JP2002517558A - Process for producing alkyl polyglycoside-containing granules - Google Patents

Abstract

The invention relates to granulates containing alkylpolyglycoside (APG) having advantageous technical application properties and which can be obtained through a method whereby an aqueous APG paste is mixed with other aqueous non-surface active granulation components and sprayed on a solid mixture being agitated in a mixer.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to an alkyl polyglycoside (APG) by a mixing and granulation process.
The present invention relates to a method for producing a granular material containing:

BACKGROUND OF THE INVENTION Granular detergent compositions are often manufactured by spray drying. In the spray drying method, components such as a surfactant and a builder containing about 35 to 50% by weight of water are mixed to form an aqueous suspension known as a slurry, and the resulting mixture is placed in a spray drying tower. And spray into a hot gas stream to obtain detergent particles. Both equipment and operation for such a process is expensive, as about 30-40% by weight of the water in the slurry must be evaporated. In addition, granules produced by spray drying generally exhibit good solubility, but have a low bulk density, which results in a large packaging volume and a large storage volume for transportation and storage. Also, the fluidity of the spray-dried granules is far from optimal due to the irregular surface shape which also affects the appearance.

[0003] Further, there are other problems with spray drying nonionic surfactants. In view of the relatively low melting point and relatively high volatility, nonionic surfactants are partially entrained in the hot drying gas during spray drying and become waste gases (this can be "pluming" or " This is a phenomenon known to those skilled in the art as "blue smoke".) The spray-drying process has many other disadvantages, so it implements a method of producing detergent without spray-drying anyway. At least some attempts were made.

[0004] For example, W. Hermann de Groot, I. Adami, GF Moretti, "The Manufacture
of Modern Detergent Powder ", Hermann de Groot Academic Publisher, Wassen
aar, 1995, pp. 102 et seq., describe various mixing and granulation methods for detergent production. A feature common to all these methods is that the premixed solid is granulated in the presence of the liquid component and optionally dried in the next step.

[0005] There is an extensive prior art in the patent literature relating to the production of detergents without a tower.
As is usually the case with nonionic surfactants, alkyl polyglycosides (A
Since the aqueous solution or paste of PG) cannot be easily used as a granulating liquid,
The production of surfactant particulates containing APG involves additional difficulties. This is APG
When attempting to apply a solution to a flowing solid, the resulting granules have only limited absorption capacity for the other desired ingredients of the detergent and, in addition, tend to agglomerate into clumps Because. This method also has the disadvantage that the mixture to be granulated adheres strongly to the agitator and walls of the mixer, thus hindering continuous production.

(Disclosure of the Invention) (Technical Problems to be Solved by the Invention) An object to be solved by the present invention is to provide a method for producing an APG-containing granular material without the above-mentioned disadvantages. is there. The present invention provides a granulation method that enables a discontinuous or continuous process for producing APG-containing granules that does not produce cakes and does not produce granules having undesirable properties.

(Solution method) The above-mentioned problem is solved by using an APG solution or paste as a mixture with another aqueous solution of a non-surface-active granulation component, instead of using the APG solution or paste as it is as a granulation liquid. be able to. The present invention relates to a method for producing a granular material containing an alkyl polyglycoside (APG), wherein a water-containing APG paste is mixed with another aqueous solution of a non-surface-active granulating component, and the resulting mixture is mixed with a mixer. Spraying onto a solid mixture being stirred in.

[0008] Alkyl polyglycosides suitable for use in accordance with the present invention have the formula: RO (G) _z Wherein R is a straight or straight chain having 8 to 22, preferably 12 to 18 carbon atoms.
G is a branched or branched, especially 2-methyl branched, saturated or unsaturated aliphatic group;
Or a glucose unit having 6 carbon atoms, preferably representing glucose)
Corresponding to Glycosidation degree z is 1.0 to 4.0, preferably 1.0 to 2.0.
, More preferably in the range of 1.1 to 1.4.

A linear alkyl polyglucoside, ie, a polyglycosyl component is a glucose unit, and an alkyl component is an alkyl polyglycoside which is an n-alkyl group. Such an alkyl polyglucoside has the formula:

Embedded image (Where x is a number that is one less than the glycosidation degree z, and desirable x is 0
A number between 0 and 3, preferably between 0 and 1, more preferably between 0.1 and 0.4. ). The number n of methylene groups is preferably 7 to 21, more preferably 11
~ 17 carbon atoms.

