DE19925928A1 - Fine crystalline sodium silicate - Google Patents

Abstract

The invention relates to a finely divided crystalline layered sodium disilicate of the formula NaMSi¶x¶O¶2x + 1¶ È 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, which is characterized in that it has a content of DOLLAR A 0 to 40% by weight of alpha disodium disilicate DOLLAR A 0 to 40% by weight of beta disodium disilicate DOLLAR A 40 to 100% by weight of delta Disodium disilicate DOLLAR A has 0 to 40% by weight of amorphous components DOLLAR A, a process for its production and its use. DOLLAR A The invention also relates to detergents and cleaning agents which contain such a finely divided crystalline layered sodium disilicate, in particular, if appropriate, in addition to other ingredients, active ingredients and auxiliaries.

Description

The invention relates to a finely divided crystalline layered sodium disilicate 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, a process for its manufacture 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 substitutes are both beta and delta sodium disilicate (Na ₂ Si ₂ O ₅ .yH ₂ O), whereby beta sodium disilicate can 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.  

Basically, efforts have so far been made to produce those sodium disilicates that are possible contain the highest possible proportion of only one polymorphic phase, such as with one delta disodium disilicate content of more than 90% by weight or higher.

The sodium disilicates known to date can already provide a high proportion of them meet requirements. So they generally have a high calcium binding capacity on and their other washing and application properties are for many areas sufficient.

However, there is still a need for suitable substances that have a very high calcium content have binding capacity and at the same time produce only slight residues of solvent in water (hereinafter referred to as screen residue).

This object is achieved by a finely divided crystalline layered sodium disilicate of the type mentioned at the outset, which is characterized in that it has a content of
0 to 40% by weight of alpha disodium disilicate
0 to 40% by weight of beta disodium disilicate
40 to 100% by weight of delta disodium disilicate
0 to 40% by weight of amorphous parts
having.

The aforementioned alpha disodium disilicate corresponds to the Na-SKS-5 described in EP 0 164 514 B1, characterized by the X-ray diffraction data reproduced there, which are assigned to the alpha-Na ₂ Si ₂ O ₅ , whose X-ray diffraction diagrams at the Joint Committee of Powder Diffraction Standards numbered 18-1241, 22-1397, 22-1397A, 19-1233, 19-1234, 19-1237 are registered.

The aforementioned beta disodium disilicate corresponds to the Na-SKS-7 described in EP 0 164 514 B1, characterized by the X-ray diffraction data shown there, which are assigned to the beta-Na ₂ Si ₂ O ₅ , the X-ray diffraction diagrams of the Joint Committee of Powder Diffraction Standards with numbers 24-1123, 29-1261 are registered.

The above-mentioned delta disodium disilicate corresponds to the Na-SKS-6 described in EP 0 164 514 B1, characterized by the X-ray diffraction data shown there, which are assigned to the delta-Na ₂ Si ₂ O ₅ , whose X-ray diffraction diagrams at the Joint Committee of Powder Diffraction Standards are registered with the number 22-1396.

The finely divided crystalline layered sodium disilicate according to the present invention is characterized by increased binding capacity for compared to the prior art. Water hardness (calcium binding capacity), as well as the fact that the dissolving residues in water (hereinafter defined by the sieve residue) can be significantly reduced.

The finely divided crystalline layered sodium disilicate preferably has a content of
0 to 20% by weight of alpha disodium disilicate
0 to 30% by weight of beta disodium disilicate
50 to 95% by weight of delta disodium disilicate
0 to 20% by weight of amorphous parts
on.

The finely divided crystalline layered sodium disilicate particularly preferably has a content of
0 to 10% by weight of alpha disodium disilicate
0 to 15% by weight of beta disodium disilicate
70 to 90% by weight of delta disodium disilicate
0 to 10% by weight of amorphous parts
on.

The finely divided crystalline layered sodium disilicate is preferably free from sodium me tasilicate or NS phases. It is also free of so-called NS phases, such as those as defined in PCT / WO 97/19156 and JP 7/327995 A1 and to the here explicit reference is made.

The finely divided crystalline layered sodium disilicate preferably has ad ₉₀ value of <100 μm.

The finely divided crystalline layered sodium disilicate preferably has ad ₉₀ value of <60 μm.

The finely divided crystalline layered sodium disilicate preferably has a calcium binding capacity of more than 170 mg CaCO ₃ / g at 30 ° C. and 17 ° dH.

The finely divided, crystalline, layered form particularly preferably has a calcium binding capacity of more than 180 mg CaCO ₃ / g at 30 ° C. and 17 ° dH.

