DE19925930A1 - Granular surfactant compound - Google Patents

Abstract

The invention relates to a granular surfactant compound composed of sodium silicate and other constituents, characterized in that it contains DOLLAR A 20 to 95% by weight sodium silicate and DOLLAR A 5 to 80% by weight linear alkylbenzenesulfonates DOLLAR A, an average particle diameter> = 50 μm has an ff¶c¶ value> = 7. DOLLAR A The invention also relates to a method for producing this granular surfactant compound and its use. DOLLAR A Finally, the invention also relates to detergents and cleaning agents which contain such a granular surfactant compound, in particular, if appropriate, in addition to other ingredients, active ingredients and auxiliaries.

Description

The invention relates to a granular surfactant compound made of sodium silicate and other Be constituent parts, a process for its production and its use.

Crystalline layered sodium silicates (layered silicates), in particular those of the formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 have proven to be suitable substitutes for the builders phosphate and zeolite, predominantly in detergents and cleaning agents.

The use of the aforementioned crystalline layered silicates for softening water is described for example in EP-A-0 164 514. Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3.

Preferred feedstocks are both beta and delta sodium disilicate (Na ₂ Si ₂ O ₅ .yH ₂ O), beta-sodium disilicate being able to be obtained, for example, by the process of PCT / WO 91/08171.

A commercially available crystalline sodium disilicate, which the above For mel corresponds to, for example, the SKS-6 from Clariant GmbH. This product exposes itself the different polymorphic phases of the sodium disilicate and thus exists made of alpha disodium disilicate, beta disodium disilicate and delta disodium disilicate. Prefers is the highest possible content of delta disodium disilicate. Can as a commercial product proportions of non-crystallized sodium silicate may also be included.  

The sodium disilicates mentioned above are usually used together with surfactants in the various areas used. This also includes the well-known anionic linea ren alkylbenzenesulfonates (also known as LAS).

The aforementioned known anionic linear alkyl benzene sulfonates (LAS) are in the generally in liquid water-containing form in the detergent manufacturing process in one spray drying process together with other detergent ingredients such as soda, water glass etc. brought into a powdery dry form. The material usually has a ge rings bulk density, because the spray droplets in the spray tower due to water evaporation expand and form hollow spheres. This product form makes the production of compact wash medium difficult and the resulting powder also lacks a good flow ability, which makes transportation in the detergent manufacturing process difficult.

The spray drying process is also energy-intensive, since all components are in one aqueous slurry must be dissolved in water and this water in energy consuming Spray tower must be evaporated. The required bulk density can usually only be achieved by one another additional agglomeration step can be achieved.

The object of the invention is now to provide surfactant compounds, which have a high fluidity. It is also an object of the invention to use linear alkyl benzenesulfonates from the liquid form to a solid, granular, free-flowing form to lead.

This object is achieved by a granular surfactant compound made from sodium silicate and other constituents of the type mentioned at the outset, characterized in that it
20 to 95 wt .-% sodium silicate and
5 to 80% by weight of at least one linear alkylbenzenesulfonate
contains, has an average particle diameter ≧ 50 µm and an ff _C value ≧ 7.

The granular surfactant compound according to the invention preferably has a medium particle diameter ≧ 150 µm.  

The granular surfactant compound according to the invention particularly preferably has a medium one Particle diameter ≧ 300 µm.

The granular surfactant compound according to the invention preferably contains 60 to 80% by weight of sodium silicate and 20 to 40% by weight of at least one linear alkylbenzenesulfonate.

The granular surfactant compound according to the invention preferably has an ff _C value ≧ 10.

The aforementioned object is also achieved by a method for producing a granular surfactant of sodium silicates and other ingredients, characterized in that a finely divided crystalline sodium disilicate having a particle diameter d ₉₀ ≦ 150 microns with at least a mixed linear alkylbenzene sulphonate.

