JPH01268799A - Granular washing detergent composition - Google Patents

Abstract

PURPOSE: To provide a new low or zero phosphate subject composition which contains a particulate partially neutralized fatty acid mixture and a base acts to increase the pH of the composition.

CONSTITUTION: This composition contains (A) as a 1st particulate material a fatty acid mixture (preferably, 5-20 mol.%, unsaturated fatty acid having 16 to 18 carbon atoms and a 95-80 mol.% mixture of saturated fatty acid having 8 to 14 carbon atoms and saturated fatty acid having 16 to 18 carbon atoms in 3:1 to 1:2 proportion) which contains 35 mol.% unsaturated fatty acid and is neutralized up to 25-60 mol.% and (B) as a 2nd particulate material a base comprising sodium carbide, alkaline sodium silicate, etc., in amounts sufficient to increase the pH of the composition above 8 with a concentration of underwater 0.5 wt.%.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel granular laundry detergent compositions containing no or only a small amount of inorganic phosphate compounds. Particulate base materials suitable for use and methods of making the particulate base materials are also concerned.

Conventional laundry detergent compositions contain phosphate compounds, particularly sodium tripolyphosphate (STP), as builders.

In recent years, in view of the negative effects of phosphate compounds on the environment,
New laundry detergent compositions containing little or no phosphate are being actively developed. However, it is difficult to produce compositions with properties comparable to the superior builder properties of phosphate-containing compositions.

As is well known, zeolites are used as builders in phosphorus-free laundry detergent compositions. However, the use of zeolites in laundry detergent compositions poses a number of problems. That is, zeolites tend to deteriorate the powder structure and also tend to interact with galates, which are commonly present as corrosion inhibitors in detergent compositions, leading to dispensing problems in washing machines.
m) and the problem of deposits on laundry.

To 11 11 The present invention provides a novel low-phosphorus or phosphorus-free granular laundry detergent composition that does not use zeolite.

The compositions of the present invention contain acidic soaps on a powder basis.
base) and builder.

The composition of the invention includes a fatty acid mixture as the first particulate material, which mixture may contain up to 35 mole % unsaturated fatty acids and is neutralized to 25-60 mole %. The compositions of the present invention further include a base as a second particulate material in an amount sufficient to raise the pH of the composition to greater than 8 at a concentration of 0.5% by weight in water.

The compositions of the invention may also optionally contain conventional additives such as bleaching systems, proteolytic enzymes, antifoam agents, optical brighteners, fragrances, corrosion inhibitors, and the like.

The compositions of the present invention exhibit extremely bulky cleaning performance without the use of builders consisting of phosphates or zeolites, although it may be possible and effective to use these builders at low concentrations.

The composition of the present invention also has excellent powder properties such as flowability and compressibility. The granular laundry detergent composition of the present invention preferably contains 30 to 80% by weight of acidic soap particles.

The acid soap is a mixture of free fatty acids and soap, or a partially neutralized mixture of fatty acids. Although in principle a wide range of saturated and/or unsaturated fatty acids may be used, the powder properties of the granular composition are such that the content of unsaturated fatty acids is
Exceeding 5 mol % has been found to be less preferred, ie such powders are sticky and have little flowability. It gets expensive.

Preferably, it contains 95 to 80 mol % of a mixture of saturated fatty acids in a ratio of 3:1 to 1:2.

In addition, in this specification, 08-C14 saturated fatty acid is also called lauric acid, C14-C1B saturated fatty acid is also called stearic acid, and CI6-C18 unsaturated fatty acid is also called oleic acid.

In the fatty acid mixture, CI8-C18 saturated fatty acids or stearic acid mainly play the role of builder and hardly contribute to detergency, while 016-C18 unsaturated fatty acids or oleic acid also have builder properties, but are particularly important with respect to detergency. play a role. The 08-C14 saturated fatty acid or lauric acid contributes to both builder properties and detergency, but its primary role is to facilitate processing and provide adequate solubility of the soap/fatty acid mixture.

The laundry detergent compositions of the present invention can be prepared by triblending the various ingredients into a suitable mixture.

According to the invention, the acid soap is used in the form of particulate material, for example particles or noodles. The size (particle size) and shape of the particles can be selected at will. This will be explained in detail later. These acidic soap particles can be produced by dissolving a suitable amount of soap in a molten fatty acid mixture, allowing it to solidify and processing the resulting solid material. or,
It can also be prepared by partially saponifying or neutralizing the fatty acid mixture in situ. In this method, a solid base is gradually mixed with a molten fatty acid mixture.

