JPH0813984B2 - Detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to detergent compositions, particularly fabric laundry detergent compositions.

The fabric laundering composition contains a surfactant system as an essential component, which promotes the release of soil from the fabric and suspension in the wash liquor. Suitable detergent actives are
It can be divided into several groups such as anionic substances, nonionic substances and cationic substances, and commercial products contain substances selected from more than one group.

The most popular anionic detergent active is alkylbenzene sulfonate. These exhibit excellent effects especially when used at high temperatures. Other anionic surfactants have been sought that can be used as alternatives in environments that are unfavorable to the use of alkylbenzene sulphonates, but such other anionic detergent actives generally do not give sufficient effect. .

Such anionic surfactants that can be used as a substitute include primary alcohol sulfates (PAS), also known as alkyl sulfates. Tallow fat
It has been recommended to use PAS taken from t). For example, British Patent No. 1399966 (The Procter & Gamble Com
pany) discloses a detergent composition containing a surface-active system consisting of a mixture of sodium tallow alkylsulfate and a nonionic detergent active. However, the drawback of beef tallow PAS is that it cannot exert its full effect at low temperatures. This is a serious drawback considering that the washing temperature tends to be lowered.

Another PAS has been proposed in the industry. For example, the above-mentioned British Patent No. 1399966 also discloses the possibility of utilizing PAS taken from coconut oil. Palm oil PAS was found to be more effective than beef tallow PAS at low temperatures under certain conditions, but palm oil PAS at higher temperatures under similar conditions.
The effect of PAS is significantly inferior to that of beef tallow PAS. On the other hand, consumers expect one product to be used at both high and low temperatures to obtain sufficient effect, so palm oil PAS should be used as beef tallow P
Substituting for AS is not a valid choice.

It is an object of the present invention to propose a surfactant system containing PAS as a main component and exerting an effect maintained at a sufficient level in a series of temperature ranges.

The inventors have found that PASs with a wider distribution of alkyl chain lengths give the desired results than when the alkyl chain is derived from a source of beef tallow or coconut oil alone. PAS derived from a mixture of multiple ingredients is beef tallow PAS at low temperatures
It shows a better effect than that of palm oil PAS at high temperatures. Also, under certain conditions beef tallow PAS
Or it shows a better effect than both palm oil PAS. Beef tallow or coconut oil PAS may be more effective at limited temperatures, whereas PAS with a wide range of alkyl chain lengths may be more effective over a wide temperature range.

A characteristic of the chain length distribution is that alkyl chains containing 12 and 18 carbon atoms are included in amounts or ratios that cannot be present in alkyl chains derived from a single natural source.

Therefore, a first object of the present invention is to include a surfactant system containing an anionic surfactant based on an alkylsulfate having a mixed alkyl chain length, wherein the alkyl chain present in the alkylsulfate is a higher weight percent C ₁₂ chain, 20 wt% or more C ₁₈ chain of the alkyl chain, the ratio of C ₁₂ alkyl chain pairs C ₁₈ alkyl chains 9: 4 to 1: 6, preferably 2: 1 ~ 1: 5
To provide a fabric laundry detergent composition which is in the range of

By comparison, the amounts of C ₁₂ alkyl and C ₁₈ alkyl in coconut oil are typically 53% and 12%, the ratio of each to
3: 1 or more (actually 4: 1 or more). In addition, the beef tallow feed oil contains 70% or more of C ₁₈ alkyl chains, and contains almost no C ₁₂ alkyl chains.

In the composition of the present invention, preferably 15% by weight or more of the alkyl chain present in the alkyl sulfate is C ₁₂ and 2
5% by weight or more is C ₁₈ .

As described above, the alkyl sulfate having a mixed chain length is 50% or more of the amount of the anionic surfactant present. Of course, the sulfate salt may constitute the entire amount of the anionic surfactant present. Preferably, the alkyl sulfate corresponds to 60% or more of the amount of the anionic surfactant present, more preferably 80%.
% Or more.

