JPH07508773A - Powdered surfactant mixture - Google Patents

Abstract

In order to obtain loose and pourable, non-lumping powdery products with a process for producing an alkylbenzene sulphonate-free mixture of powdery surfactants by drying aqueous suspensions of the ingredients, while avoiding the danger of spontaneous ignition, in particular of the spray-dryed product, 10 to 40 parts by weight alkylglycoside having the formula: R?1-O(G)n?, in which R?1 represents an alkyl residue having 8 to 22 C atoms, G represents a glycose unit and n is a number between 1 and 10; 5 to 20 parts by weight alkylsulphate having the formula: R?2-OSO3?X, in which R?2 represents an alkyl residue with 10 to 20 C atoms and X represents an alkali-, ammonium- or alkyl- resp. hydroxyalkyl-substituted ammonium ion; and 40 to 80 parts by weight of an inorganic excipient constituted by at least 10 % by weight alkali silicate are mixed with enough water to obtain a fluid mixture that can be pumped at temperatures below 80 C. The weight ratio between the alkylglycoside and the alkylsulphate is comprised between 5:1 and 1:2 and the molar ratio between the SiO2? and the alkali oxide in the alkali silicate amounts to at least 2. The fluid and pumpable mixture is then dehydrated by spray-drying or in a fluidized bed or layer by means of drying gases at temperatures below 250 C. These products are used in particular as loose and pourable precursor mixtures for the production of particulate washing or cleaning agents.

Description

[Detailed description of the invention] Powdered surfactant mixture The present invention comprises an alkyl sulfate, an alkyl glycoside and an inorganic carrier material. An injectable, flowable, powdered surfactant mixture, a method for producing the same, and Concerning its use as a dung powder for the production of granular detergents.

International Patent Application Publication No. WO37102053 describes a method for producing granular detergent, 2 to 60% by weight of surfactants (at least 0.1% by weight of the solids) % consists of alkyl glycosides, and the total amount of alkyl glycosides is not more than 2% by weight. ), 5 to 70% by weight of a builder, and up to 40% by weight of a water-soluble filler. A method is described by drying a 40-80% aqueous slurry containing

Preferred surfactants are anionic surfactants, especially alkylbenzene sulfonates. type, and nonionic surfactants, especially ethoxylated fatty alcohols. .

Preferably, water is removed from the slurry by spray drying.

U.S. Pat. No. 4,536,319 discloses alkyl glycosides, water-soluble salts, and If granular detergents containing water-insoluble builders and other surfactants are listed, There is. The detergent described in the patent contains up to 3% by weight of certain alkali metal silicates. have Unfortunately, the detergents typically have insufficient flowability and form clumps. (especially when stored).

Modern powder detergents typically consist of several individually prepared powder components. their formation The components need to be prepared in different ways depending on the nature of their constituents. Like that The preferred method for preparing surfactant-containing ingredients in detergents is that it is relatively simple. and spray drying of an aqueous solution or aqueous slurry of the components. To perform spray drying , surface-active ingredients must be able to withstand high temperatures, but it is important to ensure that these conditions are met. Addition of traditional anionic surfactants, especially alkylbenzene sulfones This is the case when using the default type.

The use of alkylbenzene sulfonates in detergents is important because this surfactant is Since it is a system, it has recently become a problem. Equally good cleaning properties and ecological Anionic surfactants that are safer in terms of It is a sulfation product of compounds (especially fatty alcohols). However, alkylbenzene The aqueous slurry containing the sulfonate is dried at conventional spray drying temperatures (typically 250-3 Can be easily spray dried at 50°C) but contains the same amount of alkyl sulfate. The aqueous slurry that is used is known to pose a risk of spontaneous combustion under such conditions. Understood. This problem is caused by the presence of nonionic surfactants in the slurry being spray dried. Non-ionic surfactants are often used in detergents, which is more serious when Often desirable. Nonionic surfactants have recently become preferred due to their advantageous properties. It includes alkyl glycosides having long chain alkyl groups. This kind of a Lukyl glycosides are typically produced in the form of a highly viscous paste and are therefore spray dried. Its use at relatively high concentrations in aqueous slurries requires large mechanical stresses. It was not viewed as a promising project because of the amount of work it would entail.