In particular, the finely divided crystalline layered sodium disilicate has a calcium binding capacity of more than 190 mg CaCO ₃ / g at 30 ° C. and 17 ° dH.

The finely divided crystalline layered sodium disilicate preferably has a screen back rest of less than 60%.

The finely divided crystalline layered sodium disilicate preferably has a screen back rest of less than 40%.

The finely divided crystalline layered sodium disilicate preferably has a screen back rest of less than 30%.

The invention also relates to a process for producing finely divided crystalline layered sodium disilicate, characterized in that a layered sodium silicate with a particle diameter d ₅₀ of 80 to 400 μm is ground to ad ₉₀ value of <100 μm.

In the aforementioned process, the finely divided crystalline layered sodium disilicate is preferably ground to ad ₉₀ value of <60 μm.

The process is preferably carried out in such a way that in a vibratory mill, ball mill, Roll mill, pendulum roll mill or air jet mill.  

The invention also relates to the use of the finely divided crystalline materials according to the invention layered sodium disilicates for the production of detergents and cleaning agents finally dish detergent.

The invention also relates to the use of the finely divided crystals layered sodium disilicate as a builder.

The invention also relates to detergents and cleaning agents containing an inventive finely divided crystalline layered sodium disilicate, especially in addition to other content, Active and auxiliary substances included. The following therefore applies to the following quantities: if necessary - even if not always explicitly mentioned - by the usual Ingredients, active ingredients and auxiliaries for detergents and cleaning agents for a total of 100 % By weight are to be brought.

Such detergents and cleaning agents preferably contain 1 to 80% by weight of the invention according to finely divided crystalline layered sodium disilicate.

Such detergents and cleaning agents preferably contain 1 to 80% by weight of zeolite and 1 to 80% by weight of the finely divided crystalline layered sodium disilica according to the invention tes.

Such washing and cleaning agents preferably contain 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 inventive fine partial crystalline layered sodium disilicate.

Such detergents and cleaning agents preferably contain 1 to 80% by weight of the invention according to finely divided crystalline layered sodium disilicate and 1 to 10% by weight Citric acid or salts of citric acid.

Such washing and cleaning agents preferably contain 1 to 80% by weight of zeolite, 1 to 80 % By weight of the finely divided crystalline layered sodium disilicate according to the invention and 1 to 10% by weight of citric acid or salts of citric acid.  

Such detergents and cleaning agents preferably contain 1 to 80% by weight of the invention according to finely divided crystalline layered sodium disilicate and 0.5 to 5% by weight modified cellulose.

Such washing and cleaning agents preferably contain 1 to 80% by weight of zeolite, 1 to 80 % By weight of the finely divided crystalline layered sodium disilicate according to the invention and 0.5 to 5% by weight of modified cellulose.

Such washing and cleaning agents preferably contain 1 to 80% by weight of zeolite, 1 to 80 Wt .-% crystalline layered sodium silicate, 1 to 80 wt .-% of the finely divided against crystalline layered sodium disilicate and 0.5 to 5% by weight of modified Cel lulose.

The aforementioned cellulose can optionally be chemically and / or mechanically modified become.

Surprisingly, it was found that the finely divided crystalline sodium diis Likat also has an increased calcium binding capacity.

The crystalline sodium disilicate according to the invention also results in significantly lower residues compared to commercial crystalline sodium disilicate, which can be shown with the aid of the sieve residue test. The mesh of the metal mesh fabric used with a mesh size of 20 µm simulates the mesh of textile fabric. Instead of metal mesh, a polyester mesh with the same mesh size can also be used. In the sieve residue test, the finely divided crystalline layered sodium disilicates according to the invention with d ₉₀ values below 60 μm show significantly reduced sieve residues.

The finely divided crystalline sodium disilicate according to the invention can advantageously be used as a builder, also called builder. It can be more common across the spectrum today Detergents such as compact full detergent, compact color detergent, full detergent lower bulk density, etc. can be used.  

Detergents containing the finely divided crystalline sodium disilicate according to the invention In model washing tests, much lower inorganic incrustations, what can be done Determination of ash can show. The latter remains when the fabrics burn up.

Inorganic incrustations consist of calcium carbonate precipitated water hardness, as well as from not completely dissolved or deposited Re most of detergent builders. You reduce the wearing comfort of the laundry by the it becomes scratchy and reduce the lifespan. The use of the finely divided crystalline Sodium disilicate in detergents therefore gives an important advantage with regard to Langle texture and comfort.

The properties of the finely divided crystalline layered sodium according to the invention disilicate was determined using the following measurement methods.