Alkylsulfates are also known as sulfated fatty alcohol salts. Alkyl sulphates particularly suitable for the present invention are prepared from common natural alcohols, such as those obtained by reducing the glycerides of naturally occurring fats and oils.

As natural alcohols rich in C ₁₂ alkyl chains, there are alcohols collected from babassu palm, coconut, ouri-coury, and oil palm (palm kernel), and as alcohols rich in C ₁₈ alkyl chains, beef tallow, kapok, olives, peanuts. , Sesame, tall oil and alcohols derived from teaseed.

Natural alcohols may be cured. In this case no unsaturated alkyl chains are present. However, PAS taken from non-hardened material such as non-hardened tallow alcohol may be used such that unsaturated chains are present. The C ₁₈ unsaturated chain is usually oleyl but other unsaturations, eg linole chains may be present.

Other alkyl and unsaturated chains besides C ₁₂ and C ₁₈ chains may be present in the PAS materials useful in the present invention. These chains will usually contain from 8 to 18 carbon atoms. Materials containing small amounts of chains containing more than 18 or less than 8 carbon atoms, such as about 2% or more, are not preferred.

Considering the suitability for use, it is preferable to use PAS obtained from a mixture of beef tallow and coconut oil in a weight ratio of 3: 1 to 1: 3, and 2: 1 to
The use of PAS obtained from a 1: 2 mixture is highly preferred.

The use of water-soluble salts of these anionic surfactants, especially their alkali metal (sodium or potassium) salts, is preferred.

A preferred composition of the invention is from 2 to 50% by weight, eg 4
Contains -30% by weight of surfactant system.

The composition of the present invention also preferably contains a nonionic surfactant. Such nonionic surfactants are 10.5
Effective even with HLB above, but H less than 10.5
It was found to be extremely effective when carrying LB.

Suitable nonionic surfactants which can be used are the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, such as aliphatic alcohols, acids, amides or alkylphenols, alkylene oxides, especially ethylene oxide alone or propylene oxide. It is a reaction product with coexisting ethylene oxide. Specific nonionic detergent compounds include alkyl (C ₆ -C ₂₂ ) phenol-ethylene oxide condensates, linear or branched aliphatic (C ₈ -C ₁₈ ) primary or secondary alcohols with ethylene oxide. It is a condensation product and a composition obtained by condensation of a reaction product of propylene oxide and ethylenediamine with ethylene oxide.

When the alkyl oxide adduct of an aliphatic substance is used as the nonionic surfactant, the number of alkylene oxide groups per molecule has a considerable influence on the HLB of the nonionic surfactant. The chain length and type of the aliphatic substance also have a great influence. Therefore, the preferred number of alkylene oxide groups per molecule depends on the type and chain length of the aliphatic substance.

The weight ratio of anionic surfactant to nonionic surfactant is preferably 10: 1 to 1: 4, very preferably 4: 1 to 1: 4.
Turned out to be 2.

The surface-active system may contain other alkyl-sulfates and other surface-active substances than the non-ionic substances mentioned above.
These other surface-active substances may be selected from other anionic detergent active substances, amphoteric or amphiphilic detergent active substances or mixtures thereof.

The level of such other surfactants is up to 50% of the composition. Preferably 40% of the total amount of surfactant in the composition
It is believed that it is less than or equal to 5% of the total composition.

Another anionic detergent surfactant that may be present is from about 8 to
The usually water-soluble alkali metal salts of organic sulfonates having an alkyl group containing about 22 carbon atoms may be used. The term alkyl is understood to include the alkyl part of the higher acyl groups. Examples of suitable synthetic anionic detergent compounds are alkyl (C ₉ ~C ₂₀₎ sodium benzenesulfonate and potassium, particularly linear secondary alkyl (C ₁₀ -C
₁₅ ) Sodium benzene sulfonate; sodium alkyl glyceryl ether sulfate, especially higher alcohols derived from beef tallow or coconut oil and ethers of synthetic alcohols derived from petroleum; coconut oil fatty acid monoglyceride sodium sulfate and sodium sulfonate; higher ( C ₈ ~
C ₁₈ ) Sodium and potassium salts of sulfuric acid ester of fatty alcohol-ethylene oxide reaction product; reaction composition of fatty acid such as coconut oil fatty acid esterified with isethionic acid and neutralized with sodium hydroxide; sodium salt of fatty acid amide of methyl taurine Salts and potassium salts; alkane monosulfonates and paraffins and SO ₂ obtained by the reaction of α-olefin (C _{8 to} C ₂₀ ) with sodium bisulfite
It is an alkane monosulfonate obtained from random sulphate, which is obtained by reacting Cl ₂ with Cl ₂ and is hydrolyzed with a base.
Another anionic detergent active which may be present is a soap, especially a soap containing a high proportion of unsaturated acyl chains.