Suitable base compounds include, for example, soda ash (sodium carbonate), sodium disilicate, sodium metasilicate or sodium hydroxide.

When using soda ash, only CO2 is produced as a by-product, and this CO□ can be easily removed from the reaction mixture. alkaline sodium silicate (sodiumalk)
aline 5 ilicate) can increase the viscosity of the molten soap/fatty acid mixture due to the formation of insoluble silicates. In contrast, incorporating the silicate directly into the soap/fatty acid mixture provides favorable powder properties and avoids the problems that arise when triblending the silicate in its pure form. The operating temperature required for processing increases with increasing fatty acid chain length and degree of neutralization and is preferably between 70 and 140°C.

The detergent composition of the present invention further comprises adjusting the pH of the composition to 0 in water.
．． It also contains a sufficient amount of granular base to make the concentration greater than 8 at a concentration of 5% by weight, and the base can in principle be any material that can be made into granules and is readily soluble in water without forming precipitates with the soap fatty acid particles. You can use the base of Preferably, the same base used for partial neutralization of the fatty acid mixture is used.

The laundry detergent compositions of the present invention may further include the anionic parabolite incorporated into the granular acidic soap base or present as a separate component. The acidic soap particles may contain up to 10% by weight of anionic and/or nonionic surfactants. More than that can have an adverse effect on powder properties.

Alternatively, or in addition, anionic or non-ionic surfactants, particularly non-ionic surfactants, may be acidified; examples of such additives include those sprayed onto the Berkeite carrier. Liquid ethoxylated CI3-C15 alcohols are mentioned. When the inorganic carrier is the base material, the additive may be added to the base component (secondary component) of the composition.
granular material).

It has been found that a particularly preferred method of manufacturing acidic soap particles is the spray cooling method. Using this method, particles orprills with superior properties regarding dissolution rate, stability and cleaning performance of the final detergent composition can be obtained.
can be manufactured.

Using the spray cooling method, particles with a desired size and bulk density can be produced by adjusting the operating conditions.
250 to 11,000 III, in view of compatibility with other solid components in the composition, so that the
It preferably has an average particle size of from 400 to 750 g/e.

When producing particles by spray cooling a soap/fatty acid mixture, in addition to builder/activity and solubility requirements, a number of other considerations need to be taken into consideration, such as: 1. Appropriate handling characteristics. and storage properties, the soap/fatty acid mixture must exhibit sufficient solid state at temperatures below 35-40°C.

2. For processing reasons, it is preferred that complete liquefaction is possible at temperatures below 100°C. This means that in practical operation the maximum mixing temperature is less than 150°C.

It has been found that in order to meet this condition, the soap content of the mixture must be limited to 25-60 mol %, depending on the fatty acid composition.

3. The composition of the mixture in terms of fatty acid type and degree of neutralization must be such that it exhibits adequate solubility at low washing temperatures of 20-40°C.

As will be clear to those skilled in the art, it is not easy to satisfy all of these conditions, since many properties of the soap/fatty acid mixture must be taken into account.

First, soaps and fatty acids form various eutectic complexes.
ctic complexes). Such complexes can also be formed between soaps and fatty acids, so that these mixtures exhibit extremely complex phase diagrams.
diagram). This is especially true for 3
The problem is that it must exhibit a solid state at temperatures between 5 and 40°C. It has also been found that the relative amounts of lauric acid and stearic acid should preferably not exceed a ratio of 1:1. Even so, it is not possible to avoid the occurrence of liquefaction at a eutectic temperature of about 33°C. Although not ideal in terms of ease of handling/stability, the introduction of some lauric acid/stearic acid complex with a low melting point can be expected to have a beneficial effect on solubility at low temperatures.

Second, the structure becomes more complex due to the phenomenon of metathesis (w+etathesis). Addition of soap to a fatty acid mixture results in an equilibrium reaction such that the soap and free acid are present in specific ratios in all chain length congeners, depending on the reactivity of the acids on either side. Fortunately, in these mixtures, the different reactivities of unsaturated and saturated acids actually result in preferential conversion of oleic acid to soap.

It is only when the proportion of soap exceeds the proportion of oleic acid soap that large quantities of lauric and stearic acid soaps can be present.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

A fatty acid mixture having the composition listed in Table A was prepared. When these mixtures were heated, they began to melt at about 65°C. Continue heating until it is completely melted at about 80℃, then gradually add soda ash (sodium carbonate) at a rate of 0.1kg/min.
The mixture was neutralized to the desired degree while controlling the evolution of O2. At the same time, the temperature was gradually increased to about 140°C.