Therefore, specific amounts of alkyl sulfate, alkyl glycoside and inorganic carrier material (at least 10% by weight of which has a molar ratio of 5i02:alkali metal oxide) (consisting of alkali metal silicates exceeding 2=1) with pumpable fluidity An aqueous slurry is obtained and the slurry is converted into alkylbenzene sulfone by drying. It can be used without the above-mentioned problems in the production of surfactant-free powder mixtures. suitable for use as a so-called compound for the production of granular detergents. It was very surprising to find that it produced a storable, injectable, flowable powder. This is something that should be done.

For producing powdered surfactant mixtures free of alkylbenzenesulfonates The method of the present invention essentially comprises: Formula (I): R1-0 (G), (I) [In the formula, R1 is an alkyl group having 8 to 22 carbon atoms, and G is a glycose unit. , and n is a number from 1 to 10. ] 10 to 40 parts by weight of alkyl glycoside represented by formula (■): R20S OsX (II) [In the formula, R2 is an alkyl group having 10 to 20 carbon atoms, and X is an alkali metal group. ammonium ion or alkyl- or hydroxyalkyl-substituted It is an ammonium ion. Ko 5 to 20 parts by weight of alkyl sulfate (alkyl glycoside; The weight ratio of rusulphate is from 5:1 to 1:2, preferably from 3:1 to 1:1. ),and 40 to 80 parts by weight of inorganic carrier material (less than 10% by weight is 5in2:aluminum) From alkali metal silicate with a small molar ratio of potassium metal oxide (both 2:1) Become) of water in such an amount as to form a pumpable fluid mixture at a temperature below 80°C. and the mixture is spray-dried using drying gas at a temperature below 250°C. Water is removed by drying or fluidized bed drying to the extent that a free-flowing powder product is formed. It is characterized by The water content in such powders is typically below 15% by weight, especially It is 5 to 15% by weight. If the carrier material binds some water as water of crystallization, mixing The residual water content of a substance is as free water not bound within the crystal lattice.

In the present invention, a pumpable flowable aqueous slurry is defined as having a temperature below 80°C. can be easily handled by the pumps and piping commonly used in spray drying processes. be. Therefore, the preferred viscosity range of the slurry used in the method of the present invention is 60 to 75 using a suitable viscometer (e.g. B-type viscometer, spindle 3.20 rpm). Measured at °C, it is 3000-15000 mPa5.

Preferably in the method of the present invention, alkyl glycoside 20 of formula (I) ~30 parts by weight, 8 to 15 parts by weight of the alkyl sulfate represented by formula (II) and and 48 to 68 parts by weight of the inorganic carrier material. % of water to form a mixture containing % of water.

The aqueous slurry is spray dried in a so-called spray tower. At the top of the spray drying tower When slurry is sprayed from a pressurized nozzle into fine droplets, the droplets are formed by the action of gravity. It moves to the bottom of the spray drying tower and comes into contact with the hot drying gas. Drying gas is drying particles through the spray drying tower in co-current, or preferably counter-current, to the particles. that time, Raise the temperature of the drying gas so that the temperature of the spray-dried particles exceeds their autoignition temperature. It is important not to That is, in the present invention, the temperature of the drying gas is 250°C. preferably 120-240°C, more preferably 140-210°C, maximum The temperature is also preferably 150 to 190°C. This drying gas temperature is the highest in the spray drying tower. Measured in the so-called ring channel, which is a warm area. It's temperature. The explanation regarding temperature is based on another embodiment of the production method of the present invention (fluidized bed drying). ) also applies.

The preparation of the slurry leading to the mixture of the invention involves the production of alkyl glycosides and their Typically 30-60% by weight of alkaline, as typically produced by subsequent optional bleaching. Aqueous kill glycoside pastes may be used. Similarly, alkyl sulfate The components and especially the carrier components may also be used in the form of aqueous solutions or suspensions. sura In order for the lye to be easily flowable and pumpable at temperatures below 80°C, its (approximately 35% by weight, preferably 40 to 50% by weight) in the slurry to be dried. It has been found to be advantageous to have water present. Another advantage of the method of the invention in this regard is The point is that the viscosity of the slurry leading to the compound of the invention is particularly low at 60-75°C. in the range of 3,000 to 15,000 mPa5, and that of alkyl sulfate. Surprisingly compared to a slurry containing the same amount of alkylbenzene sulfonate instead. (The point is that it is low.