[0010] The alkyl polyglycoside (hereinafter simply referred to as APG) used in accordance with the present invention can be obtained from known raw materials by a known method. For example, dextrose is reacted with n-butanol in the presence of an acid catalyst to prepare a butyl polyglycoside mixture, which is reglycosidated with a long chain alcohol in the presence of an acid catalyst to give the desired alkyl polyglycoside mixture. Get. Dextrose may be glycosidized directly with the desired long-chain alcohol to give the desired mixture of alkyl polyglycosides.

The structure of the product can vary within certain limits. The alkyl group is determined by the choice of long chain alcohol. Industrially obtainable C _8-22 alcohols, especially natural alcohols obtained by hydrogenation of carboxylic acids or carboxylic acid derivatives, are preferred for economic reasons. Alcohols obtained by industrial synthesis of alcohols, such as oxo alcohols and Ziegler alcohols, can also be used.

The polyglycosyl units Gy are determined on the one hand by the choice of carbohydrates and on the other hand by a controlled average degree of polymerization (glycosidation degree y), as described, for example, in DE 19 43 689. In principle, polysaccharides such as starch, maltodextrin, dextrose, galactose, mannose, xylose and the like can be used. Preference is given to the industrially available carbohydrates starch, maltodextrin and especially dextrose. Alkyl polyglycosides are always mixtures of oligomers, which are mixtures of different isomers, since APG synthesis of economic interest is not regio- or stereoselective. They are intermingled with each other by pyranose and furanose forms by α- and β-glycosidic bonds. The binding positions of the two sugar units are also different.

[0013] Alkyl polyglycosides that can be used in the present invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides.
Alkyl monoglycosides are obtained from alkyl polyglycosides and can be concentrated, for example, by the method described in EP092355 using a polar solvent such as acetone. The degree of glycosidation of an alkyl polyglycoside can usually be determined by ¹ H-nuclear magnetic resonance.

According to the present invention, the alkyl polyglycoside is in the form of an aqueous solution or paste,
It is mixed with another aqueous solution of the non-surfactant granulation component and sprayed onto the solid. The APG solution or paste has an APG content of at least 40% by weight, preferably at least 45% by weight, more preferably at least 50% by weight, based on the APG solution or paste, before being mixed with said another solution. Is desirable.

An aqueous solution of the non-surfactant granulation component is mixed with the APG paste before being sprayed on a solid. The non-surfactant granulation component may be any detergent component that is soluble in water and is not selected from the group of surfactants. As non-surfactant components, mention may in particular be made of silicates, polymers, complexing agents, optical brighteners and inorganic salts.

Suitable silicates are both crystalline silicates and amorphous silicates, with alkali metal silicates being preferred. Sodium Suitable crystalline layered silicates of the _{formula: NaMSi x O 2x + 1 ·} yH in ₂ O [wherein, M
Is sodium or hydrogen, x is a number from 1.9 to 4, y is a number from 0 to 20, and preferably x is 2, 3 or 4. ]. Such crystalline layered silicates are described, for example, in European Patent Application EP-A-0164514. Preferred crystalline layered silicates of the above formula are those wherein M is sodium and x is 2 or 3. Both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are particularly preferred. β-Sodium disilicate can be obtained, for example, by the method described in International Patent Application WO-A-91 / 08171.

The modulus (Na ₂ O: SiO ₂ ratio) is 1: 2 to 1: 3.3, preferably 1:
Amorphous sodium silicate from 2 to 1: 2.8, more preferably from 1: 2 to 1: 2.6, with delayed dissolution and secondary detergency may be used. Delayed dissolution of conventional amorphous sodium silicate can be achieved in a variety of ways, such as, for example, surface treatment, compounding, compression or overdrying. In the present invention, "amorphous" is understood to include "X-ray amorphous". In other words, X-ray diffraction analysis indicates that the silicate does not exhibit the sharp X-ray reflections characteristic of crystalline materials, but only one or more scattered X-ray maxima with a diffraction angle width of several degrees. I do. However, particularly good builder performance can also be achieved if the silicate particles show a weak or sharp diffraction maximum in electron diffraction analysis. This can be interpreted to mean that the silicate has microcrystalline parts with a size of ten to several hundred nm. This value is preferably up to 50 nm, especially up to 20 nm. Such a so-called X-ray amorphous silicate which delays dissolution as compared with ordinary water glass is described in, for example, German Patent Application D.
EA-4400024. Compressed amorphous silicates, compounded amorphous silicates, and overdried X-ray amorphous silicates are particularly preferred.

