KR960000198B1 - Detergent composition - Google Patents

Abstract

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Description

Detergent composition

The present invention relates to detergent compositions, in particular detergent compositions for fabric washing.

Fabric washing compositions contain, as an essential component, a surfactant system that serves to remove dirt from the fabric and aid in suspension in the wash liquor. Suitable detergent active materials are divided into several classes, including anionic, nonionic and cationic materials, and commercial products contain materials selected from one or more of these classes.

The most widely used anionic detergent inerts are alkyl benzene sulfonates, which give satisfactory results, especially at high temperatures. Where alkyl benzene sulfonates are undesirable-it is preferred to use other alternative anionic surfactants, but generally speaking the performance of other anionic detergent active materials is not satisfactory.

Examples of such alternative anionic surfactants are primary alcohol sulfates (PAS), known as alkyl sulfates. The use of PAS derived from tallow fat is recommended. British Patent 1399966 (The Procter & Gamble Company) discloses detergent compositions in which the surfactant system is a mixture of tallow alkyl sodium sulfate and a nonionic detergent active material. However, tallow PAS suffers from poor performance at low temperatures. This is a significant disadvantage when considering the tendency of the washing temperature to lower.

Other PAS are also proposed in the art. Thus, for example, the aforementioned British patent 1399966 also discloses the use of PAS derived from coconut oil. Under some circumstances, coconut PAS may perform better than tallow PAS at low temperatures, but under these conditions, performance at higher temperatures is much poorer than tallow derived materials. Thus, while consumers expect a single product that performs satisfactorily at both high and low temperatures, replacing tallow PAS with coconut PAS is not an attractive option.

It is an object of the present invention to provide a PAS based surfactant system which can exhibit a good combination of performance levels in a series of temperature ranges.

We have found that this performance can be achieved by using PAS having a broader alkyl chain length when tallow alone or coconut alone is an alkyl chain source. The use of PAS derived from mixtures of alkyl chain members can result in better performance than tallow PAS at low temperatures and better than coconut PAS at higher temperatures. Under some circumstances, performance is better than tallow or coconut PAS. They can perform better at specific temperatures, but PAS with a wide range of alkyl chain lengths can be used to achieve good performance over a wide range of temperatures.

The range of chain lengths may be characterized by the presence of alkyl chains in amounts or proportions that do not occur when C ₁₂ and C ₁₈ are derived from a single natural chain source.

In one aspect of the invention, at least 10% by weight of the alkyl chains in the alkyl sulphate are C ₁₂ chains and at least 20% by weight of the alkyl chains are C ₁₈ chains, and the weight ratio of C ₁₂ alkyl chains to C ₁₈ alkyl chains is 9: 4. Provided is a detergent composition for fabric laundry comprising a surfactant system comprising an anionic surfactant based on alkyl sulfates of mixed alkyl chain lengths in the range of -1: 6, preferably 2: 1-1: 5 It is.

In comparison, the percentages of C ₁₂ and C ₁₈ alkyl in coconut raw materials are typically 53% and 12%, with a ratio of at least 3: 1 (actually at least 4: 1), while the alkyl chains in tallow are 70%. C ₁₈ alkyl and C ₁₂ may be nearly absent.

In the compositions of the invention it is preferred that at least 15% by weight of the alkyl chains present in the alkyl sulphate are C ₁₂ alkyl chains and at least 25% by weight thereof are C ₁₈ alkyl chains.

As mentioned above, alkyl sulfates with mixed chain lengths account for at least 50% of anionic surfactants. Of course, alkyl sulphate may comprise 100% of the anionic surfactant. Preferred is that the alkyl sulphate comprises at least 60%, or at least 80% of the anionic surfactant.

Alkyl sulfates are also known as sulfided fatty alcohol salts. In particular the alkyl sulphates used in the present invention are commonly produced from natural alcohols such as those produced by reducing the glycerides of natural fats and oils.

Natural alcohols rich in C ₁₂ alkyl chains include alcohols derived from babasu, coconut, uri-core and palm kernels, while alcohols rich in C ₁₈ alkyl chains include tallow, kapok, olives, peanuts and sesame seeds. Alcohols derived from tall oil, and oilseeds.

Natural alcohols can be cured in the absence of unsaturated alkyl chains. However, PAS derived from uncured material such as uncured tallow alcohol can be used to ensure the presence of unsaturated chains. The C ₁₈ unsaturated chain will usually be oleyl, but may be higher in unsaturation. That is, linolenic chains may be present.

PAS materials useful in the present invention may have other alkyl and unsaturated chains in addition to the C ₁₂ and C ₁₈ chains. These chains will usually be C ₈ -C ₁₈ . Materials that contain a small amount of chains greater than C ₁₈ or less than C ₈ , ie at least about 2%, are less preferred.