Injectable flowable alkylbenes of the invention prepared by the process of the invention The zenesulfonate-free powdered surfactant mixture is preferably [wherein R1 is an alkyl group having 8 to 22 carbon atoms, G is a glycose unit, and n is 1 ~10 numbers. ] 10 to 40% by weight of alkyl glycoside represented by formula (n). R20SO3X (II) [In the formula, R2 is an alkyl group having 10 to 20 carbon atoms, and X is an alkaline earth metal group. ammonium ion or alkyl- or hydroxyalkyl-substituted It is an ammonium ion. ] 5 to 20% by weight of alkyl sulfate represented by (alkyl glycoside: alkyl sulfate) The weight ratio of rusulphate is 5:1 to 1:2, especially 3:1 to 1:1), no 40-80% by weight of the carrier material (at least 1% by weight based on the total carrier material) 0% by weight means that the molar ratio of 5i02:alkali metal oxide is at least 2:1 alkali metal silicates) and up to 15% by weight of water, especially 5 to 15% by weight of water. Contains amount%.

At least 10% by weight of the inorganic carrier material present in the compound of the invention, preferably or 20 to 50% by weight, the molar ratio of 5i02:alkali metal oxide is at least Also 2:1, especially 2. A ratio of 0 to 3.5:1, preferably 2.5 to 3.5:1 Consisting of alkali metal silicate. The preferred alkali metal is sodium. a Other water-soluble inorganic carrier materials that may be used in addition to alkali metal silicates (after drying, granular carbonates, hydrogencarbonates and sulfates of alkali metals and their Mixtures are particularly suitable. In this case too, the sodium salt is preferred. water-insoluble carrier materials (especially layered silicates, such as bentonite or smectite, and Luminosilicates, including for example zeolites) may also be used.

Alkyl glycosides suitable for combination in the compounds of the invention include R1 is an alkyl group having 8 to 22 carbon atoms, G is a glycose unit, and n is 1 -10. Such alkyl glyco Sid and its preparation are described, for example, in European patent applications EP 92355 and 3012. No. 98, No. 357,969 and No. 362,671, and U.S. Pat. No. 47828. Glycoside formation of such alkyl glycosides (G) in formula (I). ] is a naturally occurring aldose or ketose mono mer (especially glucose, mannose, fructose, galactose, glucose, Gulose, aldrose, allose, idose, ribose, arabinose, xy oligomers or polymers (including loose and lyxose). the An oligomer consisting of glycosidic bonded monomers such as It depends not only on the type of sugars present but also on the number of sugars, the so-called degree of oligomerization. It is also characterized by The degree of oligomerization [n in formula (I)] is an analytical measurement. It is usually a fraction and has a value between 1 and 10. Preferred alkyl glycoside The degree of oligomerization has a value of less than 1.5, in particular from 1.2 to 1.4. Preferred monomer - unit is glucose because it is readily available.

The alkyl moiety of the alkyl glycoside present in the surfactant mixture of the invention [formula (1)] is also a derivative that is easily obtainable from renewable raw materials, especially are preferably derived from fatty alcohols, but their branched isomers, especially Suitable alkyl glycosides may also be prepared using so-called oxo alcohols. stomach. Therefore, straight chain octyl, decyl, dodecyl, tetradecyl, hexadecyl or primary alcohols having an octadecyl group and mixtures thereof are particularly suitable. It is. Particularly suitable alkyl glycosides include coconut fatty alkyl groups (i.e. Qualitatively, it has a mixture of RI = dodecyl and Rl = tetradecyl). its manufacture Due to their structure, alkyl glycosides contain a small amount (e.g. 1-2%) of unreacted free It may contain fatty alcohols, which do not adversely affect the properties of the compound. stomach.

Such alkyl glycondes are preferably present in the compounds of the invention from 10 to present in an amount of 40% by weight, more preferably in an amount of 20-30% by weight; The weight ratio of Licon, alkyl sulfate is 5:1 to 1:2, preferably 3 :1 to 1:1.