Suitable polymers are water-soluble polymers, which are often used in detergents because of their multiple wash cycle properties. This group of polymers includes, inter alia, polyacrylic acids or polyacrylates and copolymers of acrylic acid with other monomers, especially unsaturated acids, such as maleic acid. Acrylic / maleic copolymers are commercially available, for example, as Sokalan® CP5 (BASF).

Suitable complexing agents for the purposes of the present invention are, for example, alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulphonates. It is a metal salt. Also suitable are low molecular weight hydroxycarboxylic acids such as citric, tartaric, malic and gluconic acids. Suitable complexing agents are organic phosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylene phosphonic acid)
) (ATMP), diethylenetriaminepenta (methylenephosphonic acid) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM).

As the fluorescent whitening agent, a derivative of diaminostilbene disulfonic acid or an alkali metal salt thereof can be used. Suitable optical brighteners are, for example, 4,4'-bis- (2-
A salt of anilino-4-morpholino-1,3,5-triazinyl-6-amino) -stilbene-2,2′-disulfonic acid or a similar structure having a diethanolamino group, a methylamino group instead of a morpholino group, It is a compound having an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type, for example 4
, 4'-bis- (2-sulfostyryl) -diphenyl, 4,4'-bis- (4-chloro-3-sulfostyryl) -diphenyl or 4- (4-chlorostyryl) -4 '-(
Alkali metal salts of 2-sulfostyryl) -diphenyl may be used. Mixtures of the above whitening agents may be used.

Finally, if desired, inorganic salts can also be used as granulating components. In this group, alkali metal salts are preferable, and among them, carbonate, hydrogencarbonate and sulfate are particularly preferable.

The above-mentioned granulated components may be used as a mixture with each other, and the composition is not limited.
If one component is not intended to be present in large amounts in the granulate, mixing with other granulation components is always recommended. Thus, the optical brightener is usually combined with other granulating components. The active ingredient content in the aqueous solution of the granulated components before mixing with the APG paste is, for example, more than 20% by weight, preferably more than 25% by weight, more preferably more than 30% by weight, based on the aqueous solution. In one particularly advantageous embodiment, more than 20% by weight, preferably more than 25% by weight, more preferably more than 30% by weight, based on the aqueous solution, for mixing with the APG paste.
An aqueous sodium silicate solution containing more than% by weight of sodium silicate is used.

The APG paste and the aqueous solution of the granulation components are mixed, and the resulting mixture is sprayed onto the solid being stirred in the mixer. The mixture of APG paste and another aqueous solution of the granulation component is less than 70% by weight, preferably 65% by weight, based on the mixture
Less than 60% by weight of water. The APG paste and the aqueous solution of the granulation component may be mixed in various ratios, and the ratio of APG to other granulation components is advantageously in the range of 50: 1 to 1:50, based on active ingredient. is there. However, in a particularly preferred embodiment of the invention, this range is such that the ratio of APG to non-surfactant granulating component in the mixture is from 2: 1 to 1:10, preferably from 1: 1 to 1: 1, based on active ingredient. 5, more preferably in the range of 1: 1.5 to 1: 3.

The solid mixture to which the mixture of the APG paste and the aqueous solution of the non-surfactant granulating component is sprayed may include all components typically used in detergents. These components
Usually, builders and / or surfactant granules and / or bleach and / or
Or bleach activator, and optionally other typical detergent ingredients.

Next to the cleaning components, builders are the most important detergent components. According to the method of the present invention, the solid mixture is made up of builders typically used in detergents, such as zeolites, silicates, carbonates, organic cobuilders, and phosphoric acid (if their use is not ecologically problematic). Any of the salts can be included.

The microcrystalline synthetic zeolite containing bound water used according to the invention is preferably zeolite A and / or zeolite P. As zeolite P, Zeolite
MAP ™ (commercially available from Crosfield) is particularly preferred. Zeolite X and mixtures of zeolites A, X and / or P are also suitable. For example, zeolite A
And X co-crystals (about 80% by weight zeolite X) may also be used in the present invention. It is commercially available from CONDEA Augusta SpA under the name VEGOBOND AX (TM), _{wherein: nNa 2 O · (1-} n) K 2 O · Al 2 O 3 · (2-2.5) SiO 2 · (3.5 −5.5) It can be represented by H ₂ O.

