JPH0798960B2 - High bulk density granular detergent composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention is of high bulk density and good dispensing properties.
s) in the form of a granular detergent composition. Furthermore, the invention relates to a method for producing such a detergent composition, and in particular for its continuous production.

BACKGROUND AND PRIOR ART Recently, there has been considerable interest within the detergent industry in powder detergents having relatively high bulk densities, eg, 600 g / l and above. There are several methods known in the art by which densified powder detergents can be produced. Support tower processing (p
Particular attention has been paid to the densification of spray-dried powders by ost-tower treatment. For example, in the method disclosed in Japanese Patent Application Publication No. 61-069897 (Kao), a spray-dried detergent powder containing a high level of anionic surfactant and a low level of builder (zeolite) is mixed with a high speed mixer. / Sequentially pulverize and granulate in a granulator. This granulation is carried out in the presence of a "surface property modifier" and optionally a binder. In this high speed mixer / granulator, first the spray-dried powder is crushed to a finely divided state, then the surface improver and optional binder are added and the ground material is granulated, A high bulk density final product is formed. A surface modifier that is finely divided fine particles, such as finely divided sodium aluminosilicate, is clearly necessary to prevent the desired composition from forming large balls or cakes. The method described in this Japanese patent application is essentially a batch method and is therefore not very suitable for mass production of powder detergents. British Patent Application Publication No. 1,517,713
(UNILEVER) discloses a method of densifying a spray-dried or granulated powder detergent containing sodium tripolyphosphate and sodium sulphate with "Marmelizer (TM)" to spheronize. The apparatus has a substantially horizontal rough surface rotary table located at the base in a substantially vertical, smooth walled cylinder. British Patent Application Publication Nos. 1 and 4
53,697 (UNIVERS) discloses the use of "Marmelizer ™" to granulate powdered detergent ingredients together in the presence of a liquid binder to produce a granular detergent composition. The disadvantage of this device is that it results in powders or granules having a fairly wide particle size distribution, in particular a relatively high proportion of oversized particles. Such materials exhibit inadequate dissolution and dispersion properties, especially in low temperature short time machine wash in Japanese and other Far East washing machines. This is noticeable to consumers as a deposit of laundry and is wasted in machine washing. EP-A-327,963 (HENKEL) consists of a substantially horizontal stationary hollow cylinder and its central axis of rotation with several different types of blades mounted on it. By processing in a mixing device having
A continuous process for increasing the bulk density of spray-dried powder detergents is disclosed. Example 1 consists of an anionic surfactant, a nonionic surfactant, and soap, containing a three-component active system in which the amount of soap is about 13% of the active system, with a bulk density of 5
A 95 g / l densified powder detergent is disclosed. The formulation also contains a builder system consisting of 10% zeolite and 20% sodium tripolyphosphate. It is believed that the latter, sodium tripolyphosphate, is responsible for the desired favorable distribution characteristics in this composition. Related European Patent Application Publication No. 337,330 (HENKEL)
Discloses a modification of the conventional method of spraying a liquid nonionic surfactant onto a spray-dried base powder. The base powder is a low phosphate base powder and contains conventional ingredients in conventional amounts.
The bulk density increase by this method is at most 100 g / l EP 220,024 (Procter).
& Gamble), a spray-dried powder detergent containing high levels (30-85% by weight) of anionic surfactants with inorganic builders (sodium tripolyphosphate or sodium aluminosilicate and sodium carbonate). Mix and roll compressor ("chillsonator chi
lsonator ") under high pressure. After removing too large or too small, conventional equipment,
Granulate using, for example, a fluid bed tumble mixer, or a rotating drum or dish. Although powder detergents with increased bulk density can be prepared by the above method, all of the resulting powders are more difficult to dispense in European automatic washing machines than the corresponding non-densified powders. Have. As a result, a high proportion of the powder that is thrown into the machine remains in the dispenser, causing powder consumption and clogging. This problem is especially noticeable when using powder detergents containing little or no tripolyphosphate at low temperatures. The known densified powder detergents have inadequate dispensing properties and therefore these detergents must be used in combination with a dispensing tool or shuttle. Although this limits the use of the product, it is not in all cases well-understood by the consumer, and usually plastic shuttles can contribute to the disposable problem. Therefore, the object of the present invention is at least 600 g.
To provide a high bulk density granular detergent composition or components thereof having a bulk density of 1 / l, preferably at least 650 g / l, and nevertheless having good distribution properties. Another object of the invention is to provide a process for obtaining such compositions. The method is particularly suitable for mass production of such compositions, so continuous processes are preferred. It has been found that a granular detergent composition having a low phosphate content and a bulk density of at least 600 g / l and, surprisingly, having good distribution properties is obtained when certain requirements for formulation are met. .