Suitable alkyl sulfates for use in the process of the invention are those in which R1 is the number of carbon atoms. 10-20 alkyl group, X is an alkali metal ion, ammonium ion or an alkyl- or hydroxyalkyl-substituted ammonium ion. It is a compound represented by formula (n). especially fatty alcohols having 12 to 18 carbon atoms and its branched homologues (so-called oxo alcohols) are particularly suitable. Ru. The alkyl sulfates can be combined with the corresponding alcohol component in a known manner. reaction with a sulfating agent (particularly sulfur dioxide or chlorosulfonic acid), followed by alkali metal, ammonium or alkyl- or hydroxyalkyl-substituted It can be prepared by neutralization with ammonium base. Such an alkyl sur Phate is preferably present in the compound of the invention at 5-20% by weight, more preferably is present in an amount of 8 to 15% by weight.

Furthermore, the mixture according to the invention may contain other surfactants, preferably non-ionic surfactants and and/or anionic surfactants (especially those of the sulfate or sulfonate type). ) in an amount of preferably 10% by weight or less, more preferably 1 to 5% by weight. It's fine. Surfactants of the sulphate type which may additionally be used are, inter alia, those mentioned above. Sulfated alkoxylation products of alcohols (so-called ether sulfates) include. Such ether sulfates preferably contain 2 to 3 per molecule. It has 0, more preferably 4 to 10 ethylene glycol groups. other suitable Anionic surfactants are used for the reaction of fatty acid esters with sulfur dioxide and the subsequent α-sulfoester obtained by the addition of carbon atoms, especially those having 8 to 22 carbon atoms (preferably 12 to 18) fatty acids and straight chain alcohols having 1 to 6 carbon atoms (preferably 1 to 4). A sulfonated product derived from a sulfonated product obtained from the sulfonated product by saponification sulfo fatty acids, and their salts.

Suitable nonionic surfactants have from 10 to 22 carbon atoms, preferably from 12 to 18 carbon atoms. Alkoxylates of straight-chain or branched alcohols, especially ethoxylates and/or or propoxylates. The degree of alkoxylation of alcohol is 1 to 20 , preferably 3 to 10. Such alkoxylates can be prepared in a known manner by Can be prepared by reaction of the corresponding alcohol with the corresponding alkylene oxide .

Derivatives of fatty alcohols are particularly suitable, but also their branched isomers, especially the so-called Oxoalcohols may be used to prepare useful alkoxylates. follow with a straight chain dodecyl, tetradecyl, hexadecyl or octadecyl group Particularly useful are the primary alcohols ethquinate and mixtures thereof. Ma In addition, alkyl amines corresponding to the above alcohols with respect to the alkyl moiety, vicinal Corresponding ethoxylation and/or proponentation of diols and carboxylic acid amides Oxylated products may also be used.

The carrier material is present in the powder mixture according to the invention in an amount of 40 to 80% by weight, preferably present in an amount of 48-68% by weight, at least 10% by weight of the carrier material, preferably 20-50% by weight must consist of the aforementioned alkali metal silicates. do not have.

Additionally, the compounds of the invention contain other conventional detergent ingredients that are stable under drying process conditions. May be included. Such optional components include, in particular, heavy metal coagulants, such as aminopolymers. Carboxylic acids and/or polyphosphonic acids, anti-redeposition agents such as cellulose polymers, co-builders, e.g. polycarboxylic acid polymers, foam suppressants, e.g. polysiloxanes or paraffins, and optical brighteners such as stilbendisul Includes fonic acid derivatives. Such additives can be added to the powdered surfactant mixture of the present invention. Preferably present in the product in an amount of 5% by weight or less, more preferably 0.5-2% by weight. do.

The powdered surfactant mixture according to the invention can be used in particular as an injectable flowable compound. and used in the production of granular detergent.

For use as a compound for the production of powdered detergents, the mixture according to the invention has an average Particle size is 0. It is preferable that the diameter is 2 to 0.4 mm, and the diameter is less than 211 Im. It must be substantially free of large particles and particles smaller than 50 μm. Really The term "free of content" means that the content is 0.18% by weight or less. By spray drying The size of the compound of the invention obtained by Particles with sizes outside this range can be easily separated by sieving and returned to the manufacturing process. can.