In view of ease of purchase, it is preferable to use PAS derived from a mixture of tallow and coconut having a weight ratio of 3: 1-1: 3, more preferably 2: 1-1: 2.

As these anionic surfactants, it is preferable to use water-soluble salts thereof, particularly alkali metal (sodium or potassium) salts.

Preferred compositions according to the invention comprise from 2% to 50% by weight of surfactant, preferably from 4% to 30% by weight.

It is preferable that the composition of the present invention also contains a nonionic surfactant. The present inventors have found that such nonionic surfactants have an advantage even if they have an HLB of 10.5 or more, but are more advantageous than those having an HLB of less than 10.5.

Suitable nonionic surfactants include the reaction of hydrophobic groups with compounds having reactive hydrogen atoms (e.g. aliphatic alcohols, acids, amides or alkylphenols) with alkylene oxides (especially ethylene oxide alone or ethylene oxide / propylene oxide) The product can be used. Specific nonionic detergent compounds include alkyl (C ₆ -C ₂₂ ) phenol-ethylene oxide condensates, condensation products of aliphatic (C ₈ -C ₁₈ ) primary or secondary linear or branched alcohols with ethylene oxide, and propylene oxide And a product produced by the condensation of a reaction product of ethylenediamine with ethylene oxide.

When alkylene oxide adducts of fatty substances are used as nonionic surfactants, the number of alkylene oxide groups per molecule has a significant effect on the HLB of the nonionic surfactants. Since the chain length and type of fatty material also affects, the preferred number of alkylene oxide groups per molecule depends on the type and chain length of fatty material.

The inventors have found that the weight ratio of anionic surfactant to nonionic surfactant is advantageously 10: 1-1: 4, more preferably 4: 1-1: 2.

The surfactant crab may include other surfactant materials in addition to the specific alkyl sulfates and the nonionic materials described above. These other surfactant materials may be selected from other anionic detergent active materials, zwitterionic or amphoteric detergent active materials or mixtures thereof.

The content of any such additional surfactant material should not exceed 50% of the composition. The surfactant is preferably at most 40% of the total amount of the surfactant in the composition, and may be preferably at most 5% by weight of the total composition.

Used as other anionic detergent active materials are water soluble alkali metal salts of organic sulfonates which usually have alkyl groups of about C ₈ -C ₂₂ . The term alkyl is used herein to include the alkyl portion of the higher acyl group. Examples of suitable synthetic anionic detergent compounds include alkyl (C ₉ -C ₂₀ ) benzene sodium sulfonate and potassium sulfonate, especially linear secondary alkyl (C ₁₀ -C ₁₅ ) benzene sulfonate; Alkyl glyceryl ether sodium sulfate, especially ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; Coconut oil fatty acid monoglycerides sodium sulfate and sodium sulfonate; Sodium and potassium salts of sulfuric esters of higher (C ₈ -C ₁₈ ) fatty alcohol-ethylene oxide reaction products; Reaction products obtained by esterifying fatty acids such as coconut fatty acids with isethionic acid and neutralizing with sodium hydroxide; Sodium and potassium salts of fatty acid amides of methyl taurine; Alkanes such as substances derived by the reaction of alpha-olefins (C ₈ -C ₂₀ ) with sodium bisulfite, and substances derived by hydrolysis with base to generate random sulfates after the reaction of paraffins with SO ₂ and Cl ₂ Monosulfonate, and the like. Further anionic detergent actives which may also be used are soaps, in particular soaps having a high content of unsaturated acyl chains.

Compositions of the present invention may contain detergent builder materials. Detergent builder materials can be used as long as they can reduce the amount of free calcium ions in the wash liquor, and in particular, it would be desirable to provide the composition with other beneficial properties, such as the formation of alkaline pH, suspension when removed from the fabric, and the like. . The amount of builder material in the composition of the present invention may in particular range from 15% to 60% by weight of the composition.

When phosphorus-containing inorganic detergent builder is contained, for example, there are water-soluble salts, especially alkali metal salts of pyrophosphoric acid, orthophosphoric acid, metaphosphoric acid, polyphosphoric acid and phosphonic acid.

Specific examples of inorganic phosphate builders are the sodium and potassium salts of tripolyphosphoric acid, orthophosphoric acid and hexametaphosphate.

When the lean inorganic detergent builder is contained, for example, there are water-soluble alkali metal salts of carbonic acid, bicarbonate, silicic acid and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without a calcite), potassium carbonate (with or without a calcite), sodium and potassium salts of bicarbonate and silicic acid, and the like.

