JPH04363397A - Detergent composition - Google Patents

Abstract

PURPOSE: To provide a fine particulate detergent composition having a good detergency and a high bulk density by incorporating a non-soap detergent-active material including a primary alcohol sulfate, etc., a fatty acid soap, an alkali metal aluminosilicate, sodium carbonate, etc.

CONSTITUTION: This composition comprises (A) 17 to 35 wt.% non-soap detergent-active material composed of (i) 5 to 35 wt.% anionic surfactant composed of 10 to 100 wt.% primary alcohol sulfate(PAS) and 0 to 90 wt.% straight- chain alkylbenzene sulfonate, (ii) 0 to 10 wt.% fatty acid soap, and (iii) 0 to 10 wt.% anionic surfactant other than primary alcohol sulfate or alkylbenzene sulfonate, (B) 0 to 100 wt.%, fatty acid soap, (C) 25 to 45 wt.%, (anhydrous basis) crystalline or amorphous alkali metal aluminosilicate, (D) sodium carbonate in an amount of 0 to 10 wt.% in the case wherein the amount of the PAS in (i) of the component (A) is 10 to 60 wt.%, 0 to 20% in the case wherein the amount of the PAS in (i) of the component (A) is 60 to 80 wt.%, or 10 to 20 wt.% in the case wherein the amount of the PAS in (i) of the component (A) is 80 to 100 wt.%, and (E) the balance of other detergent components.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

0001

FIELD OF INDUSTRIAL APPLICATION This invention relates to particulate detergent compositions, particularly detergent compositions with high bulk density, which contain a primary alcohol sulfate (PAS), an alkali metal aluminosilicate, and optionally sodium carbonate. Regarding.

0002

BACKGROUND OF THE INVENTION A detergent composition having zeolite as a builder and containing an alkylbenzene sulfonate and PAS is disclosed in Japanese Patent No. 62 240 397A (K
ao), Japanese Patent No. 62 273 300A (Ka
o), European Patent No. 219 314A (Proc.
ter & Gamble) and European Patent No. 220 024A (Procter & Gamble)
ble).

[0003] Japanese Patent No. 01 142 000A (
Nippon Gosen Senzai) is a P.A.
A high bulk density detergent composition prepared by neutralizing S acid with sodium carbonate and zeolite is disclosed.

European Patent No. 342 917A (U
nilever) discloses detergent compositions containing PAS with a specific chain length distribution.

European Co-pending Patent No. 91 300 456.0 filed by our company on January 21, 1991
No. 1, No. 1, No. 2003-102002 discloses a detergent composition comprising a zeolite, sodium carbonate, and a branched PAS.

European Patent No. 340 013A (U
nilever) relates to high bulk density detergent powders containing moderate to large amounts of surfactants (particularly anionic surfactants) and relatively large amounts of zeolite builders. Preferred exemplary anionic surfactants are alkylbenzene sulfonates. Preferably, the powder is produced by a process consisting of granulation and densification of the spray-dried powder in a high speed mixer/granulator with stirring and cutting effects.

[0007]

SUMMARY OF THE INVENTION The present invention provides detergent compositions of the general type disclosed in European Patent No. 340 013A (Unilever), in which PAS is used in place of alkylbenzene sulfonates in part or in whole. This is based on the observation that cleaning properties can be surprisingly improved by adjusting the amount of sodium carbonate present.

Therefore, the present invention mainly comprises (a) (i) primary alcohol sulfate [10 to 100% by weight of (i)] and any alkylbenzene sulfonate [(i)
5-35% by weight of an anionic surfactant component consisting of (ii) 0-10% by weight of any nonionic surfactant and (iii) a primary alcohol sulfate or alkylbenzene sulfonate. 0~ other than
17~ consisting of 10% by weight of any anionic surfactant
35% by weight of non-soap detergent active ingredients; and (b) 0-10
% by weight of any fatty acid soap; and (c) 25-45% by weight.
(d) anionic surfactant component (a) (i) containing from 10 to 60% by weight of a primary alcohol sulfate; 0 to 10% by weight of sodium carbonate if the anionic surfactant component (a)(i) contains 60 to 80% by weight of primary alcohol sulfate; Anionic surfactant component (a) (i) is 80-100% by weight
1 if it contains primary alcohol sulfate
A particulate detergent composition is provided comprising from 0 to 20% by weight of sodium carbonate and (e) up to 100% by weight of any other detergent ingredients.