The bulk density of the compound of the present invention is preferably 200 to 500 gel. , may differ from the bulk density of the other powdered components of the detergent, and segregation typically does not occur.

The Hunbound of the present invention is a flowable, injectable powder that has a long shelf life. It does not lose its favorable properties even when The compound of the invention can be used to produce detergents. mixed with other powdered ingredients customarily used in detergents in a manner known in principle. obtain. Other ingredients may include, inter alia, abrasives such as powdered silica, bleaches such as bleaching agents, etc. udates or percarbonates, and bleach activators such as polyacylated alkylene dia amines, carboxylic acid anhydrides or polyacylated polyols. liquid, ma or liquefied or dissolved ingredients, such as enzymes, pigments, fragrances or other surfactants. agents (in particular non-ionic surfactants) can be added to the Hunbound of the present invention by methods known in principle. It may also be sprayed by method.

Example Example 1 An aqueous slurry containing 40-44% water by weight was prepared from the raw materials listed in Table 1. . Heat the alkyl glycoside component to approximately 60°C and add it to the alkyl glycoside while stirring. In addition to the aqueous sulphate solution, other ingredients were added. Sodium silicate is approximately 35% by weight was added last in the form of a water glass solution. The slurry had a viscosity shown in Table 2 (65°C It is heated to a temperature of approximately 60 to 80°C and then dried in a spray drying tower. sprayed with hot air under a pressure of 40 bar (temperature in the ring channel 150-1 90° C.) was passed through the column in countercurrent.

a) C+ 2/+ 4 alkyl glucoside, degree of oligomerization 1.4b) Straight line Cl 67I8 alkyl sulfate [Sulfopon (trademark) T1 Manufactured by Henkel KGaA] c) Si02:Na2O ratio 3 ．． 0:1 Flowable powder M1 with an average particle size of about 300I1m having the composition shown in Table and M2 were obtained. It does not contain particles larger than 1.5ma+ in diameter, and is powder-free. The dust content is between 0.1 and 65% by weight, and the bulk density is between 240 and 300 g/j! And It was.

ti-2: Stainless steel measured at 65°C with a B-type viscometer (spindle 3.20 rpm) Rally viscosity (mPas) international search report ,-PCT/EP 93101192 1.7. Yu, 1 kalpa-,, PCT/EP 93101192

Claims (14)