Preferably, the finely divided crystalline sodium disilicate has a particle diameter of d ₉₀ to ≦ 100 micrometers.

The finely divided crystalline sodium disilicate particularly preferably has a particle diameter of d ₉₀ ≦ 50 μm.

The invention also relates to the use of the granular surfactant com according to the invention pounds for the production of washing and cleaning agents including dishwashing liquid teln.

The invention also relates to detergents and cleaning agents containing an inventive granular surfactant compounds, in particular in addition to other ingredients, active ingredients and auxiliary substances, contain. The following applies to the following quantities: if - even if not always explicitly mentioned - by the usual content, effect and Bring auxiliaries for detergents and cleaning agents to the sum of 100% by weight are.  

Such detergents and cleaning agents preferably contain 1 to 80% by weight of the invention granular surfactant compounds.

Such detergents and cleaning agents preferably contain 1 to 80% by weight of zeolite and 1 to 80% by weight of the granular surfactant compound according to the invention.

Such detergents and cleaning agents preferably contain 1 to 80% by weight of zeolite, 1 to 30 % By weight of crystalline layered sodium silicate and 1 to 80% by weight of the gra nular surfactant compounds.

In the above process, commercial crystalline sodium disilicate SKS-6 as well as the fine-particle crystalline sodium disilicate used in suitable mixers Process LAS solution to a tenside compound.

Suitable mixers can be: ploughshare mixer types from Lödige, annular gap mixer type pen from Lödige (e.g. type CB30), Flexomix mixer types from Schugi, Ringspaltmi type HEC from Niro, ring layer mixer (e.g. type K-TTE4) from Drais / Mann Heim, Eirich mixer (e.g. type R02), Telschig mixer (type WPA6), Zig-Zag mixer the Niro.

The resulting water-containing product mixture is in a suitable dryer dried. Dryers according to the invention can be: fluid bed dryers from Hosokawa Schugi (types: Schugi Fluid-Bed, Vometec fluid bed dryer), fluid bed dryer from Waldner or Glatt, turbo flight layer dryer from Waldner, spin-flash dryer from Anhydro and drum dryer.

The dryer should preferably agglomerate through a suitable movement of the material Support a granular material. The agglomeration at this stage performing leads to more uniform products than continuing mixing in the mixer.  

Even then, agglomeration is obtained. However, the grain size is less uniform and strong sticking and caking occur.

Preferred operating conditions in the fluid bed dryer are: air inlet temperature 120-180 ° C, product temperature approx. 60 ° C.

As previously described, it has now surprisingly been found that the aforementioned Depending on the type of silicate used, the flowability of surfactant compounds is greatly below divorced.

Assuming the same content of linear alkylbenzenesulfonate in the surfactant compound as given, granular surfactant compounds according to the invention, produced from finely divided sodium disilicate with ad ₉₀ value below 150 μm, preferably below 100 μm and particularly preferably below 50 μm, surprisingly show much better results Flow properties as ten-side compounds with coarser silicate starting material. Such surfactant compounds made from finely divided crystalline sodium disilicate and linear alkylbenzenesulfonate are thus considerably more advantageous for the detergent production process than surfactant compounds which are produced with coarse-particle sodium disilicate.

If, on the other hand, a certain flow behavior is specified, then fine crystalline Sodium disilicate a much larger amount of linear alkylbenzenesulfonate in the gra nular, flowable form can be brought as with coarse crystalline sodium disili cat.

The surfactant compounds according to the invention are common in the entire range of today Can be used with powder detergent. It is preferable to bring the layered silicate part and especially more preferably the LAS content in the formulation via the surfactant com according to the invention pounds.

Examples 6 to 9 show that the surfactant compounds according to the invention (produced with finely divided crystalline sodium silicate) can be used advantageously in detergent formulations  and with regard to the main parameter important for the detergent builder "inorganic" "incrustations" equal to tenside compounds made from coarse-particle crystalline sodium silicate are valuable.