The partially neutralized fatty acid mixture was then cooled and solidified. The coagulum was shaped into noodles using a sodium press. Noodles with a diameter of III and a length of approximately 51 cm were obtained. Table A shows the properties and handling properties of these noodles. Solubility was determined by determining the rate of dissolution of soap/fatty acid noodles by monitoring the increase in conductivity caused by dissolution of the soap portion of these noodles. In this method, while stirring with a magnetic stirrer, 3 g
/l sample was added into deionized water 11 at 25°C. The dissolution rate is expressed as the time required for 50% of the soluble portion of the soap/fatty acid mixture to dissolve (tl/2). The maximum conductivity is measured when heated above the melting point of the fatty acid and then cooled to room temperature. As is clear from Table A, these noodles had good handling properties and high solubility.

It was operated in the same manner as in Examples 1-3. However, in this case the particles were produced by spray cooling the molten acid/soap mixture in a spray tower. The spray cooling conditions are as shown in Table B.

The powder properties of the resulting particles are shown in Table C.

Air volume: 7,000 kg/h Tower pressure: -27-1On+m H20 nozzle pressure = 178 bar Throughput: 60-150 kg/h Liquid temperature in tank 286-120°C Incoming air temperature (countercurrent)
: 22~24℃ Outflow air temperature: 22~25℃ Particle temperature at the bottom of the column 227~33℃ Nozzle height: 12m Example 4 5 6 Bulk density
565 533 570D, F, speed (i
f/s) 152 145 152 Compressibility (%v/v) 7 15 10 Particle size;
607 853 558d(n
+) n 2.89 6.74 3.
0312 mesh/1400Ll+II O,1
4,40,216 mesh/11000u 1.
4 15.4 1.122 mesh 7710μm
13.3 50.5 15.230 mesh 1500
1+m 34.4 26.6 30.944 mesh/355pm 22.7 1.9 26.
060 mesh/250um 14.1 0.
1 17.580 mesh/180pm 5.
7 0.1 7. L120 mesh/125um
1.4 0.1 1.1> 120 mesh 0.1 0.6 0.1 Solubility: tl/2 (min) 2 2.75
2.75tl (min) 10 7
12 As is clear from the comparison of Examples 1-3 and Examples 4-6, spray cooling of partially neutralized fatty acid mixtures yields particles with high solubility and excellent powder properties.

Nioleic acid = 20% by weight CI2 to C14 fatty acids: 45% by weight stearic acid: 35% by weight These mixtures were heated to 65°C and solidified while continuing to heat. Sodium carbonate was added until a degree of saponification of 33% was reached. The molten soap/fatty acid mixture was then spray cooled according to the conditions of Table B at a temperature of 110°C.

As a result, as shown in the table, high-density particles with extremely favorable powder handling properties were obtained.

Repeat the procedure of Example 7 using a fatty acid mixture with the following composition: Nioleic acid: 30% by weight C12-C14 fatty acids = 40% by weight Stearic acid = 30% by weight Molten fatty acid mixture using solid sodium disilicate was partially neutralized and then spray cooled. The obtained particles had the characteristics shown in the table and were extremely easy to handle.

The final laundry detergent composition was prepared by tri-blending the acidic soap particles prepared in Example 7 with various other ingredients, such as non-ionic detergents, bleaching systems and enzymes carried in a barkeite carrier. manufactured something.

The composition of this final detergent powder is shown in Table E, which also lists two commercially available laundry detergent compositions.

Composition B is low in phosphorus, Composition A is phosphorus-free, and both use zeolite.

The cleaning performance of these three compositions was evaluated according to the standard 40°C cotton cycle program "C".
F822W) Measured using a large drum type washing machine. 2.5 kg of laundry, a mixture of clean cotton cloth and moderately soiled test cloth, was mixed with a liquid/fabric ratio of approximately 6.
and washed. Water temperature is 20℃, pressure is 2.0kg/c
I made it m2. The water hardness was 9, or 25°GH.

Detergent powder was added at a dose of 7.5 g/l. The reflectance (R*460) of the test fabric was recorded before and after washing.

Standard EHP^-101 and W in two different water hardness
Table F shows the results of testing four types of fabrics, including the FK-IOC fabric. As is clear from these results, despite not containing phosphate or zeolite builder,
Extremely high cleaning performance was observed even at high water hardness.

