GB2208297A - Liquid detergent composition containing natural fruit juice - Google Patents

Abstract

A liquid detergent composition comprises:- (A) 5-60 wt.% of at least one non-soap synthetic surfactant selected from anionic surfactants, nonionic surfactants and amphoteric surfactants, (B) 0.05-5 wt.% of a dicarboxylic-acid-type surfactant, and (C) 0.01-4.5 wt.% of a natural fruit juice containing organics acids and reduced sugars, the pH of said composition in its undiluted form being 4-6.5. Ingredient (B) may be of formula:- <IMAGE> where R1 is C8-15 alkyl or alkenyl; R2 and R3 are each -(CH2CH2O)n-(CH2)m- (where m=1-5 and n=0-5) and may contain one or more branched chains; and M1 and M2 are each H, alkali or alkaline earth metal or alkanolamine. The composition has improved colour stability and rinsability, and may be used as a laundry, dishwashing, house- cleaning, hair or body detergent.

Description

TITLE OF THE INVENTION: LIQUID DETERGENT COMPOSITION BACKGROUND OF THE INVENTION 1) Field of the Invention: This invention relates to a liquid detergent composition usable widely as a laundry detergent, dish-washing detergent, housecleaning detergent, hair detergent, body detergent or the like, and especially to a detergent composition containing a natural fruit juice and improved in coloration resistance and rinsability.

2) Description of the Prior Art: In recent years, it has begun to add a natural fruit juice to a liquid detergent composition with a view toward improving the detergency, rinsability, fragrance, color, touch feeling to the skin, etc. of the detergent composition and also removing offensive odor from items to be cleaned. Among those reported, there are, for example, a detergent composition comprising 30-80 wt.% of water, 0.1-35 wt.% of a detergent and 0.1-15 wt.% of a citrus juice and adapted to remove fishy stink (U.S.Patent No. 3,650,968) as well as a liquid detergent composition which comprises 5-60 wt.% of an organic synthetic surfactant composed of at least two surface active agents and 5-50 wt.% of a citrus juice and is effective for hardly removable dirtsuch as burnt protein and starch (Japanese Patent Publication No. 50680/1983).

However, a product containing a natural fruit juice is generally known to undergo browning and to be significantly deteriorated in quality during its storage. This browning is said to be attributed primarily to reactions (aminocarbonyl reactions) between carbonyl compounds (including sugars) and amino compounds such as amino acids contained in natural fruit juices. Such browning occur likewise in detergent compositions which contain a natural fruit juice, such as those described above. Research has therefore been conducted to prevent such browning. For example, it has been proposed to incorporate, as a browning preventive, a substance capable of coupling to carbonyl compounds as basic reactants in the above-described aminocarbonyl reactions and stopping the reactions (namely, a substance capable of serving as a carbonyl indicator), sulfurous acid, a salt thereof or the like.These substances are however not fully effective and moreover, are accompanied by a drawback that in a detergent composition containing a coloring material, the coloring material is considerably faded due to their reducing action.

Since browning of a natural fruit juice is also affected to a significant extent by organic acids contained in the fruit juice such as citric acid and malic acid [Kato & Sakurai: "Journal of the Agricultural Chemical Society of Japan", 38(11), 536-541 (1964)], there has been a particularly strong demand for the development of a browning-preventing measure for products containing a natural fruit juice in which both organic acids and sugars (reduced sugars in particular) are contained together.

bn the other hand, a detergent containing an anionic surfactant as a principal detergent base has excellent cleaning power and high foaming power. It however has high foaming power even in a low concentration, leading to a drawback that its rinsability is poor.

Rinsability is a property important for detergents such as laundry detergents and dish-washing detergents. Needless to say, poor rinsability results in longer rinsing time, so that a great deal of water is needed for rinsing. This is certainly uneconomical.

Moreover, poor rinsability gives anxiety to consumers in regard to the problem of frothing of sewage (socalled frothing pollution), whereby it may potentially lead to a social problem.