[0009] The object of the present invention is to provide a suitable to large amount of an anionic surfactant based or as the sole component of a primary alcohol sulfate, a relatively large amount of an aluminosilicate builder, and a zero to moderate amount of an aluminosilicate builder. This is a fine granular detergent composition characterized by comprising sodium carbonate appropriately selected within the range of .

The weight ratio of aluminosilicate builder (c) to all non-soap surfactants (a) is preferably 0.
．． 9:1 to 2.6:1, more preferably 1.2:
The ratio is 1 to 1.8:1.

It has been found that these amounts and ratios provide excellent cleaning properties and that preferred embodiments of the invention in which the bulk density of the composition is high provide improved processability and powder properties.

Surfactant System The detergent compositions of the present invention contain from 17 to 35% by weight of non-soap detergent active materials based on a specific anionic surfactant component. The particular anionic surfactant component, which constitutes 5-35% by weight of the total composition, consists solely of primary alcohol sulfate (PAS) or a mixture of PAS and linear alkylbenzene sulfonate (LAS). If both LAS and PAS are present, P
AS is at least 10% by weight of these two mixed components;
Although preferably at least 20% by weight, LAS may represent up to 90% by weight of the mixture components, preferably 8% by weight.
It may constitute up to 0% by weight.

As will now be explained in more detail, the amount of LAS present and the relative proportions of LAS and PAS determine the amount of sodium carbonate present.

The main component of primary alcohol sulfate surfactant systems is primary alcohol sulfate (PAS), also known as alkyl sulfate. PAS constitutes 10-100% by weight of the major anionic surfactant component of the compositions of the present invention. The anionic surfactant component itself constitutes 5-35% by weight of the total composition.

Although these anionic surfactants have recently received much attention as potential replacements for alkylbenzene sulfonates due to environmental concerns, they have slightly lower overall cleaning performance under a wide range of laundering conditions. It was missing.

Alcohol sulfates are obtained from both synthetic and natural alcohols containing about 8 to 22 carbon atoms. Examples of suitable alcohols that can be used in the production of PAS include decyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol and stearyl alcohol, as well as mixtures of fatty alcohols obtained by reducing the glycerides of tallow and coconut oil. Can be mentioned. In natural alcohols (e.g. tallow alcohol or coconut alcohol) linear PA
Synthetic alcohols (e.g. those produced by the oxo process) yield linear or branched PAS.
is obtained. Both linear and branched PAS are suitable for use in the present invention.

Most commercially available PAS are mixtures containing a wide range of chain lengths. The PAS used in the compositions of the invention preferably have a relatively short chain length, i.e. the PAS consists entirely or mainly of materials with an alkyl chain length of C16 or less, more preferably wholly or mainly It is made of a material with an alkyl chain length of C14 or less. P with short chain length
AS is particularly suitable for products used alone or as a main component under low temperature (below 25° C.) washing conditions.

Preferred PAS of natural source are coconut oil, palm kernel oil, babassu palm oil or macauba.
Obtained from oil.

Mainly linear C12 alcohol and linear C14
C12 alcohol and C12 alcohol as a natural material or obtained by fractionation, consisting of alcohol and containing smaller amounts of materials with shorter and longer chain lengths than alcohol.
14 alcohol-rich “narrow-
Coconut alcohol PAS (coc) as a material
oPAS) is particularly preferred. cocoPAS has excellent cold cleanability, is made from renewable natural sources, and is biodegradable.

In products used alone or as a main component under low temperature washing conditions, long chain PAS (eg beef tallow PAS) are absent or present in relatively small quantities due to their poor washing performance at low temperatures. Preferably present.

Linear Alkylbenzene Sulfonates As mentioned above, the main anionic surfactant component constituting 5 to 35% by weight of the composition is PAS, which accounts for at least 10% by weight, preferably at least 2% by weight of the mixed component of PAS and LAS.
If it constitutes 0% by weight, linear alkylbenzene sulfonate (LAS) may be included in addition to PAS.

Linear alkylbenzene sulfonates are very well known components of textile laundry detergent compositions. Alkyl chain lengths are generally in the range C8-C15. These materials are described in references, e.g. “Surface-
Active Agents and Deterg
ents” (VolumesI and II,b
ySchwartz, Perry and B.
erch).

Optional Nonionic Surfactants The compositions of the present invention may further contain up to 10% by weight of nonionic surfactants. Nonionic surfactants that can be used include primary and secondary alcohol ethoxylates, especially alcohol 1
Included are aliphatic C12-C15 primary and secondary alcohols and alkyl polyglycosides ethoxylated with an average of 3 to 20 moles per mole of ethylene oxide.