Tomo-Kage Example 9 Weight % Soap/fatty acid particles of Example 7 45.0TAED
3.0 Sodium perborate-
Hydrate 6. O5CMC2・0 EDT^ 0.2 enzyme
0.5 soda
18.3 Alkaline sodium silicate 5.0
(Ratio 2) ---,,,,
-10(),00 Composition B (low phosphorus) wt% LAS
8.5 Non-ionic system
3.2 Soap 1.0
Sodium perborate hydrate 5.5 Enzyme
0.5T8ED
5.1 Alkaline sodium silicate 2.0 (ratio 2) STP 18.0 Zeolite 13. O5CMC0.5 Soda 5.0EDT^
0.15 Sodium Sulfate・
25.0 water/miscellaneous ingredients 10
Composition ^ (phosphorus-free) until 0.0 Weight % LAS 7.8 Nonionic 4.8 Soap
0.6 Sodium perborate hydrate 17.
9 Enzyme 0.4 Alkaline 5 ilicate 4.3 Zeolite 21. lSCMC0,
8 Soda 5.8 Deques
t O,9 Sodium sulfate
19.5NT^
3.5 Polymer 2.4 Water/
Miscellaneous ingredients: Batter until it reaches 100, -,,
, B = 9@G41 25°G ■ 9 8 B 9 8 B Test cloth 1 (Protein stain) 27 28 29 24 27 2
6 Test cloth 2 (oil 33 26 37 32 25
36 Test fabric 3 (EMP 8-1 (H) 17 1
4 18 17 12 17 Test cloth 4

Claims (15)

[Claims] (1) 25-6 which may contain up to 35 mol% of unsaturated fatty acids
a fatty acid mixture neutralized to 0 mole % as a first particulate material, and a sufficient amount of base as a second particulate material to cause the pH of the composition to be greater than 8 at a concentration of 0.5% by weight in water. A granular laundry detergent composition comprising: 2. The granular laundry detergent composition of claim 1, comprising 30 to 80% of a partially neutralized fatty acid mixture. (3) The fatty acid mixture mainly contains 5 to 20 mol% of C16-C18 unsaturated fatty acids and 95-80 mol% of a mixture of C8-C14 saturated fatty acids and C16-C18 saturated fatty acids in a ratio of 3:1 to 1:2. The granular laundry detergent composition according to claim 2, comprising: (4) The granular laundry detergent composition according to any one of claims 1 to 3, wherein the base is sodium carbonate or alkali sodium silicate. (5) A granular laundry detergent composition according to any one of claims 1 to 4, further comprising a non-soap detergent active. (6) A granular laundry detergent composition according to claim 5, comprising up to 10% by weight of anionic and/or nonionic detergent materials in the first granular material. (7) The granular laundry detergent composition of claim 5, comprising a liquid nonionic material held in a porous inorganic carrier. (8) The granular laundry detergent composition according to any one of claims 1 to 7, further comprising a peroxide bleaching system and/or an alkali sodium silicate and/or an antifoaming compound and/or an enzyme. (9) A granular acidic soap material suitable for use as a base powder for the manufacture of laundry powders, which may contain up to 35 mole % of unsaturated fatty acids, substantially between 25 and 6
A granular acidic soap material consisting of a fatty acid mixture neutralized to 0 mol%. (10) C1 in which the fatty acid mixture is mainly 5 to 20 mol%
6-18 unsaturated fatty acids and 95-80 mol% C8-C1
Ratio of 4 saturated fatty acids and C16-C18 saturated fatty acids 3:1
10. The granular produced soap material of claim 9 comprising a 1:2 mixture. (11) The granular acidic soap composition according to claim 9 or 10, which has a particle or noodle shape. (12) The granular acidic soap material according to any one of claims 9 to 11, having a degree of neutralization of 30 to 40 mol%. (13) A method for producing a granular acidic soap material according to claim 9, wherein a fatty acid mixture optionally containing one or more soaps is melted and the mixture is partially dissolved by adding a base if necessary. A method characterized in that it comprises the steps of neutralizing and converting this mixture into a particulate solid form. 14. The method of claim 13, wherein the granular acidic soap material is produced by spray cooling a partially neutralized molten fatty acid mixture to form particles. (15) Process according to claim 13 or 14, characterized in that the fatty acid mixture is partially neutralized by adding sodium carbonate and/or alkali sodium silicate.