It may be contemplated of adding a rinsing agent in order to solve the above problem. However, longchain fatty acid salts and nonionic surfactants of a low HLB such as sorbitan fatty acid esters and glycerin fatty acid esters, which have heretofore been used widely as rinsing agents, have to be added in a relatively large amount in order to exhibit their effects. In the case of a liquid detergent such as a laundry detergent or dish-washing detergent, its lowtemperature stability is deteriorated considerably by their addition in such a large amount. Furthermore, foaming is impaired not only at the time of rinsing but also during washing or cleaning, so that the above approach has not been considered to be fully satisfactory.

SUMMARY OF THE INVENTION With the foregoing in view, there has been a strong demand for the development of a detergent which can be easily rinsed away, in other words, has good rinsability while having excellent detergency and assuring ample foaming during washing or cleaning.

With a view toward providing a solution to such problems, the present inventors have carried out an extensive research so as to develop a liquid detergent composition featuring less coloration during its storage and excellent rinsability without impairing most important detergency and foaming power. As a result, it has been found that a liquid detergent composition featuring less coloration during its storage and improved rinsability can be obtained by mixing a dicarboxylic-acid-type surfactant in a specific proportion to a liquid detergent composition, which contains at least one non-soap synthetic surfactant selected from anionic surfactants, nonionic surfactants and amphoteric surfactants and a natural fruit juice, and maintaining the pH of the resultant undiluted mixture within a weak acidic range, leading to completion of this invention.

In one aspect of this invention, there is thus provided a liquid detergent composition comprising the following components (A), (B) and (C): (A) 5-60 wt.% of at least one non-soap synthetic surfactant selected from anionic surfactants, nonionic surfactants and amphoteric surfactants, (B) 0.05-5 wt.% of a dicarboxylic-acid-type surfactant, and (C) 0.01-4.5 wt.% of a natural fruit juice containing organic acids and reduced sugars, the pH of said composition in its undiluted form being 4-6.5.

The liquid detergent composition of this invention undergoes extremely little color variations during its storage and exhibits excellent rinsability after cleaning without being sacrificed at its most important functions, i.e., detergency and foaming power when provided as a laundry detergent, dish-washing detergent, housecleaning detergent, hair detergent, body detergent or the like. It therefore has a high - practical value.

The above and other objects, features and advantages of the present invention will become apparent from the following description of the invention and the appended claims.

DETAILED DESCRIPTION OF-gEE INVENTION AND PREFERRED EMBODIMENTS As surfactants usable as the component (A) in this invention, the following surfactants may be mentioned.

(1) Anionic surfactants: (i) Sulfonates: Straight-chain or branched C8-C22-alkyl benzene sulfonates, straight-chain or branched C8-C22-alkyl sulfonates, long chain C8-C22-olefin sulfonates, etc.

(ii) Sulfates: Long-chain mono-(C8-C22-alkyl) sulfates, polyoxyethylene (1-6 moles) long-chain C8-C22-alkyl ether sulfates, polyoxy ethylene (1-6 moles) C8 -C18-alkylphenyl ether sulfates, etc.

(iii) Phosphates: Long-chain mono-, di- and sesqui-(C8-C22 alkyl) phosphates, polyoxyethylene (1-6 mole) mono-, di- and sesqui-(C8-C22-alkyl) phosphates, etc.

(iv) Others: Polyoxyethylene (1-7 moles) straight-chain or branched C8-C22-alkyl ether carboxy lates, long-chain (C8-C22) N-acyl glutamates, long-chain (C8-C22) N-acyl sarcosinates, straight-chain or branched di(C6-C14-dialkyl) sulfosuccinates, etc.

The counter ion (cation) in each of the above anionic surfactants may be any one of alkali metal and alkaline earth metal ions such as sodium, potassium and magnesium ions and alkanolamine ions such as monoethanol amine, diethanolamine and triethanolamine ions.

(2) Nonionic surfactants: Polyoxyethylene (1-20 moles) long-chain C8-C22 alkyl ethers, polyoxyethylene (1-20 moles) C8-C18-alkylphenyl ethers, polyoxyethylene poly oxypropylene block polymers, higher fatty acid alkanolamides and alkylene oxide addition products thereof, straight-chain and branched C10-C15- alkyl tertiary amine oxides, etc.

