic esters, especially sodium nonanoyloxybenzene sulfonate, sodium isononanoyloxybenzene sulfonate, and acylated sugar derivatives such as pentaacetylglucose. The addition of these substances can enhance the bleaching action of the aqueous peroxide solution, so that even at a temperature lower than 60 ° C., the effect is substantially the same as when only the aqueous peroxide solution is used at 95 ° C. Arise.

European patent application EP0464880 discloses a bleaching enhancing cationic nitrile represented by the following general ^{formula: R'R''R '''N + -CR} 1 R 2 -CN X - [ In the formula, R ₁ And R ₂ is hydrogen or a substituent having at least one carbon atom; R ′ is a C _1-24 alkyl, alkenyl or alkyl ether group, or a —CR ₁ R ₂ —CN group; 'And R''' are each a C _1-24 alkyl or hydroxyalkyl group; the counter anion X ^- is an organic sulfonate, organic sulfate or carboxylate].

International patent application WO 98/23719 discloses that compounds of the following general formula can be used as activators, in particular as activators for inorganic peroxygen compounds in dishwashing aqueous solutions: R ^{1 _{R 2 R 3 N + CH 2}} CN X - in [wherein, R ^1, R ² and R ³ are, independently of one another, alkyl having 1 to 18 carbon atoms, alkenyl or aryl group, R ² And the R ³ group may be part of a heterocycle having an N atom and optionally further heteroatoms; X is a charge balancing anion].

  This provides an improvement in the oxidizing and bleaching action of inorganic peroxygen compounds, especially at low temperatures below 80 ° C., especially at temperatures of about 15-55 ° C. However, cationic nitriles are generally not very storage stable and are particularly sensitive to moisture, especially when combined with other components of cleaning and cleaning agents.

  International patent application WO 00/50556 discloses the production of a solid preparation comprising a cationic nitrile and a solid carrier material by a vacuum vapor drying process in a mixer.

  The object of the present invention is to introduce granules comprising cationic nitrile into granular detergents and cleaning agents so that the loss of bleaching activation of cationic nitriles is as small as possible even after storage. Was to provide a way to make it possible. It has now been found that production of preparations meeting this requirement is possible by the fluidized bed coating process. In a simple manner, this makes it possible to apply a protective coating to the granules without suffering from the reduced action of the bleach activator.

[式中、Ｒ¹は、-Ｈ；-ＣＨ₃；Ｃ_2-24アルキルまたはアルケニル基；-Ｃｌ、-Ｂｒ、-ＯＨ、-ＮＨ₂、-ＣＮの群からの少なくとも１個の置換基を有する置換Ｃ_2-24アルキルまたはアルケニル基；Ｃ_1-24アルキル基を有するアルキルまたはアルケニルアリール基；または、Ｃ_1-24アルキル基および芳香環上の少なくとも１個のさらなる置換基を有する置換アルキルまたはアルケニルアリール基であり；
Ｒ²およびＲ³は、互いに独立して、-ＣＨ₂-ＣＮ、-ＣＨ₃、-ＣＨ₂-ＣＨ₃、-ＣＨ₂-ＣＨ₂-ＣＨ₃、-ＣＨ(ＣＨ₃)-ＣＨ₃、-ＣＨ₂-ＯＨ、-ＣＨ₂-ＣＨ₂-ＯＨ、-ＣＨ(ＯＨ)-ＣＨ₃、-ＣＨ₂-ＣＨ₂-ＣＨ₂-ＯＨ、-ＣＨ₂-ＣＨ(ＯＨ)-ＣＨ₃、-ＣＨ(ＯＨ)-ＣＨ₂-ＣＨ₃、-(ＣＨ₂ＣＨ₂-Ｏ)_nＨ(ここで、ｎは１、２、３、４、５または６である)から選択され；
Ｒ⁴およびＲ⁵は、互いに独立して、Ｒ¹、Ｒ²またはＲ³に関して前記した意味を有し；
Ｘは、電荷均衡化アニオンである]
で示される化合物を含んでなる被覆粒状調製物の製造方法であって、
固体形態、特に微粉形態で存在する式(Ｉ)の漂白活性化剤に、必要であればビルダーおよび／または固体充填剤との混合物においてまたは予備製造グラニュールの形態において、流動床装置において同時乾燥しながら、被覆および固結活性成分として高分子ポリカルボキシレートおよび／またはホスホン酸またはアルカリ金属ホスホン酸塩を含んでなる酸性水溶液を吹付けることを特徴とする方法を提供するものである。 The present invention provides a compound of formula (I):