Determination of calcium binding capacity

A mixture of a buffer stock solution and deionized water is placed in an ErWeKa disolution tester, stirred and heated to 30 ° C. The buffer stock solution is an aqueous solution of glycine, sodium chloride, calcium chloride and sodium hydroxide in suitable concentrations. The calcium-sensitive electrode model 932001 from Orion is immersed in the solution and calibrated by adding a calcium stock solution to the solution. This is done with the evaluation unit EA 940 from Orion. After the addition, the solution contains a water hardness of 17 degrees German water hardness (17 ° dH). The Orion EA 940 is started simultaneously with the addition of the test substance (1 g). The pH of the measuring solution is 10.2. The Orion EA 940 releases the concentration of free calcium ions at certain intervals. Using the known weight of calcium, the concentration of free, unbound calcium ions after 10 minutes indicates the amount of bound calcium, the calcium binding capacity. This is given in mg CaCO ₃ / g.

Determination of the grain distribution with the Microtrac granulometer

The particle size in aqueous dispersion is determined using a Granulometer Microtrac ASVR / FRA from Leeds u. Northrup determined. The reflection or diffraction of a laser beam is measured when penetrating the dispersion. For this, 400 ml of ethanol are pumped through the laser measuring cell. The solid sample (e.g. 70 mg) is metered in automatically and the particle size distribution is determined after 10 min. The evaluation unit of the device calculates the d ₅₀ and d ₉₀ values.

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.

Sieve residue test

For this purpose, 800 ml of tap water [water hardness 14 ° dH (degree of German hardness)] to 20 ° C tempered and stirred with a propeller (bar) stirrer. 2 g of the test substance added and stirred for 20 min. With the slight vacuum of a water jet pump, the Dispersion sucked through a 20 µm metal mesh. The sieve becomes one at 80 to 100 ° C Dried for an hour in a forced-air drying cabinet. The weight gain is on the weight related and standardized to 100% and referred to as residue.

Preparation of the test detergents (Table 2)

The optical brighteners are mixed in a quarter of the nonionic amount and in one Household multimixer (Braun) mixed with half the amount of soda. In ploughshare The remaining soda and the total amounts of zeolite and polymer 15 Mi grooves at 300 rpm. mixed. Then half of the remaining nonionic amount in 5 Minutes sprayed on. Then the SKS-6 or the ground product is added and 10 minutes mixed. The remaining second half of Nonionic is then applied in a further 5 minutes sprays. Finally, anionic, soap, anti-foam, phosphonate and optical brighteners added and 10 minutes at 300 rpm. mixed. The Mi from the Lödige mixer under low shear stress with perborate, TAED and En zymen added and mixed for 15 minutes.  

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 the test detergent washed repeatedly (15 times) at a dosage of 65 g test detergent / wash. The test fabrics, in particular a cotton terry (from Vossen), each one Cotton double rib, polyester / cotton blend (type 20A) and standard tree wool fabric (type 10A) from the laundry research Krefeld Testgewebe GmbH and a Stan dardbaumwollgewebe from the Federal Material Testing Institute St. Gallen, Switzerland additional laundry ballast (3.75 kg) added. After 15 washes each of the tissues taken a sample and placed it in a muffle furnace at a temperature of 1,000 ° C and ashed for a period of 24 hours.

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%
<710µm: 2.15%
<500 µm: 6.9%
<300µm: 13.7%
<150 µm: 26.9%
d ₅₀ = 68 µm
d ₉₀ = 321 µm.

The sieve residue test showed 91.3% residue.

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%.

According to sieve analysis, it had the following particle size distribution:
<1000 µm: 3.4%
<500 µm: 17.5%
<300 µm: 26.6%
<150 µm: 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.  

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.

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%
<150µm: 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.

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.  

Example 6 (Invention)

In a pendulum roller mill (type PM00) from Neuman & Esser with a rotating classifier, fan, dust separator and filter system, 1000 kg of SKS-6 with the particle size distribution according to the starting product from Example 1 were ground. The throughput was 83.5 kg / h (material for the filter: 5.5 kg / h, air pressure in the air classifier: 290 mmWS).
a) At a classifier speed of 250 rpm, a ground product with the following grain size distribution (Microtrac) was obtained: <1 µm: 0.6%, <1.5 µm: 1.2%, <2 µm: 3.3% , <3 µm: 6.2%, <4 µm: 8.7%, <6 µm: 12.6%, <8 µm: 16.9%, <12 µm: 24.8%, <16 µm: 33.1%, <24 µm: 49.8%, <32 µm: 67.2%, <48 µm: 89.8%, <64 µm: 96.2%, <96 µm: 100%, d ₅₀ = 24.1 µm, d ₉₀ = 48.5 µm.

