JPH03210398A - Manufacture of super high density detergent powder containing clay - Google Patents

Abstract

PURPOSE: To obtain a detergent powder of a high bulk density having good dissolving characteristics and softening characteristics by adding a swellable clay to a specified granular starting substance and treating both of them with a high speed mixer/granulator.

CONSTITUTION: 35 wt.% or less of a swellable clay is added to a granular starting substance containing 10-70 wt.% of a non-soap detergent active substance (a) and at least 10 wt.% of a water-soluble crystalline inorg. salt (b) including sodium tripolyphosphate and/or sodium carbonate so that the wt. ratio of the components (a), (b) is max. 25 and the obtained mixture is treated by using a high speed mixer/granulator having both of stirring action and cutting action to obtain the objective granular detergent compsn. or component having bulk density of 550 g/l or more. A usable suitable detergent compd. is a synthetic anionic compd. and a nonionic compd.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for producing granular detergent compositions or ingredients having high bulk density and good powder properties. More particularly, the present invention relates to a method for producing granular detergent compositions having good powder dissolution properties and good softening properties in washing performance.

[Prior art] In recent years, relatively high bulk densities (for example, 550 g/1 or more) have been developed.
There is considerable interest in the detergent industry in the production of laundry powders having a

Generally speaking, there are two main methods by which detergent powders can be manufactured. The first type of method is
It involves spray drying an aqueous detergent slurry in a spray drying tower. In a second type of method, the various components are dry mixed and optionally coagulated with a liquid (eg, a non-ionic substance).

The most important factors governing the bulk density of detergent powders are the bulk density of the starting materials in the case of dry mixing methods and the chemical composition of the slurry in the case of spray drying methods. Both factors can only be varied within limited ranges. For example, the bulk density of a dry-blended powder can be increased by increasing the content of relatively dense sodium sulfate, but since that content does not contribute to the detergent properties of the powder, its overall use as a laundry powder is generally adversely affect the character of the

A practical increase in bulk density can therefore only be achieved by additional processing steps resulting in densification of the detergent powder. Several methods are known in the art to provide this type of densification. For this reason, particular attention is paid to the densification of the spray-dried powder by post-tower treatment.

For example, Japanese Patent Application No. 61 [169897 (Kao) discloses that a spray-dried detergent powder containing high levels of anionic surfactants and low levels of bilgu (zeolite) is sequentially applied to a high speed mixer/granulator. Discloses a method of subjecting it to powdering and granulation treatment. Granulation is carried out in the presence of "surface property-enhancing agents" and optionally binders.

Furthermore, it is also known to incorporate smectite-type clays into detergent powders in order to obtain a fabric softening effect. Furthermore, British Patent No. 2.063.289 (Unilever)
detergent powder containing less than 20% by weight phosphate and more than 20% by weight anionic surfactant.
The patent discloses adding bentonite or kaolin to the clarification slurry to make it hard and free-flowing.

However, one of the inherent problems with detergent compositions having high bulk densities is that their solubility properties are generally reduced compared to corresponding compositions having lower bulk densities. This is believed to be due to the lower porosity of the powder particles.

Surprisingly, we have discovered that by mixing swellable clay with granular detergent starting material and then processing this mixture in a high-speed mixer/granulator that has both stirring and cutting effects, the clay can be turned into a clarification slurry. It has been found that a high bulk density detergent powder with much better dissolution and softening properties is obtained than by mixing and then spray drying.

SUMMARY OF THE INVENTION The present invention is a method for producing a granular detergent composition or ingredient having a bulk density of at least 550 g/l, comprising: (a) up to 35% by weight of swellable clay;
% by weight of a non-soap detergent active and (b) at least 10% by weight of a water-soluble crystalline inorganic salt including sodium tripolyphosphate and/or sodium carbonate; (bl
Provided is a method for producing a granular detergent composition or component, characterized in that the weight ratio of do.

[In the method of the detailed description of the invention, the granular starting material is mixed with the swellable clay and then processed in a high speed mixer/granulator.

The starting materials used in the process of the present invention include (i) 10 to 70% by weight of non-soap detergent actives;
Both contain 15% by weight of a water-soluble crystalline inorganic salt, and the ingredients (
The weight ratio between (b) and (b) is at most 2.5. Preferably, the ratio of components (a) and (b) is between 0.1 and 2.0.
, more preferably 0.1 to 0.4.

The starting materials include, for example, compounds conventional in detergent compositions such as detergent actives, virgoos, all well known in the art.