[Wherein R ¹ represents at least one substituent from the group of —H; —CH ₃ ; C _2-24 alkyl or alkenyl group; —Cl, —Br, —OH, —NH ₂ , —CN. A substituted C _2-24 alkyl or alkenyl group having; a C _1-24 alkyl group having an alkyl or alkenyl aryl group; or a C _1-24 alkyl group and a substituted alkyl having at least one additional substituent on the aromatic ring or An alkenylaryl group;
R ² and R ³ are independently of each other —CH ₂ —CN, —CH ₃ , —CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₃ , —CH (CH ₃ ) —CH ₃ , — CH ₂ —OH, —CH ₂ —CH ₂ —OH, —CH (OH) —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —OH, —CH ₂ —CH (OH) —CH ₃ , —CH ( OH) —CH ₂ —CH ₃ , — (CH ₂ CH ₂ —O) _n H, where n is 1, 2, 3, 4, 5 or 6;
R ⁴ and R ⁵ , independently of one another, have the meanings given above for R ¹ , R ² or R ³ ;
X is a charge balancing anion]
A process for producing a coated granular preparation comprising a compound represented by
Co-drying in a fluid bed apparatus, if necessary, in a mixture with the builder and / or solid filler or in the form of pre-manufactured granules, to the bleach activator of formula (I) present in solid form, in particular finely divided form However, it provides a process characterized by spraying an acidic aqueous solution comprising polymeric polycarboxylates and / or phosphonic acids or alkali metal phosphonates as coating and consolidation active ingredients.

  This allows the bleach activator of formula (I) or the particles comprising it to be completely coated with the coating material. Furthermore, an increase in the granule strength of the bleach activator particles is observed when using a solution comprising polymeric polycarboxylate and / or phosphonic acid or alkali metal phosphonate.

  The compounds of formula I are described, for example, in the aforementioned patent literature or Abraham [Progr. Phys. Org. Chem. 11 (1974), p.1 or later] or Arnett [J. Am. Chem. Soc. 102 (1980), p. 5892 et seq.] Or according to known methods.

Preference is given to using compounds of the formula I in which R ¹ , R ² and R ³ are the same. Of these compounds, compounds in which the group is a methyl group are preferred. On the other hand, compounds in which at least one or two of the groups are methyl groups and the other groups have two or more carbon atoms are also preferred.

Anions X ⁻ include, in particular, halides such as chlorides, fluorides, iodides and bromides, nitrates, hydroxides, phosphates, hydrogen phosphates, dihydrogen phosphates, pyrophosphates, metaphosphates, hexafluorophosphate, carbonate, bicarbonate, sulfate, hydrogen sulfate, C _1-20 alkyl sulfates, C _1-20 alkyl sulfonate, an optionally C _1-18 alkyl-substituted aryl sulfonate, chlorate Perchlorate and / or anions of C _1-24 carboxylic acids, such as formate, acetate, laurate, benzoate or citrate, alone or in any mixture.

X ⁻ is chloride, sulfate, hydrogen sulfate, _ethosulphate , C _12/18 , C _12/16 or C _13/15 alkyl sulfate, lauryl sulfate, dodecylbenzene sulfonate, toluene sulfonate, cumene sulfonate, Preferred are compounds of formula I which are xylene sulfonate or methosulfate, or mixtures thereof. Toluene sulfonate or cumene sulfonate is understood here to mean the ortho-, meta- or para-isomeric anion of methylbenzene sulfonic acid or isopropylbenzene sulfonic acid, respectively, and any mixtures thereof. Para-isopropyl-benzenesulfonic acid is particularly preferred.