DEFINITION OF THE INVENTION In a first aspect, the present invention relates to a granular detergent composition having a bulk density of at least 600 g / l or a component thereof, wherein the builder 10 is at least 50% by weight non-phosphate material. 70% by weight and one or more nonionic surfactants, anionic surfactants and soaps, the weight ratio of anionic surfactant to nonionic surfactant is less than 5: 1, and soap The amount of active system is 10
A composition or ingredient is provided which comprises ˜90 wt% of the ternary active system 5-45 wt%. In a second aspect, the invention provides that the particulate starting material is (i) in a high speed mixer / densifier having an average residence time of about 5 to 30 seconds, and then (ii) in a drying and / or cooling device. The present invention provides a method for producing the granular detergent composition or component of the present invention, which is treated.
Preferably, the particulate starting material is in the first stage brought to, or maintained in, the deformable state.

DETAILED DESCRIPTION OF THE INVENTION The granular detergent composition of the present invention comprises:
Includes 10-70% by weight builder system and 5-45% by weight active system. The builder system of the compositions of the present invention may be a single detergent builder in an amount of 10-70% by weight of the total formulation or a mixture of one or more detergent builders. However, the present invention is particularly applicable to powder detergents in which at least 50% by weight of the builder system is a non-phosphate material. This is because the distribution properties of the densified powders of conventional formulations are particularly poor in such cases. The builder can be any substance capable of reducing the level of free calcium ions in the wash liquor, preferably producing an alkaline pH, suspending soils removed from textiles, suspending textile soft clay substances. A composition is obtained that has other beneficial properties such as turbidity. The level of detergent builder is preferably 15-60% by weight. Examples of suitable detergent builders that can be used in the present invention include alkali metal carbonates, bicarbonates, precipitation builders such as orthophosphates, sequestration builders such as alkali metal tripolyphosphates or nitrilotriacetic acid salts. , Or ion exchange builders such as alkali metal aluminosilicates or zeolites, or layered silicates such as Na-S
KS-6 (Hoechst) may be mentioned. Preferably, the detergent builder is a non-phosphate builder such as zeolite. The active system of the composition of the present invention is a three component detergent active system consisting of an anionic surfactant, a nonionic surfactant, and soap. It is 5 to 45% by weight of the total formulation
Present in an amount of. It has been found essential that the weight ratio of anionic surfactant to nonionic surfactant is less than 5: 1, preferably less than 4: 1. In addition, the amount of soap must be at least 10% and less than 90% by weight of the active system in order to obtain the desired good distribution properties. Preferably, the amount of soap is 10-60 of the active system.
% By weight. The three-component active type anionic surfactant is
Water-soluble alkali metal salts of organic phosphoric and sulphonic acids, usually with alkyl groups containing about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of the higher acyl groups. . Examples of suitable synthetic anionic detergent compounds, for example those obtained by tallow or alkyl sulfates of sodium and potassium are generated from coconut oil, in particular higher _(C 8 ~C ₁₈₎ alcohol sulfating; sodium and alkyl _(C 9 _{~C 20)} benzenesulfonate potassium, particularly sodium linear secondary alkyl _(C 10 _{~C 15)} benzenesulfonate; and sodium alkyl glyceryl ether sulfates, obtained especially from tallow or coconut oil Ethers of higher alcohols and ethers of synthetic alcohols obtained from petroleum. Preferred anionic detergent compounds are sodium _(C 11 _{~C 15)} alkylbenzene sulfonates, and sodium _(C 16 _{~C 18)} alkyl sulphates. Suitable nonionic detergent compounds which can be used in the three-component active system include, in particular, reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, such as aliphatic alcohols, acids, amides or alkylphenols and alkylene oxides ( In particular, a reaction product with ethylene oxide alone or a mixture with propylene oxide) can be mentioned. Specific nonionic detergent compounds, alkyl _(C 6 _{-C 22)} phenols - ethylene oxide (typically 3～25EO, i.e. 1 ethylene oxide per mole 3-25 units) condensates ,, and aliphatic _(C 8 ~ C ₁₈ ) There are condensation materials of first or second straight or branched chain alcohols with ethylene oxide, typically on average 3-40 EO. Alkoxylated fatty alcohols, especially ethoxylated alcohols, are the preferred nonionic surfactants. The soap used in the composition of the present invention is a sodium salt of a natural or synthetic fatty acid. The alkyl group of the fatty acid may be a branched or straight chain alkyl group containing 8 to 22, preferably 12 to 20 carbon atoms.