(3) Amphoteric surfactants: Ami no-acid- type amphoteric surfactants, betaine-type amphoteric surfactants such as alkylsulfobetaines and alkylacetic acid betaines, imidazoline-type amphoteric surfactants, etc.

Surface active agents including the aboveexemplified typical examples may be used as the component (A) either singly or in combination. The proportion of the surfactant is in a range of 5-60 wt.%, preferably, 10-40 wt.% of the detergent composition. Any proportions smaller than 5 wt.% cannot have the surfactant exhibit its detergency and foaming power fully. On the other, no substantial improvement can be expected in detergency even when the surfactant is incorporated in any proportions greater than 60 wt.%. On the contrary, such a high proportion of the surfactant deteriorates foam break-down readiness and rinsability and also renders the handling difficult due to higher viscosity upon production.

Such a low or high proportion is therefore not preferred.

As the component (B), i.e., the dicarboxylicacid-type surfactant in this invention, any one or more of the compounds represented by the following general formula (I), (II) or (III) can be used.

wherein R1 means a straight-chain or branched alkyl or alkenyl group having 8-16 carbon atoms, R2 and R3 denote individually a -qW CH2-CH2-0 t CH2 group (m: 1-5, n: 0-5) which may contain one or more branched chains, and M1 and M2 are individually a hydrogen, alkali metal or alkaline earth metal atom or an alkanol amine residue. In view of the stability and the like of the resulting composition, the dicarboxylic-acidtype surfactants represented by the general formula (I) are particularly preferred.

The component (B) may preferably be added in a range of 0.05-5 wt.%, especially, 0.1-3 wt.% based on the composition.

If the component (B) is added in any proportion outside the above range, the intended improvements in coloration resistance and rinsability can be hardly expected.

As natural fruit juices which contain organic acids and reduced sugars and are usable as the component (C) in this invention, the following fruit juices may be mentioned.

(a) Temperate zone fruits: Grape (Vitis vinifera), apple (Malus pumila), pear (Pyrus communis), peach (Prunus persica), plum (Prunus domestica, Prunus salicina, Prunus americana), melon (Cucumis melo), etc.

(b) Subtropical fruits: Orange (Citrus sinensis), grape fruit (Citrus paradisi), lemon (Citrus limon), lime (Citrus aurantifolia), guava (Psidium guajava), passion fruit (Passiflora edulis), etc.

(c) Tropical fruits: Pine apple (Ananas comosus), mango (Mangifera indica), papaya (Carica papaya), etc.

It is preferable to use a natural fruit juice having a sugar/acid ratio (the ratio of a sugar content to an acid content, i.e., sugars/organic acids) of 0.1-25 in this invention from the viewpoint of the touch feeling of the detergent composition to the skin upon its use. Any sugar/acid ratios smaller than 0.1 give squeak feeling to the hand, while any sugar/acid ratios greater than 25 result in increased sticky feeling to the hand. Accordingly, sugar/acid ratios outside the above range are not preferred.

Further, the proportion of the natural fruit juice is within a range of 0.01-4.5 wt.%, preferably, 0.1-3 wt.% of the detergent composition. If its proportion is smaller than 0.01 wt.%, the intended improvement in rinsability is insufficient. If its proportion exceeds 4.5 wt.% on the other hand, the coloration resistance and low-temperature stability of the detergent composition are deteriorated. It is hence not preferable to add the natural fruit juice in any proportion outside the above range.

The liquid detergent composition of the present invention in its undiluted form may preferably have a pH in a range of 4-6.5, with pH 5-6 being particularly preferred.

Other optional components may also be added to the detergent composition of this invention to extents not impairing the separation-resistant stability, cleaning performance and foaming performance of the detergent composition. It is therefore possible to add, for example, a lower aliphatic alcohol such as ethyl alcohol, a solubilizing agent such as the sodium or potassium salt of toluenesulfonic acid or xylene sulfonic acid or urea, a viscosity regulator such as a clay mineral or water-soluble high molecular substance, a water-insoluble abrasive such as calcite, silica, potassium phosphate, zeolite, polyethylene, nylon or polystyrene, a moisturizing agent such as glycerin or sorbitol and/or a touch feeling improver such as cationized cellulose, and/or an enzyme, perfume base, pigment, antiseptic and/or the like.