The zeolite may be used as a builder in the granular formulation or may be used to “powder” the entire mixture to be compressed, and in any case, the zeolite will typically be incorporated into the premix. Used for Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measured by the Coulter Counter method) and preferably contain 18 to 22% by weight of bound water, more preferably 20 to 22% by weight.
In a preferred method, the solid mixture stirred in the mixer is a zeolite in an amount of more than 10% by weight, preferably more than 20% by weight, more preferably more than 30% by weight, based on the solid mixture. Contained in.

Well-known phosphates can of course also be used as builders, unless their use is to be avoided for ecological reasons. Orthophosphates, pyrophosphates, and especially tripolyphosphates in the form of the sodium salt are particularly suitable. Useful organic builders are, for example, polycarboxylic acids which can be used as sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), Those whose use is not ecologically disadvantageous, and mixtures thereof. Preferred salts are polycarboxylic acids,
For example, citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, salts of sugar acids, and mixtures thereof.

The silicates mentioned above may be present both as a granulating component (aqueous solution as a mixture with an APG paste) and in a solid mixture.

[0030] In addition to the builder, the solid mixture may comprise a cleaning component, preferably selected from anionic and / or nonionic surfactants. Such surfactants can be used as pure components as long as they are solid at the processing temperature. However, these surfactants can be used as formulated ingredients or applied to a carrier material for incorporation into a solid mixture.

[0031] Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C _9-13 alkyl benzene sulfonates, olefin sulfonates, ie, C _12-18 monoolefins having, for example, terminal or non-terminal double bonds, are sulfonated with gaseous sulfur trioxide and then sulfonated. Includes mixtures of sulfonates and disulfonates of alkenes and hydroxyalkanes obtained by alkali or acid hydrolysis of the product. Alkanesulfonates are also suitable and are obtained, for example, by _{sulfochlorinating} or sulfoxidizing _C12-18 alkanes followed by hydrolysis or neutralization. Also suitable are esters of α-sulfo fatty acids (ester sulfonates), for example α-sulfonated methyl esters of fatty acids of hydrogenated coconut oil, palm kernel oil or tallow.

[0032] Other suitable anionic surfactants include sulphonated fatty acid glycerol esters. Fatty acid glycerol esters are mono-, di- and triesters and mixtures thereof obtained by esterifying monoglycerol with 1-3 mol of fatty acids or transesterifying triglycerides with 0.3-2 mol of glycerol. It is understood to include Preferred sulphonated fatty acid glycerol esters are sulphonated products derived from saturated fatty acids having 6 to 22 carbon atoms, such as caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. It is.

Alkyl (alkenyl) sulfates include C _12-18 fatty alcohols, such as coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or sulfuric acid _{semiesters of} C _10-20 oxo alcohol, and Alkali metal salts, especially the sodium salts, of the sulfuric acid semiesters of secondary alcohols having a similar chain length are preferred. Another preferred alkyl (alkenyl) sulfate is an alkyl (alkenyl) sulfate having the above-mentioned chain length having a synthetic linear alkyl chain derived from petrochemicals, which has a degradability comparable to the corresponding compound derived from a fat and oil chemical raw material. Have C _12-16 alkyl sulfate, C _12-15 alkyl sulfate, and C _14-15 alkyl sulfate are
Particularly preferred in terms of cleaning performance. Other suitable anionic surfactants include 2,3-alkyl sulfates, such as those described in US Pat. No. 3,234,258 or US 507.
5041 and is commercially available from Shell Oil Company under the name DAN ™.

[0034] Linear or branched C _7-21 alcohol ethoxylated with 1 to 6 moles of ethylene oxide, eg 2-methyl branched C _9-11 alcohols + 3.5 moles on average EO (ethylene oxide) or C _12-18 Sulfuric acid monoesters of fatty alcohols +1 to 4 EO are also suitable. Because of their high foaming properties, relatively small amounts (for example, 1 to 5) are used in dishwashing detergents.
(% By weight).