Optional anionic surfactant compositions include LAS and PA in place of or in addition to nonionic surfactants.
It may contain up to 10% by weight of one or more anionic surfactants other than S. Examples of suitable anionic surfactants include:
Mention may be made of alkyl ether sulfates, alkyl xylene sulfonates, olefin sulfonates, dialkyl sulfosuccinates and fatty acid ester sulfonates.

These examples are not exhaustive, and other examples can be found in standard references, such as “Surface-A
active agents and deterrence
gents” (Volumes I and I
I, by Schwartz, Perry
and Berch).

[0026] As with any non-soap detergent, the compositions of the present invention may contain up to 10% by weight of fatty acid soap to provide suds control as well as additional cleaning and builder power. Non-soap surfactants are 17-35% by weight, but soaps, if any, are not within this 17-35% by weight range.

Aluminosilicate Detergent Builder The alkyl metal (preferably sodium) aluminosilicate builder present in the compositions of the present invention may be a crystalline or amorphous aluminosilicate or a mixture thereof. Sodium salt has general formula: 0.8-1.5Na2
O. Al2O3.0.8-6SiO2.

These materials must contain some bound water and have a calcium ion exchange capacity of at least about 50 mg CaO/g. Preferred aluminosilicates contain from 1.5 to 3.5 SiO2 units (in the above formula) and have a particle size of no more than about 100 microns, preferably no more than about 20 microns. Both amorphous and crystalline aluminosilicates can be easily prepared by reacting sodium silicate and sodium aluminate, as described in detail in the references.

Crystalline aluminosilicates (zeolites) are preferred for use in the present invention. Suitable materials are for example British Patent No. 1 473 201 (Henkel)
and British Patent No. 1 429 143 (Proct.
er & Gamble). Preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof. Zeolites of type 4A are particularly preferred for use in the present invention.

European Patent No. 384 070A (U
Also of interest is a new zeolite (maximum aluminum zeolite P) disclosed in NILEVER).

A relatively large amount of aluminosilicate detersive builder is present, in an amount of 25 to 45% by weight (based on anhydride), preferably 28 to 45% by weight. This provides processing advantages for compositions with high bulk density (see below)
It was found that good cleaning performance was obtained.

Optional Supplemental Detergency Builders Supplemental builders may be added if desired. Preferred supplemental builders are organometallic sequestrant builders. Examples include polycarboxylate polymers (e.g. polyacrylates, acrylic/maleic copolymers and acrylic phosphinates), monomeric polycarboxylates (e.g. citrate, gluconate, oxydisuccinate,
glycerol monosuccinate, glycerol disuccinate, glycerol trisuccinate, carboxymethyloxysuccinate, carboxymethyloxymalonate, dipicolinate and hydroxyethyliminodiacetate). Alternatively, organic precipitant builders such as alkyl malonates, alkenyl malonates, alkyl succinates, alkenyl succinates and sulfonated fatty acid salts may be used.

Particularly preferred supplementary builders are polycarboxylate polymers (polyacrylates and acrylic/maleic copolymers, preferably used in amounts of especially 0.5 to 15% by weight, especially 1 to 10% by weight) and monomeric polycarboxylates. (Citric acid and its salts, particularly preferably used in an amount of 3 to 20% by weight, more preferably 5 to 15% by weight).

The compositions of the present invention preferably do not contain more than 5% by weight of inorganic phosphate builders, and are desirably substantially free of phosphate builders.

Sodium Carbonate The amount of sodium carbonate present is a key feature of the invention.

Main anionic surfactant components (a) (i)
is 80-100% by weight of PAS and 0-20% by weight of L
AS, the composition of the invention contains sodium carbonate as a main component in an amount of 10 to 20% by weight. Surprisingly, the presence of this level of sodium carbonate provides a detergency advantage over similar compositions containing small amounts of sodium carbonate or no sodium carbonate; It was found that the amount of sodium carbonate did not significantly affect similar compositions.

On the other hand, the main anionic surfactant component (a)
If (i) consists of 10-60% by weight of PAS and 40-90% by weight of LAS, the amount of sodium carbonate will be small, 0-10% by weight, to optimize cleaning performance. Or it should be zero. Surprisingly, in this range, the cleaning performance obtained by combining PAS and LAS is better than the cleaning performance obtained from either surfactant alone.

Preferred anionic surfactant components within this range where low amounts of sodium carbonate are desired include 20-50% by weight PAS and 50-80% by weight L.
AS, more preferably 30 to 40% by weight
of PAS and 60-70% by weight of LAS.