The compositions of the present invention may contain a detergency builder material. This can be any substance capable of lowering the level of free calcium ions in the wash liquor, preferably providing an alkaline pH. It provides advantageous properties such as suspending soil removed from the fabric. The amount of builder material in the composition according to the invention may in particular be 15 to 60% by weight of the composition.

Phosphorus-containing inorganic detergency builders which may be present are water-soluble salts, especially alkali metal pyrophosphates, orthophosphates,
Includes metaphosphate, polyphosphate and phosphonate.
Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, sodium and potassium orthophosphate, sodium and potassium hexametaphosphate.

Phosphorus-free inorganic detergency builders which can be present are water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and non-quality aluminosilicates. Specific examples are sodium carbonate (optionally with calcite seeds), potassium carbonate (optionally with calcite seeds), sodium and potassium bicarbonate and sodium and potassium silicates.

Examples of organic detergency builders are alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetylcarboxylates and polyhydroxysulfonates. Specific examples are ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid,
Sodium, potassium, lithium, ammonium and substituted ammonium salts of meritic acid, benzene polycarboxylic acid and citric acid.

The composition of the present invention is preferably alkaline. That is, a pH of 8 or more at a concentration of 1 g / in 25 ° C. groundwater, preferably
Must be 10 or more. For this purpose, the composition may contain a water-soluble alkali salt. This salt may be a detergency builder or it may be an alkaline substance which has no builder effect.

 Many optional components other than the above components may be present.

Examples of further ingredients that may be present in the composition are fabric softeners such as aliphatic amines and fabric softening clay materials, alkanolamides, especially foaming enhancers such as monoethanolamide taken from palm kernel fatty acids and coconut oil fatty acids. Agents, foam inhibitors, oxygen free bleaching agents such as sodium perborate, sodium percarbonate, peracid bleach precursors, chlorine free bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and usually extremely It is a fluorescent agent present in a small amount, a fragrance such as a deodorant, an enzyme such as protease, cellulase, amylase and lipase, a bactericide and a coloring agent.

The method of preparing the detergent composition of the present invention can be selected from a number of different methods depending on the respective physical form. For granular products, the compositions are prepared by dry blending or core glomerulation. The preferred physical form is granules mixed with detergency builder salts, the most suitable method of preparing compositions of this form is to spray dry at least a portion of the composition. In this method, a slurry is prepared containing a heat-sensitive component of the composition such as a surfactant system, a builder substance and a salt of a filler and the slurry is spray dried to form granules of base powder. This is mixed with solid heat sensitive ingredients such as bleach and enzymes. Certain nonionic surfactants are liquefied by melting or solvent dissolution and sprayed onto the base powder granules without mixing with the spray drying slurry.
The invention is explained in more detail below on the basis of non-limiting examples.

Examples 1 to 6 A washing liquid was prepared using water having a hardness of 25 ° FH (hardness corresponding to a free calcium ion concentration of 2.5 × 10 ^-3 mol). The washing liquor contained the following compositions in an amount corresponding to 6 g / wt%.

Specific anionic surfactant 9% Specific nonionic surfactant 4% Sodium tripolyphosphate 23% Sodium carbonate 6% Sodium alkali silicate 5.5% Sodium sulfate 30.8% Sodium chloride 2.93% Water Remaining sodium chloride is actually Is included at an ionic strength corresponding to 5% sodium monohydrate perborate present. Bleach was omitted from the experiment to avoid confusion between detergency and bleaching effect when interpreting the results.