The compounds of the general formula I can be used as starting materials in the coating process according to the invention, either as they are in solid form, or formulated into granular forms, ie applied to organic and / or inorganic carrier materials. it can. In this regard, the compound of formula (I) is optionally added to a solution of the compound of formula I formed during its manufacture with stirring, with the carrier material, optionally under reduced pressure and at elevated temperature, optionally in an aqueous solvent. Can be applied to the carrier material. However, it is also possible to spray a solution of the compound of formula I onto the carrier material and subject it to a drying process during this operation or optionally afterwards. The coating of bleach activator granules produced by the method disclosed in German patent application DE 19740668 or DE 19740671 is also possible by the method of the invention, which is a preferred embodiment of the method of the invention. The particles produced by the blending process preferably have a diameter of 0.4 mm to 3 mm. Suitable carrier materials are any material that does not unduly deleteriously interact with the compounds of formula I, such as alkali metal cumene sulfonates, surfactants, organic acids and polymers, alkali metal carbonates, alkali metal sulfates. Salts, alkali metal hydrogen sulfates, alkali metal hydrogen carbonates, alkali metal phosphates, alkali metal dihydrogen phosphates, dialkali metal hydrogen phosphates and alkali metal silicates and mixtures thereof. Internal surface area of 10m ² / g~500m ² / g, preferably used carrier materials are particularly 100m ² / g~450m ² / g. Silicate carrier materials are particularly suitable for the purposes of the present invention and include, for example, alkali metal silicates, as well as silica, silica gel and clay, and mixtures thereof. However, it is preferred that the carrier material does not contain zeolite. In addition to the silicate component, the silicate-containing carrier material optionally comprises other particulate inert components that do not unduly compromise the stability of the compound of Formula I. Silica (so-called fumed silica) produced by heat treatment (flame hydrolysis of SiCl ₄ ) is suitable for use, as is silica produced by a wet process. Silica gel is a colloidal silica with an elastic to solid consistency and a generally loose pore structure and has a high liquid uptake capacity. These can be produced by allowing an inorganic acid to act on water glass. Clay is a natural crystalline or amorphous silicate composed of aluminum, iron, magnesium, calcium, potassium and sodium, such as kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillonite and bauxite. It is also possible to use aluminum silicate as a carrier material or as a component of a carrier material mixture. The carrier material preferably has a particle size of 100 μm to 1.5 mm.

In a further preferred embodiment of the invention, the method comprises the following steps:
a) An aqueous solution comprising a cationic nitrile, preferably in an amount of 10% to 90% by weight, in particular 15% to 50% by weight, and optionally an alkali metal cumene sulfonate, in particular sodium cumene sulfonate, is prepared. Process;
b) optionally adjusting the solution to an acidic pH, in particular by adding sulfuric acid and / or citric acid;
c) misting the solution in a fluid bed apparatus and drying;
d) optionally powdering the primary granules thus obtained in a fluidized bed using silica, zeolite and / or alkali metal cumene sulfonate, in particular sodium cumene sulfonate;
And optionally spraying the resulting powdered granule with coagulation and coating aqueous solution while simultaneously drying in the same fluidized bed apparatus or optionally in the downstream second fluidized bed apparatus. The granules can then be removed from the fluid bed apparatus and, if necessary, separated into acceptable and coarse / fine granules, especially by sieving. If necessary, this is followed by returning the fine granules and / or ground coarse granules to the fluidized bed of step c) and / or powdering the fine granules and / or fine ground granules. ).

  The coated bleach activator granule obtained by the process of the present invention, or its acceptable granule fraction, preferably has an average particle size of 0.2 mm to 2.5 mm, especially 0.4 mm to 2.0 mm. . The bulk density is preferably 300 g / L to 1000 g / L, particularly 400 g / L to 800 g / L. The proportion of compounds of the formula (I) is preferably 10% to 90% by weight, in particular 15% to 50% by weight. This is preferably used for the production of granular detergents or purifiers.

  Fluid bed devices that can be used in the process according to the invention are known, for example, from European patent specification EP 603 207 B1 or German patent application DE 19750424. In order to further reduce the possibility of the granules falling from the opening in the inflow bottom and consequently coming into contact with the relatively hot surface, the opening has a grid with a mesh width of especially less than 600 μm. Can be covered. In this case, the grid may be arranged in or on the opening. However, as is known in principle from German patent application DE 197504424, the grid is preferably directly under the opening in the inlet bottom. In one practical embodiment, a wire mesh of suitable mesh width can be sintered or attached in some other way under the inflow bottom known per se. The wire mesh is preferably made of the same material as the inflow bottom, particularly stainless steel. The fine mesh grid prevents the particles from falling, especially when the plant is shut down unexpectedly and especially in the case of particularly heavy particles with a bulk density of about 1000 g / L during operation. The grid width of the grid is preferably 200 to 400 μm. Furthermore, it is advantageous if the inlet bottom used has a pressure loss of at most 10 mbar, in particular at most 6 mbar.

  According to the invention, the consolidated and coated aqueous solution is applied to a fluid bed apparatus. Suitable consolidation and coating active ingredients are polymeric polycarboxylates, in particular the polymerization products of acrylic acid, methacrylic acid or maleic acid, or at least two copolymers thereof, which are completely or partially neutralized In particular, it can be used in the form of an alkali metal salt. Instead of or in addition to the polymeric polycarboxylate, phosphonic acids and / or alkali metal phosphonates can also be used. In the alkali metal salt, sodium is the preferred alkali metal in each case. The solution is preferably adjusted to the lowest possible viscosity for good droplet distribution when sprayed into a fluidized bed with simultaneous drying. If the pH of the solution is not initially in the acidic range, the pH is adjusted to an acidic pH, in particular by adding sulfuric acid and / or citric acid, in particular by adding sulfuric acid and / or citric acid. . Based on the granules to be coated, it is preferred to spray in an amount of an aqueous solution such that the coating constitutes 1% to 25% by weight, in particular 2% to 15% by weight.