The main advantage of surfactant compounds made from finely divided crystalline sodium silicate is the better flowability of the resulting surfactant compound and the possibility of Dispense with the energy and costly spray tower technology.

The properties of the granular surfactant compounds according to the invention were determined using fol gender measurement methods determined.

Determination of the grain distribution by sieve analysis

The inserts with the desired sieves are inserted into a Retsch sieving machine. The mesh size of the sieves decreases from top to bottom. 50 g of the powder to be examined are placed on the widest sieve. The powder material is conveyed through the various sieves by the oscillating movement of the sieving machine. The residues on the sieves are weighed and arithmetically related to the weight of the material. From the values, d ₅₀ and d ₉₀ values can be calculated.

Flowability

He describes the ability of powders and granules to move freely and to flow freely Expert as a fluidity. This is a very important parameter because it is a measure like the material is easy to handle, d. H. transportable, storable in containers and especially the Can be removed again. For the production of modern detergents in powder or Granular form, the raw materials already have a number of beneficial properties point. Both the detergent itself (corresponds to the sum of all ingredients) and the Intermediate stages in the manufacture must have a sufficiently high flowability in order to good handling in the production of detergents and on the way to and during Ver secure users. Good handling means, for example, simple Transport of the material during production (free-flowing), no clumping conditions and caking during manufacture and finally also in the final packaging.  

The flowability of bulk goods can be characterized using the ff _C value. The flow properties are measured in a ring shear device. For this purpose, a material sample is solidified in the cylindrical ring measuring chamber under the action of tension and simultaneous rotation of the chamber bottom against the chamber cover. Driving plates are attached to the chamber bottom and cover for better power transmission. Then the tension is determined at which the material is just sheared by the torsional movement. This is described by D. Schulze in Chem.-Ing.-Techn. 67 (1995) 60-68. The ff _C value is equal to the quotient of the strengthening stress Sigma ₁ by the bulk strength Sigma _c .

According to this, ff _C values from 2 to 4 cohesive bulk goods, values from 4 to 10 easily flowing and values above 10 free flowing products.

Production of compounds from finely divided crystalline sodium disilicate and linear Al kylbenzenesulfonate (LASS

1750 g of SKS-6 powder are placed in a M 20MK mixer from Lödige. With continuous mixing, 1000 g of Marlon as linear alkylbenzenesulfonate A 375 (Hüls) was quickly added dropwise. It is mixed for 1/2 min. The product comes in one Laboratory dryer from Retsch dried at 100 ° C air inlet temperature for 25 min, then as Granulate) sifted through a sieve with a mesh size of 1180 µm and the slight excess grain content discarded.

Production of test detergents

The optical brighteners are mixed in a quarter of the nonionic amount and in Household multimixer (Braun) mixed with half the amount of soda. In ploughshare The remaining soda and the total amounts of zeolite and polymer 1.5 Mi grooves at 300 rpm. mixed. Then half of the remaining nonionic in 5 minutes sprayed on. Then the SKS-6 is added and mixed for 10 minutes. Then the rest  second nonionic sprayed on for another 5 minutes. Eventually Anionic, Soap, anti-foam, phosphonate and opt. Brightener added and 10 minutes at 300 RPM mixed. The mixture from the Lödige mixer is placed in the tumble mixer low shear stress mixed with perborate, TAED and enzymes and 15 minutes ver mixes.

It is of course also possible to change the order in which the substances are combined to change.

Washing attempts

In a household washing machine (type: Novotronic 927 WPS, Miele) at 60 ° C and a water hardness of 18 ° dH special test fabric with this test detergent washed repeatedly (15 times) at a dosage of 65 g / wash. The test fabrics, these are in particular a cotton terry (Vossen), each a double-ribbed cotton, Polyester / cotton blended fabrics (type 20A) and standard cotton fabrics (type 10A) Fa. Laundry research Krefeld Testgewebe GmbH and a standard cotton fabric from Federal Material Testing Institute St. Gallen, Switzerland, will be another laundry ballast (3.75 kg) attached. After 15 washes, a sample is taken from each of the tissues and this in a muffle furnace at a temperature of 1000 ° C and a period of 24 Hours ashes.