[0039] PAS is 60-80% by weight, LAS is 20% by weight.
Beyond the range of ~40% by weight, the amount of sodium carbonate does not seem to affect detergency as significantly and may therefore be in the range of 0 to 20% by weight. However, especially for surfactant components consisting of 60-75% by weight PAS and 25-40% by weight LAS, 0-10% by weight
and a small amount of sodium carbonate are preferred.

High Bulk Density In a preferred embodiment of the invention, the bulk density of the composition is at least 650 g/liter, more preferably at least 7
00g/liter. The porosity of the particles is preferably 0
．． It does not exceed 25, more preferably it does not exceed 0.20.

The high bulk density compositions of the present invention may be produced in a variety of ways (batch or continuous). Post-tower densification of spray-dried powder
Some methods consist of a process using no column at all.

One type of process consists in subjecting the granular starting material (actually a granular detergent of conventional bulk density) to a granulation/densification process. The starting materials themselves may be prepared by spray drying or by tower-free methods (eg dry mixing or granulation).

European Patent No. 340 013A (
This process may be carried out in a high speed batch mixer/granulator with agitation and cutting functions, as described in J.D. Unilever. Preferably, the stirrer and cutter may be operated separately from each other and at separately varying speeds. Such mixers can combine high energy agitation input with cutting action, but can also be used to provide a gentler agitation regime with or without the cutting machine activated. Therefore, this mixer is a highly versatile and flexible part of the device.

A preferred type of high speed batch mixer/granulator is ball-shaped, preferably with the agitator axis substantially vertical. Japanese Fukae Powte
chKogyo Co. , manufactured by Fukae (registered trademark)
Mixers of the FS-G series are particularly preferred. The device is primarily in the form of a ball-shaped vessel into which the material is introduced through an upper port, with an agitator having a substantially vertical axis and a cutting machine located on the side wall near the bottom of the device. We are prepared. The stirrer and cutter may be operated separately from each other and at individually varying speeds.

[0045] Using a Fukae mixer, the compositions of the present invention may be produced directly from raw materials with high speed mixing and granulation. PAS and LAS may be introduced into the mixer, for example, in the form of powder, flakes, noodles or paste. For example, European Patent No. 352135A (Unilever
) and our European Co-pending Patent No. 91 300
PAS or LAS as described in subheading 422.2
Alternatively, it is also possible to use a method of neutralizing both of these on the spot.

As previously mentioned, the Fukae mixer requires batch operation. Alternatively, use a continuous high speed mixer/granulator, such as a Loedige® recirculator, and then optionally a Loedige® recirculator.
Continuous methods may be employed using medium speed continuous mixers/granulators such as Ploughshare. As with the Fukae mixer, this device can be used for post-column and column-free processes, including in-situ neutralization methods. Suitable methods are described in EP 367 339A, EP 390 251A, EP 420
317A (Unilever) and our European co-pending patent no. 91 200 740.8.

The granules obtained in the mixer/granulator may even be used as complete cleaning compositions. Alternatively, the resulting granules may be mixed with other ingredients or separately prepared mixtures to form a major or minor portion of the final product.

Other Ingredients The cleaning compositions of the present invention may optionally or suitably contain other functional ingredients. Some of these, e.g. sodium silicate, inorganic salts (e.g. sodium sulfate) and fluorescent agents, can survive the granulation/densification process and any steps before it, but then other ingredients, e.g. bleaching ingredients It is further preferred to add foam regulators, enzymes and fragrances. Those skilled in the art will readily determine when and how to incorporate the various ingredients that make up the fully prepared detergent composition.

[0049]

EXAMPLES The following examples illustrate the invention. Examples indicated by numbers are within the scope of the present invention, while examples indicated by letters are comparative examples. Unless otherwise specified, parts and percentages by weight are expressed.

Examples 1 to 5, Comparative Examples A to E Tables 1 and 2
A detergent powder having the composition shown below was manufactured. The PAS used was
Finely cut (C12/C14 rich) cocoPAS
(sodium salt), Albright &
It was Empicol® LX manufactured by Wilson.

Examples 1, 2, A, B, and C in Table 1 are compositions with a high content of sodium carbonate, and Examples D and C in Table 2 are compositions with a high content of sodium carbonate.
3, 4, 5, and E were compositions that did not contain sodium carbonate.

Spray drying the aqueous slurry containing all ingredients except sodium carbonate, sodium sulfate and the enzyme.
Generate a common base powder and then European Patent No. 34
Fuk as described in issue 0013A (Unilever)
This base powder was densified using an ae FS-100 high speed mixer/granulator and then mixed with appropriate inorganic salts (sodium carbonate or sodium sulfate) and enzymes to produce comparative powders C, E containing only LAS. was manufactured.