Other preferred anionic surfactants are sulfosuccinates or sulfosuccinates, which are monoesters and / or diesters of sulfosuccinic acids with alcohols (preferably fatty alcohols, more preferably ethoxylated fatty alcohols) Also known as alkyl sulfosuccinic acid salts. Preferred sulfosuccinates have _C8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates have a fatty alcohol moiety derived from an ethoxylated fatty alcohol (described below) which is itself a nonionic surfactant. Among such sulfosuccinates, those having a fatty alcohol moiety derived from a narrow range ethoxylated fatty alcohol are particularly preferred. Alkyl (alkenyl)
Alkyl (alkenyl) succinic acids having preferably 8 to 18 carbon atoms in the chain or salts thereof may be used.

Other suitable anionic surfactants are, inter alia, soaps. The soaps are derived from saturated fatty acid soaps, such as salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and especially natural fatty acids (such as coconut oil fatty acids, palm kernel oil fatty acids or tallow fatty acids). Soap mixtures.

Anionic surfactants (including soaps) can be present in the form of sodium, potassium or ammonium salts, and in the form of soluble salts with organic bases (eg, mono, di or triethanolamine). The anionic surfactant is preferably in the form of a sodium or potassium salt, with the sodium salt being particularly preferred.

According to the invention, the solid mixture preferably comprises from 5 to 60% by weight, more preferably from 10 to 50% by weight, most preferably from 20 to 40% by weight of anionic surfactant.

As far as the choice of anionic surfactant used in the method of the present invention is concerned,
There is no fundamental requirement to limit the freedom of prescribing. However, preferred solid mixtures have no soap content of more than 0.2% by weight, based on the total weight of solids introduced. Preferred anionic surfactants are alkyl benzene sulphonates and fatty alcohol sulphates; preferred solid mixtures are 2 to 20% by weight, preferably 5 to 15% by weight, more preferably 5 to 15% by weight, based on the total weight of solids introduced. Is 7
. It contains 5 to 12.5% by weight of fatty alcohol sulfate.

Preferred nonionic surfactants are alkoxylated (preferably ethoxylated)
Particularly preferred are primary alcohols which comprise alcohols having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, wherein the alcohol residues are linear or preferably 2- It may be methyl-branched or may have a mixture of straight-chain and methyl-branching groups as in normal oxo alcohol residues. However, alcohol ethoxylates having straight-chain groups of C _12-18 alcohols of natural origin (eg coconut oil alcohol, palm oil alcohol, tallow alcohol or oleyl alcohol) and an average of 2 to 8 EO per mole of alcohol are preferred. Preferred ethoxylated alcohols are, for example, C _12-14 alcohol + 3EO or 4EO, C _9-11 alcohol + 7EO, C _13-15 alcohol +
Encompasses 3EO, 5 EO, 7 EO or 8EO, C _12-18 alcohol + 3EO, 5 EO or 7 EO, and mixtures thereof (for example mixtures of C _12-14 alcohol + 3EO and C _{12-1 8} alcohol + 5 EO). The degree of ethoxylation is an average value which can be an integer or a non-integer depending on the product. Alcohol ethoxylates with a narrow homolog distribution (narrow range ethoxylates, NRE) are preferred. In addition to such nonionic surfactants, fatty alcohols with EO greater than 12 may also be used. Examples are tallow fatty alcohol + 14EO, 25EO, 30EO or 40
EO.

Another preferred group of nonionic surfactants for use as the only nonionic surfactant or in combination with other nonionic surfactants are fatty acid alkyl esters (preferably having 1 to 4 carbon atoms in the alkyl chain). ), Especially alkoxylated, especially ethoxylated or ethoxylated / propoxylated, fatty acid methyl esters, which are described, for example, in Japanese patent application JP 58/217598 or preferably in international patent application WO-A -90/13533.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,
N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and nonionic surfactants of the fatty acid alkanolamide type may also be suitable. The amount of these nonionic surfactants used preferably does not exceed the amount of ethoxylated fatty alcohol used, more preferably not more than half.

Other suitable surfactants are of formula (I):

Embedded image [Wherein, RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ¹ is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, and [Z] is a 3 to 10 carbon atoms.
/ A straight-chain or branched polyhydroxyalkyl group having 3 to 10 hydroxyl groups. ] It is a polyhydroxy fatty acid amide shown by these. Polyhydroxy fatty acid amides are known substances and are typically obtained by reductive amination of reducing sugars with ammonia, alkylamines or alkanolamines, and then acylating with fatty acids, fatty acid alkyl esters or fatty acid chlorides.