At higher speeds, finer material is also deposited in the classifier (b and c):
b) At a classifier speed of 340 rpm, a ground product with the following particle size distribution (Microtrac) was obtained: <1 µm: 0.5%, <1.5 µm: 1.1%, <2 µm: 3.5% , <3 µm: 6.3%, <4 µm: 8.5%, <6 µm: 13.3%, <8 µm: 18.2%, <12 µm: 27.8%, <16 µm: 36.3%, <24 µm: 56.8%, <32 µm: 74.9%, <48pm: 93.6%, <64 µm: 98.8%, <96 µm: 100%, d ₅₀ = 21.4 µm, d ₉₀ = 44.9 µm.
c) At a classifier speed of 450 rpm, a ground product with the following particle size distribution (Microtrac) was obtained: <1 µm: 0.6%, <1.5 µm: 1.5%, <2 µm: 4.8% , <3 µm: 8.8%, <4 µm: 12.8%, <6 µm: 18.5%, <8 µm: 24.6%, <12 µm: 37.8%, <16 µm: 53.8%, <24 µm: 81.2%, <32 µm: 93.7%, <48 µm: 100.0, d ₅₀ = 15.1 µm, d ₉₀ = 29.6 µm.

The mill products had the following phase distributions: alpha disodium disilicate 8.3%, beta disodium disilicate 7.5%, delta disodium disilicate 82.8%, amorphous content 1.4%.  

Table 1

Sieve residue and calcium binding capacity

Example 7 (Invention)

In accordance with the general rule "preparation of the test detergents", a Test-Compact detergent with 31% by weight of finely divided crystalline sodium disilicate from Bei game 4 made. In model washing tests according to the general regulation "Washing trials" examined the formation of inorganic incrustations. The The average ash value of all five fabrics is 1.50%.

Example 8 (Invention)

In accordance with the general rule "preparation of the test detergents", a Test-Compact color detergent with 35 wt .-% fine-particle crystalline sodium disilicate Example 4 prepared. In model washing tests according to the general regulation "Washing trials" examined the formation of inorganic incrustations. The The average ash value of all five fabrics is 1.53%.

Example 9 (Invention)

In accordance with the general rule "preparation of the test detergents", a Test-Compact detergent with 12% by weight of finely divided crystalline sodium disilicate from Bei  game 5 made. In model washing tests according to the general regulation "Washing trials" examined the formation of inorganic incrustations. The The average ash value of all five fabrics is 1.71%.

Example 10 (Invention)

In accordance with the general rule "preparation of the test detergents", a Test laundry detergent with 4% by weight of finely divided crystalline sodium disilicate from Example 6c posed. In model washing tests according to the general regulation "washing tests" the formation of inorganic incrustations was examined. The mean of the Ash values of all five fabrics is 1.86%.

Example 11 (comparison)

A test was carried out in accordance with the general rule "preparation of the test detergents" detergent with 12 wt .-% SKS-6 prepared from Example 1. 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 2.54%.  

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, Matthese & Weber
Bicarbonate: Solvay
Percarbonate: Oxyper C, Solvay Interox
Perborate monohydrate: Degussa
Perborate tetrahydrate: Degussa
TAED: TAED 4049, Clariant
Anionic: ARL, Fa. 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: from Fluka
Polyvinylpyrrolidone: Sokalan HP50, from BASF
Soil release polymer: SRC 1, Clariant
CMC: Tylose 2000, from Clariant
Sulphate: light sulphate, from Solvay

Claims (26)