PAS (in powder form) is dry mixed in a Fukae mixer with sodium carbonate, sodium sulfate and all other ingredients except enzymes to form a base material, then densified and then mixed with suitable inorganic salts ( Powder 1, D containing only PAS was prepared by mixing sodium carbonate or sodium sulfate) and enzyme.

Mix appropriate amounts of the LAS-based powders of Examples C and E and the PAS-based powders of Examples 1 and D,
Then, LAS/PAS powders (Examples 2, A, B, 3, 4, and 5) were produced by processing in the same manner as in other Examples.

The bulk density of the final powder was over 720 g/l. These powders were free-flowing and showed no tendency to cake.

Two different test fabrics were used to measure washability. Test Fabric 1 contained a mixture of fat and particulate soil, and Test Fabric 2 contained a mixture of fat soil, particulate soil, and casein. Made in Japan (National (registered trademark) Electronic W100)
35 liters of washing machine water (5° containing Ca2+)
0.96 g/liter of the powder was added into French hard water (2° French hard water containing Mg2+). The test fabric was laundered with 2.0 kg of dirty cotton laundry. The washing time was 8 minutes, and the rinsing time was also 8 minutes (rinsing with running water).

Reflectance data at 460 nm of the washed test fabrics was measured using a Micromatch® reflectometer. The results are also shown in Tables 1 and 2.

Comparing Example 1 with Comparative Example D, coc
It can be seen that in the presence of oPAS and in the absence of LAS, the cleaning performance was significantly better in the presence of 15.51% by weight sodium carbonate than in the absence of sodium carbonate.

In the case where PAS was 75% by weight and LAS was 25% by weight (Examples 2 and 3), good cleaning performance was obtained even when the amount of sodium carbonate was large or zero.

When PAS is 50% by weight and LAS is 50% by weight (Comparative Example A, Example 4) and when PAS is 25% by weight and LAS is 75% by weight (Comparative Example B, Example 5)
) showed significantly better cleaning performance in the absence of sodium carbonate.

[0061] LAS exists and PAS does not exist (
In Comparative Examples C, E), the amount of sodium carbonate did not affect the detergency.

A comparison of Examples 3, 4, and 5 with Comparative Examples D and E also shows synergistic advantages. That is, in the absence of sodium carbonate, the cleaning properties obtained from the PAS/LAS mixture were better than those obtained using either surfactant alone.

[0063]

[Table 1]

[0064]

[Table 2]

Claims (5)

[Claims] Claim 1: (a) 5 consisting mainly of (i) a primary alcohol sulfate [10 to 100% by weight of (i)] and an optional alkylbenzene sulfonate [0 to 90% by weight of (i)]; -35% by weight of anionic surfactant component, (ii) 0-10% by weight of any nonionic surfactant, and (iii) 0-10% by weight of any anion other than primary alcohol sulfate or alkylbenzene sulfonate. 17-35% by weight of non-soap detergent active materials consisting of surfactants; (b) 0-10% by weight of any fatty acid soap; and (c) 25-45% by weight (based on anhydrous). crystalline or amorphous alkali metal aluminosilicate, and (d) anionic surfactant component (a) (i)
contains 10-60% by weight of primary alcohol sulfate, 0-10% by weight of sodium carbonate, and 60-80% by weight of anionic surfactant component (a)(i).
0 if it contains primary alcohol sulfate
~20% by weight sodium carbonate, 10-20% by weight sodium carbonate if anionic surfactant component (a) (i) contains 80-100% by weight primary alcohol sulfate, and (e) A particulate detergent composition comprising up to 100% by weight of any other detergent ingredients. Claim 2: Anionic surfactant component (a)(i)
comprises 60-75% by weight of primary alcohol sulfate and 25-40% by weight of linear alkylbenzene sulfonate, and the composition comprises 0-10% by weight of sodium carbonate. 1. The detergent composition according to item 1. Claim 3: Anionic surfactant component (a)(i)
comprises 20-50% by weight of primary alcohol sulfate and 50-80% by weight of linear alkylbenzene sulfonate, and the composition comprises 0-10% by weight of sodium carbonate. 1. The detergent composition according to item 1. 4. Detergent composition according to claim 1, characterized in that the primary alcohol sulfate consists entirely or mainly of a material having an alkyl chain length of C14 or less. 5. Detergent composition according to claim 1, characterized in that it contains 28 to 45% by weight (based on anhydride) of crystalline or amorphous alkali metal aluminosilicate.