When organic detergent builders are contained, examples thereof include alkali metal salts, ammonium salts and substituted ammonium salts of polyacetic acid, carboxylic acid, polycarboxylic acid, polyacetylcarboxylic acid and polyhydroxysulfonic acid. Specific examples include sodium salts, potassium salts, lithium salts, ammonium salts and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melic acid, benzene polycarboxylic acid and citric acid.

The composition according to the invention is preferably alkaline. That is, the pH should be at least 8, preferably at least 10 at a concentration of 1 g / 1 in distilled water at 25 ° C. For this purpose the composition may comprise a water soluble alkali salt. This salt may be a detergent builder or an alkaline material that is not a builder.

In addition to the components described above, it may also contain various optional components.

Other components that may be included in the composition include, for example, fabric softeners such as fatty amines, fabric softening clay materials, foam accelerators such as alkanolamides (especially monoethanolamides derived from palm kernel fatty acids and coconut fatty acids), foam control agents. , Oxygen releasing bleaches such as sodium perborate and sodium percarbonate, peroxide bleaching precursors, chlorine releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulfate, etc. Enzymes such as amylases and lipases, fungicides and coloring agents and the like are also added in trace amounts.

Detergent compositions according to the invention can be prepared by a variety of different methods depending on their physical form.

In the case of granular products, they are produced by dry mixing or coagulation. Preferred physical forms are granules incorporating detergent builder salts which can be most conveniently prepared by spray drying at least a portion of the composition. In this process, slurries containing heat resistant components such as surfactants, builder materials and filler salts are prepared. The slurry can be spray dried to form basic powder granules, which can then be mixed with any solid ingredients that are weak to heat such as bleach and enzyme. Rather than incorporating certain nonionic surfactants into the slurry to be spray dried, it is preferred to liquefy by melting or solvent dissolution to spray onto the base powder granules. The invention will now be described in more detail in the following non-limiting examples.

Example 1-6

The wash liquor was made using water with a hardness of 25 FH (corresponding to a free calcium ion concentration of 2.5 × 10 ⁻³ molal concentration). The wash contained 6 g / l levels of a composition containing the following ingredients.

weight%

Specific Cationic Surfactants 9%

Specific nonionic surfactant 4%

Sodium Tripolyphosphate 23%

Sodium carbonate 6%

Alkaline sodium silicate 5.5%

Sodium sulfate 30.8%

Sodium Chloride 2.93%

Water-rest-

Sodium chloride was actually used in an amount corresponding to the ionic strength for the 5% sodium perborate monohydrate added. In describing the results, the use of bleach was omitted in this experiment to avoid confusion between the cleaning power and the bleaching effect.

The test cloth was washed with the wash solution so that the ratio of wash solution to wash cloth was 50: 1. As a laundry, a polyester monitor to which C ¹⁴ label-triolein was applied in advance was used. After washing, the amount of label-triolein achieved was determined by measuring the amount of label-triolein using standard radiotracer techniques to determine the degree of clearance achieved.

Washing was performed for 20 minutes under 70 rpm stirring. The washing temperature was kept at the temperature as recorded below.

The anionic surfactants used are listed in the following table.

TABLE 1

1-Akzo Products

2-Henkel Products

As nonionic surfactants in Examples 1 to 6, SYNPERONIC A7 (manufactured by ICI), a C ₁₃ / C ₁₅ alcohol, ethoxylated mainly with an average of 7 mol ethylene oxide was used. The HLB of this nonionic surfactant is 11.7.

The obtained result is as follows.

TABLE 2

From the above results it can be seen that at 60 ℃ Elpan KT550 is superior to PAS derived from coconut only, that is, Elpan 280. It can be seen that at low temperature 30 ℃ Elpan KT550 is superior to the material derived from coconut only and the material derived from tallow only.

Example 7-12

Examples 1-6 were repeated except that the nonionic surfactants were 1 part of synferonic A7 and sinferonic A3 (an analog of ethoxylated alcohol with an average of 3 moles of ethylene oxide per molecule). A mixture of 3 parts was used. The HLB of this nonionic surfactant mixture was about 9.0.

the results are as follow.

TABLE 3

From the above results, it can be clearly seen that, as in Examples 1 to 6, Elpan KT550 is superior to PAS derived from coconut only, that is, Elpan 280 at 60 ° C. At low temperatures, Elpan KT550 is superior to PAS derived from talommann, ie sulfophon T55, and there is no significant difference compared to the scrubbing ability of materials derived from coconut only.

Comparing the results of Examples 7-12 with the results of Examples 1-6, it can be seen that it is advantageous to use nonionic surfactants with lower HLB.

Example 13-24

The procedure of Example 1-3 was repeated except test with varying the content and proportion of surfactant. The change in composition and the results are shown in the table below. Here, “A3” and “A7” mean synferonic A3 and synferonic A7, respectively. Washing temperature was maintained at 30 ° C. in each case as in Examples 1-3.