Detergent actives can be non-soap, anionic, zwitterionic,
It is possible to choose from zwitterionic or non-ionic detergent actives or mixtures thereof. Particularly suitable are mixtures of all anionic active substances or nonionic detergent active substances, such as mixtures of alkali metal salts of alkylbenzenesulfonic acids with alkoxylated alcohols.

Suitable detergent compounds for use are synthetic anionic and nonionic compounds. The former are generally water-soluble alkali metal salts of organic sulfates and sulfonates with alkyl groups having from about 8 to about 22 carbon atoms, where the term alkyl is used to encompass the alkyl portion of higher acyl groups. Ru. Examples of suitable synthetic anionic detergent compounds are alkyl sodium and potassium sulfates, especially those obtained by sulfating higher (Cs-Cl8) alcohols made, for example, from tallow oil or coconut palm; alkyl (09-C2o) benzenes. Sodium and potassium sulfonates, especially linear secondary alkyl (C1
G”” Cis) Sodium benzene sulfonate; Sodium alkyl glyceryl ether sulfates, especially ethers of higher alcohols derived from tallow oil or coconut parts and synthetic alcohols derived from petroleum; Coconut oil aliphatic monoglycerides sulfates and sulfones Sodium and potassium salts of sulfuric esters of higher (Ca-Cl8) aliphatic alcohol-alkylene oxide (especially ethylene oxide) reaction products; coco esterified with isethionic acid and neutralized with sodium hydroxide Reaction products of fatty acids such as fatty acids; sodium and potassium salts of fatty acid amides of methyltaurine;
Alkane monosulfonates, such as α-olefins (
those obtained by reacting Ca-C20) with sodium bisulfite and those obtained by reacting paraffins with So and C12, followed by hydrolysis with base to give random sulfonates; and olefin sulfone-1. [This term refers to olefins (especially C
1o to C20 α-olefin) is reacted with S03,
is then used to describe a material created by neutralizing and hydrolyzing the reaction product]. Preferred ionic detergent compounds are (011-C15)
Sodium alkylbenzenesulfonate and (016
~018) Sodium alkyl sulfate.

Suitable nonionic detergent compounds that can be used are, in particular, compounds having hydrophobic groups and reactive hydrogen atoms (for example aliphatic alcohols, acids, amides or alkylphenols).
and alkylene oxide (especially ethylene oxide) alone or in mixtures with propylene oxide.

Certain nonionic detergent compounds include alkyl (C6-C22) phenol-ethylene oxide condensates, generally having 5 to 25 EO (i.e., 5 to 25 units of ethylene oxide per molecule), aliphatic (Ca ~C
18) Condensation products of a first or second linear or branched alcohol with ethylene oxide; and also products produced by condensing ethylene oxide with the reaction product of propylene oxide and ethylenediamine.

Other so-called non-ionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.

Mixtures of detergent compounds, such as mixtures of anionic compounds or mixtures of anionic and nonionic compounds, can also be used in detergent compositions, giving suppressed and low foaming properties, especially in the latter case. . This is advantageous for compositions intended for use in automatic washing machines that cannot withstand foaming.

Although certain amounts of amphoteric or zwitterionic detergent compounds may also be used in the compositions of the present invention, this is generally undesirable due to their relatively high cost. When amphoteric or zwitterionic detergent compounds are used, they are used in smaller amounts in the composition relative to the more commonly used anionic and/or nonionic synthetic detergent compounds.

The detergent builder can be any substance that reduces the level of free calcium ions in the wash liquor, preferably for example the generation of alkaline PI, the suspension of soils removed from fabrics, and the softening of clay materials. It imparts other advantageous properties to the composition, such as suspension.The amount of detergent builder can be from 10 to 70% by weight, particularly preferably from 25 to 50% by weight.

Examples of detergent builders are precipitable builders such as e.g. alkali metal carbonates, bicarbonates, orthophosphates; metal sequestrant builders such as e.g. alkali metal tripolyphosphates or nitrilotriacetates; or e.g. amorphous Includes ion exchange builders such as alkali metal aluminosilicates or zeolites.

The starting materials can be prepared by any suitable method, such as spray drying or dry mixing. Furthermore, suitable particulate materials can also be produced by a dry neutralization process, in which a liquid acidic anionic surfactant precursor is reacted with a solid alkaline inorganic component, such as a carbonate. This type of dry neutralization method is described, for example, in British Patent No. 2,166,452 (Kao), No. 1.404.317.
(Bell Corporation) or No. 1.369.269 (Colgate Corporation).