Example 1 (comparison)

10 kg of commercially available SKS-6 (Clariant GmbH, Frankfurt) are placed in portions on an electric vibrating screen (type TMA 3070 from Siemens) with a metal screen with a mesh size of 1000 μm. After this sieve analysis, the starting material has the following particle size distribution:
<1000 µm: 5.5%
<500 µm: 19.8%
<300 µm: 27.9%
<150 µm: 42.2%
<75 µm: 63.2%
d ₅₀ = 122 µm
d ₉₀ = 843 µm.

About 9 kg of SKS-6 powder with the following particle size distribution (sieve analysis) were obtained as undersize:
<1000 µm: 0.2%
<850 µm: 0.4%
<710 µm: 2.15%
<500 µm: 6.9%
<300 µm: 13.7%
<150 µm: 26.9%
d ₅₀ = 68 µm
d ₉₀ = 321 µm.

The sieve residue test showed 91.3% residue.

According to the general rule "Production of compounds from finely divided crystalline sodium disilicate", this coarse-particle product was processed with Marlon A 375 to form a surfactant compound. The starting material had an ff _C value of 10.0, the surfactant compound of 6.1. The surfactant compound is therefore less flowable than the starting material. The further analysis data are listed in Table 1.

Example 2 (comparison)

SKS-6 powder was sieved as in Example 1. The starting material had the following phases Distribution: alpha disodium disilicate 5.6%, beta disodium disilicate 2.3%, delta disodium disilicate 90.4%, amorphous content 1.4% (% by weight).

According to sieve analysis, it had the following particle size distribution:
<1000 µm: 3.4%
<500 µm: 17.5%
<300 µm: 26.6%
<150µm: 44.6%
<75 µm: 65.9%
d ₅₀ = 131 µm
d ₉₀ = 766 µm.

As undersize, approx. 8 kg of SKS-6 powder with the following particle size distribution (sieve analysis) were obtained.
<500 µm: 0.1%
<300 µm: 9.1%
<150 µm: 29.8%
<100 µm: 51.7%
d ₅₀ = 81 µm
d ₉₀ = 245 µm.

The sieve residue test showed 86.9% residue.

According to the general rule "Production of compounds from finely divided crystalline sodium disilicate", this coarse-particle product was processed with Marlon A 375 to form a surfactant compound. The surfactant compound had an ff _C value of 5.6. The further analysis data are listed in Table 1.

Example 3 (comparison)

SKS-6 powder was sieved as in Example 1. The starting material had the following phases Distribution: alpha disodium disilicate 10.8%, beta disodium disilicate 4.4%, delta disodium disilicate 79.4%, amorphous portion 5.4%.

According to sieve analysis, it had the following particle size distribution:
<1000 µm: 4.4%
<500 µm: 18.3%
<300 µm: 26.9%
<150 µm: 43.6%
<75 µm: 64.4%
d ₅₀ = 127 µm
d ₉₀ = 799 µm.

The oversize was milled in a ball mill for 3 hours with a U 280A0 ball mill from Welte, which is metal-lined on the inside and whose drum rotates at approx. 50 rpm. 44 kg of porcelain balls with diameters of 1.8, 2.9, 3.5 and 5 cm are used as grinding media. Then it was sieved again. The undersize fractions, totaling 9 kg, were combined and had the following particle size distribution (sieve analysis):
<150 µm: 13.8%
<75 µm: 44.3%
<63 µm: 54.3%
<53 µm: 67.1%
d ₅₀ = 72 µm
d ₉₀ = 157 µm.

The sieve residue test showed 73.5% residue.