The group of polyhydroxy fatty acid amides has the formula (II):

Embedded image [Wherein, R is a linear or branched alkyl or alkenyl group having 7 to 12 carbon atoms, and R ¹ is a linear, branched or cyclic alkyl or aryl group having 2 to 8 carbon atoms. R ² is a linear, branched or cyclic alkyl or aryl or oxyalkyl group having 1 to 8 carbon atoms, preferably a C _1-4 alkyl group or a phenyl group, and [Z] is And a linear polyhydroxyalkyl group having an alkyl chain substituted by at least two hydroxyl groups, or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. ] It also includes the compound shown by these.

Preferably, [Z] is derived by reductive amination of a reducing sugar, such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compound is then reacted with the fatty acid methyl ester in the presence of an alkoxide as a catalyst, for example according to International Patent Application WO-A-95 / 07331, to give the desired polyhydroxyfatty acid amide. Can be converted to

In a preferred embodiment of the invention, the solid mixture comprises 5 to 40% by weight, preferably 7.
It contains 5 to 30% by weight, more preferably 10 to 20% by weight of a nonionic surfactant.

In addition to the above components, bleaching agents, bleaching activators, enzymes, fragrances, fragrance carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-staining agents, fluorescent brighteners, and anti-tarnish agents Other conventional ingredients selected from the group consisting of color transfer inhibitors and corrosion inhibitors can be used according to the method of the present invention.

Of the compounds that form H ₂ O _{2 in} water, which act as bleaches, sodium perborate tetrahydrate and monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxy pyrophosphates, citrate perhydrate and H ₂ O ₂ generating persalts and peracids (e.g., perbenzoic acid salts, par oxo phthalate, di- Perazellaic acid, phthaloimino peracid or diperdocanedioic acid).

To improve the bleaching action when washing at temperatures of 60 ° C. and below, a bleach activator can be incorporated into the solid mixture. The bleach activator is a compound which produces, under perhydrolysis conditions, an aliphatic peroxocarboxylic acid having preferably 1 to 10 (more preferably 2 to 4) carbon atoms and / or optionally substituted perbenzoic acid. possible.
Substances having O- and / or N-acyl groups of the above carbon number and / or optionally substituted benzoyl groups are suitable. Preferred bleach activators are polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED)
Acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycoluril,
Inter alia, tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate
(n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to or in place of the conventional bleach activators described above, a “bleach catalyst” may also be incorporated into the molded article. A bleaching catalyst, a transition metal salt or a transition metal complex having a bleach-enhancing action,
For example, Mn, Fe, Co, Ru or Mo-Salen complex, or carbonyl complex. Mn, Fe, Co, Ru, Mo, with a nitrogen-containing tridentate ligand
Ti, V and Cu complexes such as Co, Fe, Cu and Ru-ammine complexes may be used as bleach catalysts.

[0051] Enzymes that can be used include those selected from the group consisting of proteases, lipases, amylases, cellulases or mixtures thereof. Bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis, and Streptomyces gr
Enzymes obtained from iseus are particularly suitable. Preference is given to using subtilisin-type proteases, particularly preferred proteases obtained from Bacillus lentus. Enzyme mixtures, such as protease / amylase or protease / lipase, or protease / cellulase mixtures, or cellulase / lipase mixtures, or protease / amylase / lipase, or protease / lipase / cellulase mixtures, are particularly preferred, with cellulase-containing mixtures being more preferred. Peroxidase or oxidase may be appropriate. The enzyme can be adsorbed on a carrier and / or encapsulated in an encapsulating material to protect it from premature degradation. In a solid mixture, the content of enzyme, enzyme mixture or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition, ingredients that have a positive effect on the removal of oils and fats from textiles by washing can be used (known as “antifoulants”). This effect is particularly evident when textiles already washed repeatedly with the inventive detergents containing such oil and fat-dissolving components become soiled. The oil and fat dissolving components are, for example, nonionic cellulose ethers (for example, methyl cellulose and 15-30% by weight of methoxyl group / hydroxyproxyl group 1 to 15% by weight based on nonionic cellulose ether).
And known polymers of phthalic acid and / or terephthalic acid or derivatives thereof (especially polymers of ethylene terephthalate and / or polyethylene glycol terephthalate,
Or anionic and / or nonionic modified derivatives thereof). Among them, the sulphonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Dyes and fragrances are used to improve the aesthetic impression created by the product and to provide consumers with a visual and sensory “typical and error-free” product as well as the required washing performance. Can be added to Individual perfume compounds may be used as perfume oils or perfume substances, examples being compounds of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples of ester-type fragrance compounds include benzyl acetate, phenoxyethyl isobutyrate, pt-butylcyclohexyl acetate, linalyl acetate,
Dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styryl propionate, and benzyl salicylate. Ethers include, for example, benzyl ethyl ether; aldehydes include, for example, linear alkanals having 8 to 18 carbon atoms, citral, citronellal,
Includes citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and burgeonal; ketones include, for example, yonones, α-isomethylionone and methylseryl ketone; alcohols include anethole, citronellol, eugenol, Geraniol, linalool,
Phenylethyl alcohol and terpineol; hydrocarbons include terpenes, such as limonene and pinene, among others. However, it is preferred to use a mixture of different fragrances which together produce a pleasant scent.