In the method of the invention, the starting material is fed to a high speed mixer/granulator having both stirring and cutting functions. The type of high speed mixer/granulator suitable for use in the process of the invention is bowl-shaped and has a substantially vertical agitator axis. This is particularly suitable if the mixer/granulator further has cutting means on the side wall. These stirring and cutting means are
Advantageously, they can be operated independently of each other and at separate variable speeds. Furthermore, it is preferable to equip the mixer container with a jacket for cooling or heating purposes. If necessary, cooling can also be provided by a cryogenic unit.

An example of a suitable mixer is the Fukani® FS-C series, such as the Fukani F83G manufactured by Fukae Powtech Industries Co., Ltd. (Japan). The device is primarily in the form of a bowl-shaped container accessible through a top port, with a stirrer having a substantially vertical axis near its bottom and a cutter in the side wall.

A similar mixer made in India is the Sapphire® RMG series of rapid mixers/granulators, which, like the hook-and-loop mixer, are available in different sizes. This device is primarily in the form of a bowl-shaped container that is pneumatically raised and sealed against a fixed lid. 3
A blade agitator and a four blade cutter share a substantially vertical axis of rotation mounted on the lid. The agitator and cutter can be operated independently of each other, and the agitator is 75+p
m or 150 rpm:: and the cutting machine is 144
It can be operated at speeds of 0 rpm or 288 rpm. The container can be equipped with a water jacket that can be used to cool or heat the contents of the container.

The Sapphire RM G-100 mixer, suitable for handling 60 kg detergent powder batches, has a bowl of 1 m diameter and 0.3 m depth. The working capacity is 2001. The stirring blade has a diameter of 1m, and the cutting blade has a diameter of 011m.
It is m.

Other similar mixers found suitable for use in the method of the invention are the Geosna® V series manufactured by Sierx & Söhne, West Germany; and the T
, K., Pharma Matrix® manufactured by Fielder Limited. Other mixers considered suitable for use in the method of the present invention are the Fuji® VG-C series manufactured by Fuji Sangyo Co., Ltd. (Japan); and the Zanchetta Kai & Co. Sr.
It is Roto (registered trademark) manufactured by one company.

A further mixer that has been found suitable for use in the process of the invention is the Lodige(R) FM series batch mixer manufactured by Morton Machine Company Limited, Scotland. This differs from the mixer described above in that its stirrer has a horizontal axis.

These devices (which can be continuous or batch fed) essentially consist of a large stationary hollow cylinder and a central rotating shaft. The shaft has several different types of vanes attached to it. The rotation speed is variable and depends on the desired degree of densification and particle size. The vanes on the shaft provide a good mixing effect of the solids and liquids being mixed at this stage. The average residence time depends in part on the rotational speed of the shaft and the position of the vane relative to the continuous plant. Independently driven high speed cutting blades can also be integrated into this type of mixer and operated relative to the main stirrer (eg Lodige® KM series or Drais® KT series).

The use of high speed mixers/granulators is important to achieve granulation and densification. Before granulating the starting material, a pretreatment, for example a powdering step, can be carried out. Whether this is necessary depends, inter alia, on the method of preparation of the starting materials, their particle size and water content. For example, spray-dried powders more often require powdering pretreatment than dry-blended powders.

To carry out pulverization, a suitable stirring/cutting regime must be chosen, which is generally characterized by relatively high speeds for both the stirrer and the cutting machine and relatively short residence times, for example from 1 to 4 minutes. .

Similarly, the granulation step is carried out by operating the stirrer and cutter at relatively high speeds, which requires the presence of a liquid binder. The preferred binder is water. The amount of binder added should preferably not exceed 6% by weight. This is because higher amounts will adversely affect the flow properties of the final product.

The liquid binder can be added before or during granulation, preferably by spraying it while the equipment is running. Furthermore, the starting material may already contain sufficient water so that the addition of other liquid binders is not necessary. In this case, powdering and granulation can be carried out in a single operation.

According to a preferred embodiment of the invention, granulation is carried out at a temperature above room temperature, for example above 30°C or 45°C. For example, spray-dried detergent base powder exiting the tower at a temperature of about 45° C. or higher can be fed directly to the process of the invention. Of course, the spray-dried powder can also first be cooled, for example by an air lift.

In the process of the invention, swellable clay (gvelliB clxr) is added to the mixer/granulator in an amount of up to 35% by weight, based on the starting materials.