According to the general rule "Production of compounds from finely divided crystalline sodium disilicate", this coarse-particle product was processed with Marlon A 375 to form a surfactant compound. The surfactant compound had an ff _C value of 6.8. The further analysis data are listed in Table 1.

Example 4 (Invention)

10 kg of SKS-6 powder were ground analogously to Example 3. According to sieve analysis, it had the following particle size distribution:
<1000 µm: 3.9%
<500 µm: 19.5%
<300 µm: 28.8%
<150 µm: 47.1%
<75 µm: 68.6%
d ₅₀ = 140 µm
d ₉₀ = 805 µm.

The ground product obtained (approx. 10 kg) has the following particle size distribution (Microtrac):
<53 µm: 0.5 µm
<33 µm: 10 µm
<20 µm: 30.6 µm
d ₅₀ = 11.9 µm
d ₉₀ = 33.9 µm.

The mill product had the following phase distribution: alpha disodium disilicate 22.0%, beta disodium disilicate 12.1%, delta disodium disilicate 65.3%, amorphous portion 0.6%. The sieve residue test showed 20.3% residue.

In accordance with the general rule "preparation of compounds from finely divided crystalline sodium disilicate", this finely divided product was processed with Marlon A 375 to form a surfactant compound. The starting material had an ff _C value of 5.6, the surfactant compound of 10.0. The surfactant compound is therefore more fluid than the starting material. Further analysis data are listed in Table 1.

Example 5 (Invention)

In an Aeroplex fluidized bed counter-jet mill from Hosokawa-Alpine AG (type AFG-200), SKS-6 was ground at a material input of 6-10 kg / h and a classifying disc speed of 6000 rpm. According to sieve analysis, it had the following particle size distribution:
<1000 µm: 5.8%
<500 µm: 20.0%
<300 µm: 28.3%
<150 µm: 45.5%
<75 µm: 68.6%
d ₅₀ = 135 µm
d ₉₀ = 852 µm.

The ground product obtained (approx. 600 kg) gave the following particle size distribution (Microtrac):
d ₅₀ = 5.5 µm
d ₉₀ = 12 µm.

The mill product had the following phase distribution: alpha disodium disilicate 10.6%, beta disodium disilicate 6.9%, delta disodium disilicate 80.3%, amorphous portion 2.3%. The Sieve residue test showed 21.1% residue.

In accordance with the general rule "preparation of compounds from finely divided crystalline sodium disilicate", this finely divided product was processed with Marlon A 375 to form a surfactant compound. The surfactant compound had an ff _C value of 12.3. The further analysis data are listed in Table 1.

Table 1

Characteristics of the surfactant compounds

Example 6 (Invention)

In accordance with the general rule "preparation of the test detergents", a Test-Compact detergent with 27.4% by weight of surfactant compound from Example 5 and 13.8% by weight commercially available SKS-6 powder (this corresponds to 31% by weight of silicate and 10% by weight on linear alkylbenzenesulfonate). In model washing tests according to the General rule "washing tests" was the formation of inorganic incrustation gen examined. The average of the ash values of all five fabrics is 1.7%.

Example 7 (Invention)

In accordance with the general rule "preparation of the test detergents", a Test compact color detergent with 20.8 wt .-% surfactant compound from Example 4 and 21.3% by weight of commercially available SKS-6 powder (this corresponds to 35% by weight of silicate and 7% by weight of linear alkylbenzenesulfonate). Ent in model washing experiments  According to the general rule "washing tests", the formation of inorganic Incrustations examined. The average of the ash values of all five fabrics is 1.9%.

Example 8 (Invention)

In accordance with the general rule "preparation of the test detergents", a Test-Compact heavy-duty detergent with 27.4 wt .-% surfactant compound from Example 5 and 3.1% by weight of commercially available SKS-6 powder produced (this corresponds to 20.3% by weight of silicate and 10% by weight of linear alkylbenzenesulfonate). Ent in model washing experiments According to the general rule "washing tests", the formation of inorganic Incrustations examined. The average ash value of all five fabrics was 1.9%.