[Examples] The present invention will hereinafter be described in further detail by the following examples It should however be borne in mind that this invention is not necessarily limited to or by the following examples.

Testing Methods and Evaluation Standards: (1) Foaming power test: Tested is foaming power upon addition of 0.1 wt.% of commercial butter as a dirt component to a detergent solution whose detergent concentration was 0.5 wt.%. The measurement method comprises placing 40 ml of the butter-added detergent solution in a glass cylinder having a diameter of 5 cm, stirring the detergent solution for 10 minutes, and then measuring the height of foam immediately after the stopping of the stirring.

(2) Detergency test: Beef tallow is added with 0.1 wt.% of Sudan III (red pigment) as an indicator. A porcelain dish (diameter: 25 cm) is coated with 3 g of the resultant mixture and then rubbed and cleaned with a sponge with 10 g of a detergent and 20 g of water absorbed therein.

Detergency is indicated by the number of dishes cleaned until beef tallow was no longer wiped off from the dish.

(3) Rinsability: Three liters of a sample solution, which has a concentration of 0.25% and is contained in a vat having a diameter of 30 cm and a height of 12 cm, are stirred for 10 minutes. A cock provided in the bottom of the vat is opened to discharge the solution only. The vat is then charged with 3 of tap water. Similarly, the water is stirred for 10 minutes and then discharged.

These procedures are repeated until absolutely no foam is observed in the vat, while changing the tap water.

Rinsability is evaluated by the number of replacements of the city water.

(4) Coloration resistance: A detergent composition is filled in a trans parent polyester bottle having a capacity of 300 m and then left over for 20 days in a thermostatic chamber of 500C. After that, the degree of coloration is observed visually.

(Evaluation standard) 0: No coloration.

1: Slight coloration.

2: Substantial coloration.

3: Considerable coloration.

4: Extremely considerable coloration.

(5) Low-temperature stability: A detergent composition is filled in a transparent polyester bottle having a capacity of 300 mi and then left over for 10 days in a thermostatic chamber of -50C. After that, the state of the liquid contents is observed visually.

(Evaluation standard) A: Absolutely no changes.

B: Some clouding.

C: Substantial clouding.

Example 1: Liquid detergent compositions shown in Table 1 were prepared, followed by evaluation of their detergency, foaming power, coloration resistance, rinsability and low-temperature stability. Results are summarized in Table 1.

Table 1

Invention composition Comparative composition Component (wt.%) 1 2 3 4 5 6 7 8 Sodium laurylbenzenesulfonate 20 15 20 20 Sodium polyoxyethylene (p=3) 20 5 20 laurylsulfate Sodium &alpha;-olefin(C14)sulfonate 20 20 Monosodium octenylsuccinate 1 1 1 1 1 1 1 Lemon juice (sugar/acid ratio: 0.5) 3 3 3 3 3 3 6 Ethanol 5 5 5 5 5 5 5 5 Water Balance Balance Balance Balance Balance Balance Balance Balance pH (undiluted, 20 C) 5.0 5.5 6.0 5.5 3.5 7.0 6.0 5.5 Detergency (number of dishes) 9 8 9 10 4 9 8 6 Foaming power (mm) 90 87 88 93 60 90 87 70 Coloration resistance 0 0 1 0 2 4 0 4 Rinsability (times) 5 6 5 5 7 8 10 9 Low-temperature stability A A A A B B A C Example 2: Detergency, foaming power, rinsability and coloration resistance were tested with respect to the following liquid detergent compositions. Results are summarized in Table 2.