A particularly preferred three component active system is the sodium salt of alkylbenzene sulfonic acid, an ethoxylated alcohol, and 1
It is a mixture of sodium soaps having 2 to 20 carbon atoms. Minimal amounts of amphoteric or zwitterionic detergent compounds may be used in the compositions of the present invention, but this is generally undesirable due to their relatively high cost. The powder detergents of the present invention may contain any of the ingredients conventionally present in compositions for laundering textiles. If desired, the powder of the invention may contain sodium silicate. High levels of silicates in the composition have a beneficial effect on partitioning and on powder structure and prevention of washing machine corrosion, but because the two components react together to form an insoluble silicon species, Not desirable in powders containing salt. Thus, the present invention is particularly applicable to powders containing less than 5% by weight, especially less than 2% by weight sodium silicate, which is expected to exhibit poor distribution properties.
The granular detergent composition or ingredient of the present invention may be used as a powder detergent by itself, but with the addition of other ingredients,
It may also be used as a base powder for formulating a complete textile cleaning powder. Examples of such ingredients include inorganic salts such as sodium carbonate, sodium silicate, bleach,
Fluorescent agents, foam control agents, oxygen and fragrances are included. The final material is usually 50-95% by weight of the above base powder.
contains. When higher density materials such as perborate and / or small particle size materials are added, the bulk density value is 700.
It can be increased up to g / l or more. The granular detergent composition or component of the present invention can be prepared by any method (batch or continuous) suitable for producing a detergent composition having an increased bulk density of 600 g / l or greater. In a preferred method, the granular starting material is treated (i) in a high speed mixer / densifier with an average residence time of about 5 to 30 seconds, and then (ii) in a drying and / or cooling device. In the first stage of this process, the particulate starting material is thoroughly mixed in a high speed mixer / densifier for a fairly short period of about 5-30 seconds. The particulate starting material may be prepared by any suitable method such as spray drying or dry mixing. Therefore, the method is very flexible with respect to the chemical composition of the starting materials. Phosphate-containing and zeolite-containing compositions, and compositions with low or high active ingredient contents may be used.
The method is also suitable for densifying calcite / carbonate containing detergent compositions. If a spray-dried powder is used as the granular starting material, its particle porosity is large and the method of the invention can significantly increase the bulk density. It has been found that it is important to subject the granular starting material to a two-step densification process to obtain optimum densification. The first step is
It is carried out in a high speed mixer / densifier, preferably under conditions in which the starting material is or is maintained in a deformable state as described below. As a high speed mixer / densifier, Loedige (trademark) CB 30 or CB 1
It is beneficial to use a 00 Recycler. These devices consist essentially of a large stationary hollow cylinder and its central axis of rotation. Several different types of blades are attached to this shaft. The axis may range from 100 to 2500 depending on the degree of densification and the desired particle size.
It can rotate at rpm. The on-axis blade provides a good mixing action of solids and liquids that can be mixed at this stage. The average residence time depends somewhat on the rotational speed of the shaft, the position of the blade, and the weir (resistance) at the exit. It is also possible to add solid material into the Loedige recirculator. Other types of high speed mixers / densifiers with similar efficacy on detergents are also envisioned. For example, Shugi ™ Gran
ulator or Drais (TM) K-TTP 80
Can be used. Obviously, for use, handling and storage, the detergent powder should no longer be in a deformable state. Therefore, in the final processing step of the present invention, the densified powder is dried and / or cooled. This step is carried out by known methods, for example in a fluidized bed apparatus (drying) or by air lift (cooling). From a processing point of view, it is beneficial if the powder requires only a cooling step. This is because the required device is relatively simple in that case. The detergent material after the first step of the process according to the invention still has a considerable porosity such that the bulk density can be further increased. It has been found to be particularly beneficial to subject the powder to a further densification step, instead of choosing a long residence time in the high speed mixer / densifier to try to increase the bulk density even further. In that case, the process is the same as that described in the applicant's co-pending unpublished European patent application No. 367,339. In this further processing step, a medium speed granulator /