Example 9 (comparison)

In accordance with the general rule "preparation of the test detergents", a Test Compact heavy-duty detergent with 30.4 wt .-% surfactant compound from Example 1 (das corresponds to 20.3% by weight of silicate and 10% by weight of linear alkylbenzenesulfonate). In Mon dellwaschversuche according to the general rule "washing tests" was Formation of inorganic incrustations examined. The average of the ash values of all five tissues is 2.2%.  

Table 2

Composition of the test detergent

Substances used

Zeolite A: Wessalith P, Degussa
SKS-6: Layered silicate SKS-6 powder, from Clariant
Polymer: Sokalan CP5, from BASF
Soda: heavy soda, Matthes & Weber
Bicarbonate: Solvay
Percarbonate: Oxyper C, Solvay Interox
Perborate monohydrate: Degussa
Perborate tetrahydrate: Degussa
TAED: TAED 4049, Clariant
Linear alkylbenzenesulfonate: Marlon A 375, Hüls
Nonionics: Genapol OAA 080, Clariant
Soap: Liga basic soap HM11E
Defoamer: 11.Plv.ASP3, Wacker
Enzyme I: Termamyl 60T, from Solvay Enzymes
Enzyme II: Savinase 6.0 TW, from Solvay Enzymes
Optical brightener I: Tinopal CBS-X, from Ciba
Optical brightener II: Tinopal DMS-X, from Ciba
Phosphonate: Dequest 2041, Monsanto
Sodium citrate: Fluka
Polyvinylpyrrolidone: Sokalan HP50, from BASF
Soil release polymer: SRC 1, Clariant
CMC: Tylose 2000, from Clariant
Sulphate: light sulphate, from Solvay

Claims (12)

1. Granular surfactant compound of sodium silicate and other ingredients, characterized in that it contains 20 to 95 wt .-% sodium silicate and 5 to 80 wt .-% of at least one linear alkylbenzenesulfonate, an average particle diameter ≧ 50 microns and an ff _C value ≧ 7. 2. Granular surfactant compound according to claim 1, characterized in that it is a has average particle diameter ≧ 150 µm. 3. Granular surfactant compound according to claim 1 or 2, characterized in that it has an average particle diameter ≧ 300 µm. 4. Granular surfactant compound according to one or more of claims 1 to 3, characterized characterized in that it contains 60 to 80% by weight of sodium silicate and 20 to 40% by weight contains at least one linear alkylbenzenesulfonate. 5. Granular surfactant compound according to one or more of claims 1 to 4, characterized in that it has an ff _C value ≧ 10. 6. A process for producing a granular surfactant of sodium silicates and other ingredients, characterized in that a finely divided crystalline Na triumdisilikat having a particle diameter d ₉₀ ≦ 150 microns with at least one alkyl benzene sulphonate mixed linea ren. 7. The method according to claim 6, characterized in that the finely divided crystalline sodium disilicate has a particle diameter d ₉₀ ≦ 100 microns. 8. The method according to claim 6 or 7, characterized in that the finely divided crystalline sodium disilicate has a particle diameter d ₉₀ ≦ 50 microns. 9. Use of granular surfactant compounds according to one or more of the claims 1 to 5 for the production of washing and cleaning agents including dishwashing average. 10. Detergent and cleaning agent, characterized in that it is 1 to 80 wt .-% of the gra contains nular surfactant compounds according to one or more of claims 1 to 5. 11. Detergent and cleaning agent, characterized in that it contains 1 to 80% by weight of zeolite and 1 to 80% by weight of the granular surfactant compound after one or more of the Claims 1 to 5 contains. 12. Detergent and cleaning agent, characterized in that it contains 1 to 80% by weight of zeolite, 1 to 80% by weight of crystalline layered sodium silicate and 1 to 80% by weight of the granular Contains surfactant compounds according to one or more of claims 1 to 5.