  The granules are then removed from the fluidized bed in a manner known in principle and classified according to the particle size if necessary and, if possible, undesirably small particles (fine particles) and undesirably large as described above. The particles (coarse particles) are optionally returned to the granulation process following the grinding step. In certain embodiments of the process of the present invention, if necessary, the classified and acceptable granules are reintroduced into the fluidized bed apparatus to further improve the product characteristics of the granules, and the caking and coating solutions are introduced into them. Can be sprayed on.

  Granules coated by the method of the present invention are storage stable, free flowing and have sufficient particle stability and can be mixed with other particulate components of cleaning or cleaning agents in the usual manner. The coated granules obtained by the process according to the invention, especially in granular detergents or cleaners, are those whose composition is from 0.1% to 10% by weight, in particular from 0.2% to 7% by weight. It is preferably used in such an amount that it has the content of the bleach activator (I).

In a fluid bed apparatus [Glatt® AGT 400 with a diameter of 40 cm], with an incoming air flow of 400 m ³ / hour, an incoming air temperature of 95 ° C. and an outgoing air temperature of 55 ° C., trimethylammonium acetonitrile methosulfate and sodium cumene sulfonate (mass) Granules were produced from a homogeneous aqueous solution (ratio 1: 1, dry matter fraction 30%) for 5 hours at a solution throughput of 3 kg / h (this granule was still very sticky). Granulating again using a 20% strength aqueous solution of the polymeric polycarboxylate [Sokalan® CP45, manufacturer BASF] under the same conditions with respect to the incoming air flow, incoming air temperature and outgoing air temperature By overcoming the stickiness. The polymer fraction of the granules thus obtained was 5% by weight. The size of the granules was 0.4 mm to 2.0 mm, and the bulk density was 700 g / L. Next, the granules were sieved and the portion with a particle size of 0.8-1.6 mm was mixed with the other detergent components of the detergent formulation. The finished detergent could be used without agglomeration.

Primary granules were produced from a 40% strength aqueous solution of the cationic nitrile used in Example 1 in a 1.8 m diameter fluidized bed apparatus [Glatt® AGT 1800] and powdered with Na cumene sulfonate powder. . The amount of incoming air was 21,000 m ³ / hour and the incoming air temperature was 145 ° C. The outflow air temperature was adjusted to 65 ° C. by evaporating the water in the solution. After 1 hour, the fluidized bed that had been operated in a batch became full, and granulation was completed. The 20% concentration polymer solution used in Example 1 was used for consolidation at an inlet air temperature of 110 ° C. The polymer content of the finished granule was 10% by weight. The obtained granules were sieved to obtain granules having a particle size of 0.8 to 1.6 mm. The bulk density was 730 g / L.
The finished granule was processed with a normal granular detergent component to obtain a granular detergent.

In a fluidized bed apparatus [Glatt (registered trademark) AGT 1800] having a diameter of 1.8 m, primary granules were prepared from a 40% aqueous solution of the cationic nitrile used in Example 1, and silica powder [Thixosil (registered trademark)] was prepared. 38A]. The amount of incoming air was 20,000 m ³ / hour and the incoming air temperature was 140 ° C. The outflow air temperature was adjusted to 65 ° C. by evaporating the water in the solution. After 1 hour, the fluidized bed that had been operated in a batch became full, and granulation was completed. The 20% concentration polymer solution used in Example 1 was used for consolidation at an inlet air temperature of 110 ° C. The polymer content of the finished granule was 7% by weight. The obtained granules were sieved to obtain granules having a particle size of 0.8 to 1.6 mm. The bulk density was 710 g / L.

  The granule obtained in Example 2 was reintroduced into the fluidized bed apparatus, in which the 20% strength polymer solution used previously at the inlet air temperature of 130 ° C. and outlet air temperature of 65 ° C. Was sprayed to give a 20 wt% coating. Similarly, the granules obtained in Example 3 were reintroduced into the fluidized bed apparatus, in which a 20% strength polymer solution was sprayed from the side at an inlet air temperature of 130 ° C. and an outlet air temperature of 65 ° C. A weight percent coating was obtained.