The above washing liquid was used so that the ratio of washing liquid to laundry was 50: 1. Mix several polyester monitors, pre-loaded with an amount of C ¹⁴ labeled triolein, with the wash cloth.
The level of labeled triolein after washing was measured by the standard radiotracer technique. This measurement is the detergency, that is, the degree of decontamination obtained (soil removal, soil remova
l) is an index.

Washed for 20 minutes with 70 rpm agitation. The constant wash temperature specified below was used.

 The anionic surfactants used are shown in the table below.

In Examples 1 to 6, SYNPER was used as the nonionic surfactant.
ONIC A7 (ICI) was used. It is a predominantly C ₁₃ / C ₁₅ alcohol ethoxylated with an average of 7 moles of ethylene oxide. The HLB of this nonionic surfactant is 11.7.
Is.

 The results obtained are shown below.

Example No. Anionic washing temperature Decontamination% 1 ELFAN 280 30 ° C 24.9 2 ELFAN KT550 30 ° C 30.0 3 SULFOPON T55 30 ° C 24.9 4 ELFAN 280 60 ° C 30.5 5 ELFAN KT550 60 ° C 36.3 6 SULFOPON T55 60 ° C 46.7 These results From this, it is clear that at 60 ° C, ELFAN KT550 exhibits a higher effect than ELFAN 280 containing PAS made from only coconut oil. ELFAN KT550 at low temperature of 30 ℃
Has a higher effect than substances made from only palm oil and beef tallow, respectively.

Examples 7-12 Tests were carried out as in Examples 1-6, except that a mixture of 1 part SYNPERONIC A7 and 3 parts SYNPERONIC A3 was used as the nonionic surfactant. SYNPERONIC A3 is a similar substance in which alcohol is ethoxylated with an average of 3 moles of ethylene oxide per molecule. The HLB of this nonionic surfactant mixture is about 9.0.

 The results are shown below.

Example No. Anionic washing temperature Decontamination% 7 ELFAN 280 30 ° C 39.0 8 ELFAN KT550 30 ° C 38.7 9 SULFOPON T55 30 ° C 30.4 10 ELFAN 280 60 ° C 44.6 11 ELFAN KT550 60 ° C 49.8 12 SULFOPON T55 60 ° C 54.4 These results As in Examples 1-6, ELFA at 60 ° C
It is clear that N KT550 shows a better effect than ELFAN 280, which contains PAS derived from palm oil only. At lower temperatures ELFAN KT550 is a SULF containing PAS derived solely from beef tallow.
There is no significant difference compared to substances derived solely from coconut oil, which show a better effect than OPON T55.

A comparison of the results of Examples 7-12 with the results of Examples 1-6 reveals that the use of nonionic surfactants with lower HLB is preferred.

Examples 13-24 The tests of Examples 1-3 were repeated with varying levels and levels of surfactant. The composition changes and the results are shown in the following table. “A3” and “A7” in the table are SYNPERONIC A
3 and SYNPERONIC A7 are shown. Examples 1-3 in any test
A wash temperature of 30 ° C was used as in.

In these tests, ELFAN KT550 was tested for all tallow SUL.
It has been found to show superior effects to EOPON T55 and close or higher effects to all palm oil based ELFAN 280. The decontamination rate of this ELFAN KT55 is higher than the average value of any of palm and beef tallow substances.

Examples 25 to 31 A washing liquid was prepared with water having a hardness of 30 ° FH (hardness corresponding to a free calcium ion concentration of 3.0 × 10 ^-3 mol). Washing liquid
The following composition was contained in an amount corresponding to 6 g / (wt%).

Specific surfactant 13% Zeolite 24% Polyacrylate 4% Sodium sulphate 20.6% Sodium carbonate 12% Water Remainder Washing solution was prepared from each composition and several test cloths were washed by heating cycle up to 60 ° C using Tergotometer. did. The test cloth after washing was measured for the increase in reflectance.

 The test cloth with the following stains was used.