TABLE 4

As can be seen in each case, the Elpan KT550 is all superior to the tallow sulfophon 55, and all are superior to or comparable to the coconut Elpan 280. In each case, the Elpan KT550 exhibits better dirt removal than the average for both coconut- and tallow-induced materials.

Example 25-31

The wash liquor was made using water at 30 ° FH (corresponding to a free calcium ion concentration of 3.0 × 10 ⁻³ molal temperature). The wash contained 6 g / l levels of a composition containing the following ingredients.

weight%

Specific Surfactant 13%

Zeolite 24%

Polyacrylate 4%

Sodium sulfate 20.6%

Sodium Carbonate 12%

Water-rest-

Several test cloths were washed using each wash liquid composition. Washing was performed using a tergotometer and the wash temperature was maintained at 60 ° C. in a heating cycle. After washing, the increase in reflectance of the test cloth was measured.

The test cloth used included several types of stains as follows.

EMPA-104: Indian Ink and Olive Oil Stain

WFK-10C: Stain whose main component is wool, small amount of kaolin, carbon black and iron oxide

PC-9: Peanut Oil, Indian Ink and Iron Oxide Stain

Certain surfactant (s) are ethoxylated with some or all cured tallow alcohol sulphate (TAS) and / or coconut alcohol sulphate (CAS) and synferonic A3 (average 3 moles of ethylene oxide per molecule) A mixture with nonionic surfactant (NI), which is a silicified C ₁₃ / C ₁₅ fatty alcohol).

the results are as follow.

TABLE 5

In each case it can be seen that the mixture of cured tallow based surfactants and coconut based surfactants is superior in cleaning power than if they were each used alone.

[Examples 32 and 33]

The wash liquor was made using water with a hardness of 25 ° FH. Washing liquid contained a composition containing the following components at the level of 6 g / l.

TABLE 6

In Example 32, Elfan KT550 was used as the anionic surfactant. In Example 33, PAS derived from myristyl alcohol (ie, C ₁₄ alcohol) was used as the anionic surfactant. Wash liquor was used as in Examples 1-6, but various grades of polyester were used as the test cloth.

The result of the remove function is as follows.

Example 32 (Elpan KT550) 28.1%

Example 33 (C ₁₄ PAS) 26.0%

Example 34

A composition having the following composition was prepared. That is, a slurry containing some components was spray dried to form a basic powder, followed by spraying a portion of the nonionic surfactant thereon, followed by post addition of the remaining components.

TABLE 7

This composition was used to wash various stained fabrics under various conditions and the test results were evaluated by measuring the reflectance of the treated monitor. Anionic surfactants were tallow PAS, coconut PAS and tallow / coconut PAS 50/50 mixtures.

The benefits observed in the previous examples were again observed in this case. Thus, the 50/50 mixtures generally performed better than coconut PAS alone and were better in both cases, as well as in various stains (especially dirty motor oils and cosmetic stains present on the white side).

Claims (10)

(i) at least 10% by weight of the alkyl chains of the alkyl sulfates are C ₁₂ chains and at least 20% by weight of the alkyl chains are C ₁₈ chains, and the weight ratio of C ₁₂ alkyl chains to C ₁₈ alkyl chains is from 9: 4-1 A surfactant-based detergent composition comprising an anionic surfactant based on an alkyl sulphate having a mixed alkyl chain length in the range of: 6, and (ii) a detergent builder. The detergent composition of claim 1, wherein the weight ratio is in the range of 2: 1-1: 5. 2. The detergent composition of claim 1, wherein the alkyl sulfate having a mixed chain length accounts for at least 60% of the anionic surfactant. 2. The detergent composition of claim 1, wherein the alkyl sulphate having a mixed chain length comprises at least 80% of the anionic surfactant. The detergent composition according to claim 1, wherein at least 15% by weight of the alkyl chain is a C ₁₂ chain and at least 25% by weight is a C ₁₈ chain. 4. The detergent composition of claim 1 or 3, wherein the alkyl sulfate is a mixture of tallow alkyl sulfate and coconut alkyl sulfate having a weight ratio of 3: 1-1: 3. The detergent composition according to claim 1, further comprising a nonionic surfactant. 8. The detergent composition of claim 7, wherein the nonionic surfactant has an HLB of less than 10.5. The detergent composition according to claim 7 or 8, wherein the weight ratio of alkyl sulfate to nonionic surfactant is in the range of 10: 1-1: 4. 4. The detergent composition of claim 1 or 3, wherein the alkyl sulfate is a mixture of tallow alkyl sulfate and coconut alkyl sulfate having a weight ratio of 2: 1-1: 2.