In a densifier, 1 to 1 of detergent material is provided under conditions such that the powder is or is maintained in a deformable state.
Treat for 10 minutes, preferably 2-5 minutes. As a result, the particle porosity is further reduced. The main difference from the first step is
It has a low mixing speed and a long residence time of 1-10 minutes. This further processing step is based on Loedige Plow
Loedige ™ KM, also known as share
It can be successfully carried out in a 300 mixer. The device essentially consists of a hollow stationary cylinder with a central axis of rotation, on which various plow blades are mounted. This shaft can rotate at speeds of 40 to 160 rpm. In some cases, one or more high speed cutters can be used to prevent over agglomeration. Another machine suitable for this process is, for example, Drai.
s (TM) KT160. Optionally, as disclosed in Applicant's co-pending European Patent Application No. 390,251, a high speed mixer / densifier and / or
Alternatively, a small amount of finely powdered solid such as zeolite can be added to the medium speed granulator / densifier. What is preferred for the first step and essential for the subsequent further processing steps is the deformable state that the detergent powder should assume in order to obtain optimum densification.
Is. This deformable state can be induced in various ways, for example by operating at temperatures above 45 ° C.
When adding liquids such as water or nonionics to the particulate starting material, lower temperatures may be used, for example above 35 ° C. According to a preferred embodiment of the invention, the spray-dried base powder leaving the column at a temperature above 45 ° C. is fed directly to the process of the invention. Alternatively, the spray-dried powder is first cooled, for example in an air lift, and then transported and heated again. Heat is applied externally, but can be supplemented with internally generated heat, such as the heat of hydration of anhydrous sodium tripolyphosphate. The deformability of a powder detergent can be derived from its compression modulus, which can be derived from its stress-strain properties.
To measure the compression modulus of a particular composition, a sample of the composition is compressed to form airless granules 13 mm in diameter and height. The stress-strain curve during unrestricted compression is recorded at a constant strain rate of 10 mm / min using an Instron tester. The compression modulus can be derived from the slope of the stress-relative strain curve during the first stage of the compression process, which reflects elastic deformation. The compression modulus is expressed in MPa (megapascal). The Instron instrument can be equipped with a heatable sample holder to measure the compression modulus at various temperatures. It has been found that the compression modulus measured by the above method correlates well with particle porosity reduction and concomitant bulk density increase under comparable processing conditions. This is explained in more detail in the examples below. In principle, a powder is considered to be in the deformable state if the compression modulus as described above is less than about 25 MPa, preferably less than 20 MPa. The compression modulus is more preferably less than 15 MPa, 1
Values below 0 MPa are particularly preferred. The deformability of a powder depends, among other conditions, on chemical composition, temperature and water content. Regarding chemical composition, the ratio of liquid to solid,
And the amount of polymer was found to be an important factor.
Furthermore, making the phosphate-containing powder in a deformable state was generally more difficult than with the zeolite-containing powder. The storage stability of the final powder detergent is determined by the unrestricted compressibility test (Unc
infinity Complexity T
est). In this test, the powder detergent is placed in a cylinder with a diameter of 13 cm and a height of 15 cm, then a load of 10 kg is applied to the powder (top of the cylinder), 5
After minutes, remove the weight and remove the cylinder wall. Next, a load is applied to the top of the column of the compressed powder detergent, the load is increased, and the weight (kg) at the time of column collapse is measured. This value is a function of the stickiness of the powder detergent and was found to be a good measure for storage stability. Distributing performance
Is evaluated by the following method. P of dry powder (100g)
Put it in the dry dispenser tray (shower type dispenser) of the AIPS 126/127 type front-loading automatic washing machine. Tap water with a flow rate of 5 l / min supplied at a pressure of 0.5 bar is passed through the dispenser for 1 minute. The temperature of water is 10 to 20 ° C. The remaining undistributed powder is taken out, dried at 100 ° C. for 12 hours and weighed. The partition residue is the residual dry powder expressed as a percentage of the initial sample. The average of 4 measurements is taken as the final result.