The swellable clay material can be any substance of the scale type that provides fabric softening properties. Generally, these substances are 3
It is of natural origin, containing layers of swelling smectite-type clay. Preferably the clay is of the calcium and/or sodium montmorillonite type.

The effectiveness of clay-containing materials as fabric softeners depends, among other things, on the level of smectite-type clays. For example, calcite,
Impurities such as fluorite and silica are often present.

Relatively impure clays can also be used as long as such impurities are tolerated in the composition.

The amount of fabric softening clay material in the composition should be sufficient to impart flexibility. Amounts of 1.5 to 35% by weight, preferably 4 to 20% by weight, calculated on the clay mineral itself, have been found to be effective.

In addition to detergent active substances and detergent virgoos and clay-containing substances,
The compositions according to the invention may optionally also contain other ingredients commonly found in detergent compositions, in amounts that are typical for additives of this type used in fabric laundry detergent compositions. be. Examples of additives of this type are foam promoters (e.g. alkanolamides, especially monoethanolamide obtained from palm kernel and coco fatty acids), foam suppressants, oxygen-releasing bleaches (e.g. sodium perborate and peracid bleach precursors, chlorine-releasing bleaches (e.g. trichloroisocyanuric acid), fillers (e.g. sodium sulfate), as well as fluorescent agents, fragrances, enzymes (e.g. proteases, lipases and amylases), which are generally present in very small amounts. ), fungicides and colorants.

The method of the invention allows the production of detergent compositions with a high bulk density of at least 550 g/i. A surprising advantage of the process according to the invention is that the bulk density of the powder obtained is higher than if the clay was mixed into the clutch slurry before spray drying the starting material.

Another advantage of the process according to the invention is that the softening action of the final detergent powder is improved compared to when the clay is mixed into the clutch slurry and then spray dried. This effect of the method according to the invention can be confirmed by the methods used for evaluating softening properties as described in the prior art.

Another advantage of the method according to the invention is that the storage stability of the final detergent powder is improved. This can be confirmed by the Unlimited Compressibility Test (UCT). In this test, detergent powder is placed in a cylinder with a diameter of 13al and a height of 15CXl.

A 10 kg weight is then placed on top of the powder. After 5 minutes, remove the weight and remove the cylinder wall. A load is then gradually applied to the top of the column of compressed detergent powder and the weight (kg) at which the column collapses is determined. This number is a function of the viscosity of the detergent powder and has been found to be a good measure of storage stability.

[Example] The invention will now be further illustrated by non-limiting examples.

Parts and percentages are by weight unless otherwise specified.

In the following examples, the following abbreviations are used for the materials used: LAS: linear alkylbenzene sulfonate STP nitripolyphosphate sodium silicate: alkaline sodium silicate carbonate:
Sodium carbonate sulfate: Sodium sulfate clay: Calcium or sodium montmorillonite.

Examples 1-3 The following detergent powders were made by spray drying aqueous slurries. The composition (% by weight) of the powder thus obtained is shown below.

Table 1 Example 1 2 3L A S
31 34 34 total N
S D (1) 31 34 34S
T P 41 46
46 Silicate 5 6
6 Carbonate 89 Sulfate 10 Gold salt (b) 64 52 6
1 clay 10 water
5 4
Ratio of 5 components (1): (b) 0.48 0.
65 0.56 The composition of Example 2 was made of Ca-clay (Burasa, Colin Stewart Minerals Co., II, K
) was added to the clutch file slurry and spray-dried. In this case, the sodium carbonate was omitted from the slurry to keep it at a sufficiently low viscosity to facilitate spray drying. Example 3 was a spray dried powder that did not contain clay but contained carbonate.

The compositions of Examples 2 and 3 contain higher weight percent LAS, STP, and silicates than the composition of Example 1, allowing for dilution in the subsequent addition of carbonate or clay during the densification/granulation step, respectively. I made it.

These powders were added to a Fukani FS-30 high speed mixer/granulator (10 kg - Example 1; 9.2
kg-Example 2;9. Okg-Example 3). These powders were pulverized for 2 minutes at 70° C. with a stirrer speed of 300 rpm and a cutter speed of 3000 rpm. Then 0.8 kg of sodium carbonate and 1. t
1- of Ca-clay was added to the densified powders of Examples 2 and 3. The granulation was then carried out using approximately 150 ml of water at a stirrer speed of 275+pm and 3000+pm.
The addition was carried out over a period of 1 minute at a cutting machine rotation speed of m. Of the powder obtained, oversize (>170
0 μIm) was sieved. The composition of these powders (
Weight %) were as follows: Table 2 Example 1 2 3 LAS 31 31 31STP
41 41 41 silica 1-
5 5 5 carbonate 8
8 8 Clay 1010 Sulfate 10 Water 5 5 5
The powder properties of the sieved material are shown in Table 3 below.