Such perfume oils may contain a natural perfume mixture obtained from a vegetable source such as, for example, pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Clary oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime flower oil, juniper berry oil, vetiver oil, frank oil, galbanum oil and labdanum oil, and orange flower oil, neroli oil, orange peel oil And sandalwood oil are also suitable.

The softening agents of the invention usually contain less than 0.01% by weight of a dye, while the perfume /
Fragrances can make up to 2% by weight of the total composition.

The perfume can be introduced directly into the process of the invention via a solid mixture, but it enhances the perfume attachment to the laundry and gives the textile a long lasting aroma due to the slow release of perfume. It may also be advantageous to apply a fragrance to the carrier to be applied. A suitable carrier material is, for example, cyclodextrin, and the cyclodextrin / perfume complex is optionally coated with other auxiliaries.

To improve the aesthetic impression, the detergents according to the invention can be dyed with suitable dyes. Preferred dyes, which can be selected without difficulty by a person skilled in the art, have a high stability during storage, are unaffected by other components of the detergent or light, and have a pronounced direct dyeability on the fibers so as not to dye textiles. I haven't.

The process of the present invention involves first dry mixing the solids in a suitable mixer and then combining the resulting premix in the presence of a mixture of the APG paste and an aqueous solution of a non-surfactant granulating component. It is performed by granulation. The liquid is preferably added by spraying.

The method of the present invention can be performed with various mixing and granulating equipment. 1
The solids are first introduced into an apparatus corresponding to one of the suitable mixing-granulators, for example an Eirich mixer type, a Loedige mixer type (eg a Loedige plow blade mixer) or a Schugi mixer type, and then the APG and the granulation components are mixed. Preferably 2-7 m in the presence
The granulation is carried out at a peripheral speed of the mixing tool of 1 / sec (plow blade mixer) or 5 to 50 m / sec (Eirich, Schugi), more preferably 15 to 40 m / sec. At the same time, the particle size of the granulate can be adjusted in a known manner. In this method, only a very short time, for example about 0.5 to 10 minutes, in particular about 0.5 to 5 minutes (Eirich mixer, Loedige mixer), is required for homogenizing the mixture and obtaining free-flowing particles. And not. In contrast, for a Schugi mixer, a residence time of usually 0.5 to 10 seconds is sufficient to obtain free-flowing particles. Mixers suitable for carrying out the method of the invention are, for example, those of the series R
Or RV Eirich® mixer (Maschinenfabrik Gusgav Eirich (Ha
rdheim), Schugi® Flexomix, Fukae® FS-G mixer (trademark of Fukae Powtech Kogyo Co. (Japan)), Loedige FM, KM and CB
Mixers (trademark of Loedige Maschinenbau GmbH, Paderborn) and Series T or KT Drais® mixers (trademark of Drais-Werke GmbH, Mannheim).

A mixture of the hydrous APG paste and another aqueous solution of the non-surfactant granulation component is preferably used at a temperature above room temperature. This mixture is added to the stirred solid mixture, preferably at a temperature above 60 ° C, more preferably above 70 ° C. The effect of the high temperature of the granulating liquid is that a larger amount of liquid can be used and the formed granules are less sticky.