The present invention will be further described by the following examples, but the present invention is not limited thereto. Unless stated otherwise, all parts and percentages herein are by weight. In the embodiment, the following abbreviations are used: _LAS: C 12 _{-C 15} linear alkylbenzene sulfonate nonionic (sex substance): ethoxylated _C 12 _{-C 15}
Fatty alcohol-based nonionic surfactant Soap: C _{15 to} C ₂₀ fatty acid sodium salt Zeolite: Zeolite 4A (Wessalith [trademark], D
(Sold by Egussa) Carbonate: Sodium Carbonate Sulfate: Sodium Sulfate Silicate: Alkaline Sodium Silicate; Na ₂ O: SiO
₂ ratio = 1: 2 Polymer: Copolymer of maleic acid and acrylic acid having a molecular weight of 70,000; sold by CP5, BASF Foam Inhibitor: Silicone Oil Foam Inhibiting Granules Examples 1-6 Spray drying aqueous slurries A powder detergent corresponding to the composition shown in Table 1 was prepared. Examples 1-3 relate to materials produced within the scope of the present invention. Examples 4 and 5 are comparative examples. The quantities are parts by weight.

[Table 1] In the pilot plant, 0.5-1.0 t / hour,
Alternatively, the powder was produced at full scale at 20-30 tonnes per hour. The temperature at the bottom of the tower is about 60-70 ° C.
Met. The physical properties of the spray dried powder are shown in Table 2.

[Table 2] Powder is Loedige Cycle detailed above
r CB Direct feed into continuous high speed mixer / densifier. CB 30 unit is for low throughput CB100
Was used for high throughput. The unit typically operated at a mixer tip speed of 8-30 meters per second. The comparative powder of Example 5 was processed in a conventional rotary drum mixer. The residence time in this case was about 1-2 minutes. Table 3
Various solids and / or liquids and / or binders were added into the recycler and drum as shown in. Lo
The properties of the powder after treatment on the edge recycler or rotating drum are also shown in Table 3.

[Table 3] The powder may optionally be further passed through a medium speed granulator / densifier. This was done using the powder of Example 3.
The properties obtained as a result are shown in Table 4.

[Table 4] A cooling / drying step was performed in a fluidized bed to produce the final base powder. As a result, a base powder having the properties shown in Table 5 was obtained.

[Table 5] Finally, the base powder was supplemented with bleach, enzymes, foam control granules (optionally containing silicone oil), perfumes and the like. Details of added ingredients, final powder properties, and dispensing performance are shown in Table 6.

[Table 6] The good partitioning properties of the composition of the invention are evident by a comparison of Examples 1-3 and Example 4. Detergent activity required due to too low soap content of active system Example 4
Indicates poor distribution properties. The advantages of the method of the invention are:
This is clearly illustrated by a comparison of Examples 1-3 and Example 5. The powder of Example 5 was produced in a conventional drum without a densification step and has a bulk density of 595 g / l.
Nothing more than.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C11D 3:12 9:02) (56) References JP-A-63-154799 (JP, A) Special features Kaihei 2-49099 (JP, A) JP-A-3-269098 (JP, A)

Claims (8)

[Claims] 1. A ternary activator system comprising 10 to 70 wt% of a builder, at least 50 wt% of which is a non-phosphate material, and one or more nonionic surfactants, anionic surfactants and soaps. A three-component active agent having a weight ratio of anionic surfactant to nonionic surfactant of less than 5: 1 and an amount of soap of 10 to 90% by weight of the active agent system.
~ 45 wt% and having a bulk density of at least 600 g / l, wherein the granular starting material comprises: (i) an average residence time of about 5 to 30 seconds. Process as described above, characterized in that it is processed in a high speed mixer / densifier and then (ii) in a drying and / or cooling device. 2. A method according to claim 1, wherein the particulate starting material is in a deformable state or is maintained in that state. 3. A process according to claim 1, wherein the deformable state is brought about by operating at a temperature above 45 ° C. and / or by adding a liquid to the particulate starting material. 4. The method according to claim 1, wherein the nonionic substance and / or water is sprayed onto the particulate starting material. 5. The method according to claim 1, wherein the particulate starting material is a spray-dried detergent base powder. 6. A granular detergent composition or ingredient produced by the method according to any one of claims 1 to 5. 7. A granular detergent composition according to claim 6, wherein the particulate starting material is not obtained by a spray drying method and the detergent composition or component is produced without a spray drying step. Or ingredient. 8. A powder detergent comprising 50 to 95% by weight of the granular detergent composition or component according to claim 6 or 7.