The polymer solution used in Example 1 in a granule containing trimethylammonium acetonitrile methosulfate using a two-component nozzle placed at the bottom in a fluidized bed apparatus [Glatt® AGT 1800] with a diameter of 15 cm. Sprayed. The amount of inflow air was 100 m ³ / hour, the inflow air temperature was 120 ° C., and the outflow air temperature was 60 ° C. The two-component nozzle was operated using warm air at 75 ° C. The air ratio of the nozzle was 1.5 (kg of air / kg of solution). The ratio of the coating layer of the finished granule was 10% by weight. A complete coating layer was seen under the microscope. The obtained granules consisted of particles having a diameter of 0.8 mm to 2.0 mm, and had a bulk density of 750 g / L.

Claims (12)

Formula (I):

[Wherein R ¹ represents at least one substituent from the group of —H; —CH ₃ ; C _2-24 alkyl or alkenyl group; —Cl, —Br, —OH, —NH ₂ , —CN. A substituted C _2-24 alkyl or alkenyl group having; a C _1-24 alkyl group having an alkyl or alkenyl aryl group; or a C _1-24 alkyl group and a substituted alkyl having at least one additional substituent on the aromatic ring or An alkenylaryl group;
R ² and R ³ are independently of each other —CH ₂ —CN, —CH ₃ , —CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₃ , —CH (CH ₃ ) —CH ₃ , — CH ₂ —OH, —CH ₂ —CH ₂ —OH, —CH (OH) —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —OH, —CH ₂ —CH (OH) —CH ₃ , —CH ( OH) —CH ₂ —CH ₃ , — (CH ₂ CH ₂ —O) _n H, where n is 1, 2, 3, 4, 5 or 6;
R ⁴ and R ⁵ , independently of one another, have the meanings given above for R ¹ , R ² or R ³ ;
X is a charge balancing anion]
A process for producing a coated granular preparation comprising a compound represented by
Co-drying in a fluid bed apparatus, if necessary, in a mixture with the builder and / or solid filler or in the form of pre-manufactured granules, to the bleach activator of formula (I) present in solid form, in particular in fine powder form While spraying an acidic aqueous solution comprising polymeric polycarboxylate and / or phosphonic acid or alkali metal phosphonate as coating and consolidation active ingredient.   2. The method according to claim 1, wherein the pH of the aqueous solution is adjusted to an acidic value by adding sulfuric acid and / or citric acid.   The method according to claim 1 or 2, wherein the aqueous solution has a pH of 4 to 4.4.   The amount of aqueous solution sprayed is such that the coating constitutes 1% to 25% by weight, in particular 2% to 15% by weight, based on the granules to be coated. The method according to claim 1.   The coating and caking active ingredient used are characterized by the polymerization products of acrylic acid, methacrylic acid or maleic acid, or at least two copolymers thereof, and / or phosphonic acid or alkali metal phosphonates The method according to claim 1. 6. The process according to claim ¹ , wherein R ¹ , R ² and R ³ are the same and in particular a compound of the formula I is used which is a methyl group. Anion X ⁻ is a halide, eg, chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate , carbonate, bicarbonate, sulfate, bisulfate, C _1-20 alkyl sulfates, C _1-20 alkyl sulfonate, an optionally C _1-18 alkyl-substituted aryl sulfonate, chlorate, perchlorate Using a compound of formula I which is an acid salt and / or an anion of a C _1-24 carboxylic acid, for example formate, acetate, laurate, benzoate or citrate alone or in any mixture The method according to claim 1, wherein: Anion wherein X ^-, chloride, sulfate, bisulfate, methosulfate, ethosulfate, C _12/18, C _12/16 or C _13/15 alkyl sulfates, lauryl sulfate, dodecylbenzenesulfonate, toluenesulfonate, 8. Process according to claim 7, characterized in that the compound of formula I which is cumene sulfonate, xylene sulfonate or a mixture thereof is used.   9. A process according to claim 1, wherein the coated granular preparation has an average particle size of 0.2 mm to 2.5 mm, in particular 0.4 mm to 2.0 mm.   10. The method according to claim 1, wherein the bulk density of the coated granular preparation is 300 g / L to 1000 g / L, in particular 400 g / L to 800 g / L.   11. The process according to claim 1, wherein the proportion of the compound of formula (I) in the coated granular preparation is 10% to 90% by weight, in particular 15% to 50% by weight. .   Use of a coated granular preparation obtained by the process according to any of claims 1 to 11 for the manufacture of a granular detergent or cleaning agent.