EMPA-104: Stain of Indian ink and olive oil WFK-10C: Stain consisting mainly of wool fat and containing a small amount of kaolin, carbon black and iron oxide PC-9: Stain of ground nut oil, Indian ink and iron oxide Specific surfactants include 0-100% hardened tallow alcohol sulphate (TAS) and / or coconut oil alcohol sulphate (CAS) and mixtures of these sulphates with nonionic surfactants (NI). Composed from. The nonionic surfactant (NI) is SYNPERONIC A3, a C ₁₃ / C ₁₅ fatty alcohol ethoxylated with an average of 3 moles of ethylene oxide per molecule.

 The results are shown below.

In all the examples, the mixture of hardened tallow-based and coconut oil-based surfactants showed better detergency than each used alone.

Examples 32-33 A washing liquid was prepared with water having a hardness of 25 ° FH. 6g / washing liquid
The following composition was contained in an amount corresponding to Ingredient Weight% Specific anionic 9 SYNPERONIC A7 1 SYNPERONIC A3 3 Zeolite 26.6 Sodium sulfate 19.5 Sodium carbonate 14.0 Sodium silicate 1.3 Sodium chloride 3.0 Moisture balance (up to 100%) In Example 32, ELFAN KT55 as anionic surfactant.
0 was used. In Example 33, P derived from myristyl alcohol (ie, C ₁₄ alcohol) was used as the anionic surfactant.
I used AS. The washing liquor was tested as in Examples 1-6 using different brands of polyester cloth as test cloths.

 The decontamination effect is shown below.

Example 32 (ELFAN KT550) 28.1% Example 33 (C ₁₄ PAS) 26.0% Example 34 A multi-component slurry forming a base powder is spray dried, sprayed onto a nonionic surfactant and the remaining components The following formulations were prepared by post-adding:

This composition was used to wash different soiled fabrics under different conditions. The results were evaluated by measuring the reflectance of the treated monitor fabric. Beef tallow PA as anionic surfactant
S, coconut oil PAS and a 50/50 mixture of both were used.

The advantages obtained in the previous example were confirmed in this example as well. That is, the 50/50 blends generally show superior effects over palm PAS alone and significantly outperform both beef tallow and palm oil against many stains, especially motor oils and cosmetic stains on white cotton. Showed the effect.

 ─────────────────────────────────────────────────── ───Continued from the front page (72) Inventor Dennis Gills, Merseyside El 63.0.E.H., Wilal, Broumbala, Brutskhurst Road, 33 (72) Inventor Brian Cecil Smith, Netherlands, N El-3055 Kerr el Rotterdam, Mosaltrahn 46 (56) References JP 62-240397 (JP, A) JP 62-273300 (JP, A)

Claims (7)

[Claims] 1. An alkylsulfate having a mixed alkyl chain length
What is claimed is: 1. A laundry detergent composition containing a surfactant system comprising 80% or more of an anionic surfactant, wherein 10% by weight or more of an alkyl chain present in the alkyl sulfate is C ₁₂
20% by weight or more of the alkyl chain is a C ₁₈ chain, and the weight ratio of the C ₁₂ alkyl chain to the C ₁₈ alkyl chain is 9: 4 to 1: 6.
The composition is in the range of. 2. The composition according to claim 1, wherein the weight ratio is in the range of 2: 1 to 1: 5. 3. The composition according to claim 1, wherein 15% by weight or more of the alkyl chain is a C ₁₂ chain and 25% by weight or more is a C ₁₈ chain. 4. The weight ratio of the alkyl sulfate to the tallow alkyl sulfate and the coconut oil alkyl sulfate is 3: 1 to 1: 3, preferably 2 :.
The detergent composition according to claim 1, which is a mixture of 1 to 1: 2. 5. The detergent composition according to any one of claims 1 to 4, further comprising a nonionic surfactant. 6. The detergent composition according to claim 5, wherein the nonionic surfactant has an HLB of less than 10.5. 7. Composition according to claim 5 or 6, characterized in that the weight ratio of alkylsulfate to nonionic surfactant is in the range from 10: 1 to 1: 4.