Table 3 Example 1 2 3 Bulk density 1t (g/
l) 965 738 980 Dynamic flow rate (mouth
/ri 149 145 150UCT
2.9 B, 2 2.9 Particle size (μn
) 870 699 856N
2.33 1.45 270 CUCT is the % unrestricted compressibility and N is the distribution of average particle size.

The solubility properties of the concenf+ajedl powders and the respective undensified control powders shown in Tables 2 and 3 were determined by standard conductivity measurement techniques. 500+425 μ■) were used to compare the dissolution properties of comparable particle size ranges.The rate of dissolution was scaled to the ratio SA/SAb to compensate for the inevitable differences in powder properties, e.g. bulk density. where SA is the surface area per unit weight of a given granulated powder (g) or non-densified base (b).The ratio SA/SA, therefore, gives a measure of the densification of a particular powder. The surface area (SA) per 1 kg is the following formula: %
(Formula %) [In the formula, BD represents the bulk density, and d represents the average diameter (μm'
) (assuming spherical particles).

The results of the dissolution experiments are shown in Table 4 and are further shown graphically in FIG. In this figure, a linear relationship is observed between the dissolution rate and the ratio SA 2 /SAb for the densified powders from Examples 1 and 2 and the undensified base powder of Example 1. This indicates that the rate of dissolution is a function of the surface area available for mass transfer. This diagram is
Example 3, where the clay was post-dosed before granulation, shows higher dissolution rates than expected for similar powders. This indicates that clay contributes to improving dissolution properties.

Table 4 Example 1 2 3 Dissolution rate (s ”l) 1.92 2.54
2.85SA /SA O,230,470
, 31b Softening property % Q 75.3 99.5
Table 4 also shows the softening properties of various compositions.

The softening of the densified powders of Examples 1-3 was measured on a terry towel cloth. Tergotometer washing at a powder concentration of 3.6 g/l was carried out for 30 minutes at a fabric to liquid weight ratio of 1:20. The relative degree of softening was determined according to standard methods by a panel of 10 experts, as described in the prior art.

The excellent softening properties of the composition of Example 3 according to the invention (in which the clay was post-dosed during granulation) are explained by the addition of clay powder to Example 1 during laundering in a concentration equal to that of Example 3. This can also be illustrated by a comparative experiment.

When using the composition of Example 1 and adding clay separately to the laundry, a softness value of 97.5 was measured. A comparison of this value with the flexibility value of 99.5 found in Example 3:
This shows that sufficient softening performance can be obtained by the method of the present invention. However, when clay is added to the clarification slurry before spray drying as in Example 2,
A much lower flexibility value of 75.3 was measured.

[Brief explanation of drawings]

FIG. 1 is a characteristic curve diagram showing the results of a dissolution experiment.

Claims (7)

[Claims] (1) A method for making a granular detergent composition or ingredient having a bulk density of at least 550 g/l, comprising: (a) 10 to 70% by weight of a non-soap detergent active; and (b
) at least 10% by weight of a water-soluble crystalline inorganic salt comprising sodium tripolyphosphate and/or sodium carbonate, the granular starting material having a weight ratio of components (a) and (b) of at most 2.5; A method for producing a granular detergent composition or ingredient, characterized in that the mixture is added with a high-speed mixer/granulator having both stirring and cutting effects. 2. The method according to claim 1, wherein the ratio of components (a) and (b) is between 0.1 and 2.0, preferably between 0.1 and 1.0. (3) The method according to claim 1 or 2, wherein the swelling clay is a calcium and/or sodium montmorillonite type clay. (4) A method according to any one of claims 1 to 3, wherein the mixer/granulator is a bowl-shaped high speed mixer/granulator with a substantially vertical agitator axis. 5. A method according to claim 1, wherein the particulate starting material comprises a spray-dried detergent powder. (6) A process according to any one of claims 1 to 5, wherein the particulate starting material comprises 15 to 50% by weight of sodium tripolyphosphate. (7) Claims 1 to 3, wherein the granulation is carried out at a temperature of 45°C or higher.
6. The method according to any one of 6.