[Claims] 1. Pourable, free-flowing, alkylbenzene sulfonate-free powder surfactant a sex agent mixture by drying an injectable aqueous mixture of its components. is obtained, Formula (I) R1-O(G)n(I) [In the formula, R1 is an alkyl group having 8 to 22 carbon atoms, and G is a glycose unit. , and n is a number from 1 to 10. ] 10 to 40% by weight of alkyl glycoside represented by formula (II) R2OSO3X(II) [In the formula, R2 is an alkyl group having 10 to 20 carbon atoms, and X is an alkali metal group. ammonium ion or alkyl- or hydroxyalkyl-substituted It is an ammonium ion. ] 5 to 20% by weight of alkyl sulfate represented by (alkyl glycoside: alkyl sulfate) The weight ratio of rusulphate is 5:1 to 1:2, especially 3:1 to 1:1), no 40-80% by weight of the carrier material (at least 1% by weight based on the total carrier material) 0% by weight means that the molar ratio of SiO2 to alkali metal nitride is at least 2. alkali metal silicate), and up to 15% by weight of water. A surfactant mixture containing. 2. 20 to 30% by weight of alkyl glycoside of formula (I), of formula (II) 8-15% by weight of alkyl sulfate, 48-68% by weight of inorganic carrier material, Up to 10% by weight of other anionic and/or nonionic surfactants, especially 1 to 5% by weight % and from 5 to 15% by weight of water. 3. 20-50% by weight of the inorganic support material is SiO2:moles of alkali metal oxide. Alkali metal silicates in a ratio of at least 2:1, especially 2.0 to 3.5:1 A surfactant mixture according to claim 1 or 2, comprising: 4. The alkyl glycoside represented by formula (I) is an alkyl glucoside; Any of claims 1 to 3, wherein the degree of oligomerization n is less than 1.5, in particular from 1.2 to 1.4. A surfactant mixture according to any of the above. 5. The alkyl sulfate represented by formula (II) is an alkyl sulfate having 12 to 18 carbon atoms. The surfactant mixture according to any one of claims 1 to 4, having a rukyl group R2. 6. Use of the powdered surfactant mixture according to any one of claims 1 to 5, comprising: Application as a pourable flowable compound for the production of granular detergents. 7. alkyl by drying a fluid aqueous mixture containing a surfactant. 1. A method for producing a benzenesulfonate-free powdered surfactant mixture, the method comprising formula (I) R1-O(G)n(I) [In the formula, R1 is an alkyl group having 8 to 22 carbon atoms, and G is a glycose unit. , and n is a number from 1 to 10. ] 10 to 40 parts by weight of alkyl glycoside represented by formula (II) R2OSO3X(II) [In the formula, R2 is an alkyl group having 10 to 20 carbon atoms, and X is an alkali metal group. ammonium ion or alkyl- or hydroxyalkyl-substituted It is an ammonium ion. ] 5 to 20 parts by weight of alkyl sulfate represented by (alkyl glycoside: alkyl sulfate) The weight ratio of rusulphate is 5:1 to 1:2) and the inorganic support material is 40 to 8 0 parts by weight (at least 10% by weight of which is a mole of SiO2:alkali metal oxide) alkali metal silicates in a ratio of at least 2:1) of water in such an amount as to form a pumpable fluid mixture at a temperature below 80°C. and the mixture is spray-dried using drying gas at a temperature below 250°C. thus comprising removing water to the extent that a free-flowing powdered product is produced. Method. 8. 20 to 30 parts by weight of alkyl glycoside represented by formula (I), represented by formula (II) 8 to 15 parts by weight of alkyl sulfate and 48 to 68 parts by weight of inorganic carrier material. part to form a mixture containing at least 35% by weight, especially 40-50% by weight of water. 8. The method of claim 7, wherein the method is mixed with water in an amount such that the 9. alkyl by drying a fluid aqueous mixture containing a surfactant. 1. A method for producing a benzenesulfonate-free powdered surfactant mixture, the method comprising formula (I) R1-O(G)n(I) [In the formula, R1 is an alkyl group having 8 to 22 carbon atoms, and G is a glycose unit. , and n is a number from 1 to 10. ] 10 to 40 parts by weight of alkyl glycoside represented by formula (II) R2OSO3X(II) [In the formula, R2 is an alkyl group having 10 to 20 carbon atoms, and X is an alkali metal group. ammonium ion or alkyl- or hydroxyalkyl-substituted It is an ammonium ion. ] 5 to 20 parts by weight of alkyl sulfate represented by (alkyl glycoside: alkyl sulfate) The weight ratio of rusulphate is 5:1 to 1:2) and the inorganic support material is 40 to 8 0 parts by weight (at least 10% by weight of which is a mole of SiO2:alkali metal oxide) alkali metal silicates in a ratio of at least 2:1) of water in such an amount as to form a pumpable fluid mixture at a temperature below 80°C. and from the mixture fluidized bed drying using drying gas at a temperature below 250°C. The process involves removing water to the extent that a free-flowing powder product is produced. How to do it. 10. The weight ratio of alkyl glycoside:alkyl sulfate is 3:1 to 1: 1. The method according to any one of claims 7 to 9. 11. 20-50% by weight of the inorganic support material is a SiO2:alkali metal oxide model. an alkali metal silica with a ratio of at least 2:1, especially from 2.0 to 3.5:1; In addition to the alkali metal silicate, the inorganic support material is alkali metal carbon. acid salts, alkali metal bicarbonates, alkali metal sulfates, layered silicates or Any one of claims 7 to 10 containing an aluminosilicate or a mixture thereof. The method described in. 12.Claim 7, in which drying gas is used at a temperature of 120-240°C, especially 140-210°C. 12. The method according to any one of 11 to 11. 13. The viscosity of the aqueous mixture to be dried is 3000 to 15000 mP at 60 to 75°C. The method according to any one of claims 7 to 12, wherein as. 14. Powdered surfactant produced by the method according to any one of claims 7 to 13. Use of mixtures as injectable flowable compounds for the production of granular detergents Uses of.