Example A surfactant-containing basic powder having the composition shown in Table 1 was produced by spray drying. AP
The base powder without any G was mixed with the other solids and the resulting mixture was added to the mixer. A 50% by weight APG paste and a 35% by weight solution of sodium silicate (both in water) were sprayed onto the stirred solid mixture. After the formation of the granules, a 43% by weight aqueous solution of acrylic acid / maleic acid copolymer was sprayed. In method E1 according to the invention, before spraying, the APG paste and the sodium silicate solution were mixed and the resulting mixture was sprayed onto a solid mixture. In Comparative Example 1 (C1), the APG paste was sprayed first, and then the sodium silicate solution was sprayed.

In the process E1 according to the invention, a 6% by weight copolymer solution (based on the final granulate) could be easily applied and fine free-flowing dry granules were obtained. In the comparative method (C1), only smaller amounts of the copolymer solution could be applied. If a large amount of the copolymer solution is applied, it will clump and the contents of the mixer will become sticky and block the mixer. Even with smaller amounts of the copolymer solution, the resulting granules were sticky and, in addition, were obviously coarse. Due to the lower amount of copolymer solution that can be added in the comparative example, the relative amounts (% by weight) of the other components were varied compared to Example E1 according to the invention. Except for the copolymer solution, the absolute amount (kg) is the same in Examples and Comparative Examples. Table 2 shows the composition (%) of the granular material. Table 3 shows the physical properties of the granular materials obtained by the methods E1 and C1.

[0063]

[Table 1] Composition of basic powder (% by weight)

[0064]

[Table 2] Composition of granules (% by weight) Sokalan® CP5 is an acrylic acid / maleic acid copolymer (BASF).

[0065]

[Table 3] Physical properties of granular materials

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Franz Gormans, Federal Republic of Germany Day-41812 Erkelenz, No. 49 in Inverrat 49・ Miro No.23 F term (reference) 4H003 AB03 AB19 AB27 AC05 AC08 BA10 CA15 CA20 DA01 EA15 EA16 EA28 EB22 EB23 EB32 ED02 FA41

Claims (11)

[Claims] 1. A method for producing a granular material containing an alkyl polyglycoside (APG), comprising mixing an aqueous APG paste with another aqueous solution of a non-surface-active granulating component, and mixing the resulting mixture. Spraying onto a solid mixture that is being stirred in a machine. 2. The wet APG paste has a content of at least 40 based on the paste.
2. The process according to claim 1, comprising at least 45% by weight, more preferably at least 50% by weight, of alkyl polyglycoside. 3. The APG used is 1.0 to 4.0, preferably 1.0 to 4.0.
A method according to claim 1 or 2, having a degree of glycosidation of 2.0, more preferably 1.1 to 1.4. 4. The method according to claim 1, wherein the alkyl polyglucoside is used as APG.
3. The method according to any one of 3. 5. The aqueous solution of the non-surfactant granulation component is selected from the group consisting of aqueous solutions of silicates, polymers, complexing agents, optical brighteners and inorganic salts.
The method according to any of the above. 6. An aqueous sodium silicate solution comprising more than 20% by weight, preferably more than 25% by weight, more preferably more than 30% by weight of sodium silicate, based on the aqueous solution, as the aqueous granulation component solution. The method according to any one of claims 1 to 5. 7. The solid mixture being stirred in the mixer is a builder and / or
A method according to any of the preceding claims, comprising surfactant granules and / or bleach and / or bleach activator, and other typical detergent components. 8. The solid mixture agitated in the mixer, based on the solid mixture, comprises more than 10% by weight, preferably more than 20% by weight, more preferably more than 30% by weight.
The method according to any of the preceding claims, comprising a zeolite in an amount greater than% by weight. 9. The mixture of the APG paste and another aqueous solution of the non-surfactant granulation component contains less than 70%, preferably less than 65%, more preferably less than 60% by weight of water, based on the mixture. The method according to claim 1. 10. The ratio of APG to non-surfactant granulation component in the mixture is from 2: 1 to 1:10, preferably from 1: 1 to 1: 5, more preferably 1: 1 based on the active ingredient.
. The method according to any of claims 1 to 9, wherein the method is in the range of 5 to 1: 3. 11. A mixture of the hydrous APG paste and another aqueous solution of the non-surfactant granulation component, when sprayed onto the stirred solid mixture, has a temperature above 60 ° C., preferably above 70 ° C. The method according to claim 1.