1. Fine crystalline layered sodium disilicate 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, characterized in that it a salary of
0 to 40% by weight of alpha disodium disilicate
0 to 40% by weight of beta disodium disilicate
40 to 100% by weight of delta disodium disilicate
0 to 40% by weight of amorphous parts
having. 2. Fine-particle crystalline layered sodium disilicate according to claim 1, characterized in that it has a content of
0 to 20% by weight of alpha disodium disilicate
0 to 30% by weight of beta disodium disilicate
50 to 95% by weight of delta disodium disilicate
0 to 20% by weight of amorphous parts
having. 3. Fine crystalline layered sodium disilicate according to claim 1 or 2, characterized in that it has a content of
0 to 10% by weight of alpha disodium disilicate
0 to 15% by weight of beta disodium disilicate
70 to 90% by weight of delta disodium disilicate
0 to 10% by weight of amorphous parts
having. 4. Fine-particle crystalline layered sodium disilicate according to one or more of the Claims 1 to 3, characterized in that it is free of sodium metasilicate. 5. Fine crystalline layered sodium disilicate according to one or more of claims 1 to 4, characterized in that it has ad ₉₀ value of <100 microns. 6. Fine-particle crystalline layered sodium disilicate according to one or more of claims 1 to 5, characterized in that it has ad ₉₀ value of <60 µm. 7. Finely divided crystalline layered sodium disilicate according to one or more of claims 1 to 6, characterized in that it has a calcium binding capacity of more than 170 mg CaCO ₃ / g at 30 ° C and 17 ° dH. 8. finely divided crystalline layered sodium disilicate according to one or more of claims 1 to 7, characterized in that it has a calcium binding capacity of more than 180 mg CaCO ₃ / g at 30 ° C and 17 ° dH. 9. finely divided crystalline layered sodium disilicate according to one or more of claims 1 to 8, characterized in that it has a calcium binding capacity of more than 190 mg CaCO ₃ / g at 30 ° C and 17 ° dH. 10. Finely divided crystalline layered sodium disilicate according to one or more of the Claims 1 to 9, characterized in that there is a residual screen residue of less than 60%. 11. Finely divided crystalline layered sodium disilicate according to one or more of the Claims 1 to 10, characterized in that there is a residual screen residue of less than 40%.   12. Finely divided crystalline layered sodium disilicate according to one or more of the Claims 1 to 11, characterized in that there is a residual screen residue of less than 30%. 13. A process for the production of finely divided crystalline layered sodium disilicates according to one or more of claims 1 to 12, characterized in that a sodium layer silicate with a particle diameter d ₅₀ of 80 to 400 µm is ground to a egg n d ₉₀ value of <100 µm . 14. A process for the production of finely divided crystalline layered sodium disilicates according to one or more of claims 1 to 12, characterized in that a sodium layered silicate with a particle diameter d ₅₀ of 80 to 400 µm is ground to an egg n d ₉₀ value of <60 µm . 15. Process for the production of finely divided crystalline layered sodium disilicates according to claim 13 or 14, characterized in that in a vibrating mill, Ball mill, roller mill, pendulum roller mill or air jet mill. 16. Use of finely divided crystalline layered sodium disilicates after one or more of claims 1 to 12 for the production of washing and cleaning agents including dishwashing detergents. 17. Use of finely divided crystalline layered sodium disilicate after one or more of claims 1 to 12 as a builder. 18. Detergent and cleaning agent, characterized in that it is 1 to 80 wt .-% of the fine Partial crystalline layered sodium disilicate according to one or more of the Claims 1 to 12 contains. 19. Detergent and cleaning agent, characterized in that it contains 1 to 80% by weight of zeolite and 1 to 80% by weight of the finely divided crystalline layered sodium disilicate contains one or more of claims 1 to 12.   20. 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 finely divided crystalline layered sodium disilicate according to one or more of the claims Contains 1 to 12. 21. Detergent and cleaning agent, characterized in that it is 1 to 80 wt .-% of the fine Partial crystalline layered sodium disilicate according to one or more of the Claims 1 to 12 and 1 to 10 wt .-% citric acid or salts of citric acid ent holds. 22. Detergent and cleaning agent, characterized in that it contains 1 to 80% by weight of Zeo lith, 1 to 80 wt .-% of the finely divided crystalline layered sodium disilicate according to one or more of claims 1 to 12 and 1 to 10 wt .-% citric acid or salts of citric acid. 23. Detergent and cleaning agent, characterized in that it contains 1 to 80% by weight of the fine Partial crystalline layered sodium disilicate according to one or more of the Claims 1 to 12 and 0.5 to 5 wt .-% modified cellulose contains. 24. Detergent and cleaning agent, characterized in that it contains 1 to 80% by weight of zeolite, 1 to 80 wt .-% of the finely divided crystalline layered sodium disilicate according to ei nem or more of claims 1 to 12 and 0.5 to 5% by weight of modified cellulose contains. 25. washing and cleaning agent, characterized in that it contains 1 to 80% by weight of zeolite, 1 to 80 wt .-% crystalline layered sodium silicate, 1 to 80 wt .-% of the finely divided kri Stalline layered sodium disilicate according to one or more of claims 1 contains up to 12 and 0.5 to 5% by weight of modified cellulose. 26. Detergent and cleaning agent according to one or more of claims 23 to 25, there characterized in that the cellulose is chemically and / or mechanically modified that can.