Formulation) Proportion (wt.%) Sodium polyoxyethylene (p=4) 20 laurylsulfate Sodium alkane(C14)sulfonate 5 Coconut oil fatty acid 3 diethanolamide Dicarboxylic-acid-type surfactant 0-5 (see Table 2) Grape fruit juice 1 (sugar/acid ratio: 5) 1 Ethanol 3 Sodium p-toluenesulfonate 2 Water Balance Table 2

Invention composition Comparative Dicarboxylic-acid-type R1 n m M1 M2 surfactant (wt.%) composition 9 10 11 12 13 14 (I) R1-CHCH2COOM2 C12H22 - - K H 0.1 COOM1 (unsaturated) C18H17 - - Na H 2 R2COOM1 C12H25 0 2 H Na 2 (II) R1-CON None of the dicarboxy R3COOM2 C12H25 0 2 H TEA* 2 lic-acid-type R2,R3:-(CH2CH2O)n-(CH2)m- surfactants (I), (II) and R2COOM1 C14H29 3 1 H H 2 (III) was (III) R1-N added.

R3COOM2 C8H17 1 2 Na H 5 R2,R3:-(CH2CH2O)n-(CH2)mpH (undiluted, 20 C) 4.5 5.5 5.5 6.0 5.0 6.5 5.5 Detergency (number of dishes) 11 13 13 12 11 11 10 Evaluated property Foaming power (mm) 93 95 96 95 92 93 91 Rinsability (times) 6 6 5 6 5 5 10 Coloration resistance 0 0 0 0 0 0 4 * N(CH2CH2OH)3 Example 3: Detergency, foaming power, rinsability, coloration resistance, feeling of use and lowtemperature stability were tested with respect to the following liquid detergent compositions.

[Formulation] Proportion (wt.%) Sodium laurylbenzenesulfonate 15 Sodium polyoxyethylene (p=2) 5 laurylsulfate Lauryl dimethylamine oxide 2 Monosodium octenylsuccinate 1 Natural fruit juice (see Table 3) 0.005-10 Ethanol 5 Water Balance < Evaluation Standard for Feeling of Use > A: Good touch feeling to the hand.

B: Somewhat poor touch feeling to the hand.

C: Poor touch feeling to the hand.

Table 3

Sugar Invention composition Comparative composition Natural fruit juice Organic acids(%) S/A* content (wt.%) (as citric acid) (%) 16 17 18 19 20 21 22 23 24 25 26 Grape fruit 1.3 8.0 6.2 3 2 1.3 8.0 6.2 0.005 1.3 8.0 6.2 10 Lime 6.0 0.18 0.13 3 6.5 0.5 0.08 3 Grape 0.8 12 15 3 2 Apple 0.6 11 18.3 3 0.4 12.4 31 3 Pine apple 0.6 15 25 3 Lemon 5.5 2.2 0.4 0.5 (sevenfold concentrate) pH (undiluted, 20 C) 5.5 5.5 5.8 5.5 5.0 5.5 5.5 5.5 5.5 5.0 6.0 Detergency (number of dishes) 12 12 12 12 12 12 12 12 5 12 12 Foaming power (mm) 96 96 96 96 96 96 95 96 65 96 96 Evaluated property Rinsability (time) 5 4 5 5 5 5 4 10 5 5 5 Feeling of use A A A A A A A B C** B-C C*** Coloration resistance 0 0 0 0-1 0 0 0 0 4 0 0 Low-temperature stability A A A A A A A A C A A * Sugar/acid ratio.

** Squeak feeling.

*** Sticky feeling.

Claims (5)

CLAIMS:

1. A liquid detergent composition comprising the following components (A), (B) and (C): (A) 5-60 wt.% of at least one non-soap synthetic surfactant selected from anionic surfactants, nonionic surfactants and amphoteric surfactants, (B) 0.05-5 wt.% of a dicarboxylic-acid-type surfactant, and (C) 0.01-4.5 wt.% of a natural fruit juice containing organic acids and reduced sugars, the pH of said composition in its undiluted form being 4-6.5.

2. The liquid detergent composition as claimed in Claim 1, wherein the component (B) is at least one dicarboxylic-acid-type surfactant selected from compounds represented by the following general formula (I), (11) or (III):

wherein R1 means a straight-chain or branched alkyl or alkenyl group having 8-16 carbon atoms, R2 and R3 denote individually a ( CH2-CH2-O )n( CH2 tm group (m: 1-5, n: 0-5) which may contain one or more branched chains, and M1 and M2 are individually a hydrogen, alkali metal or alkaline earth metal atom or an alkanol amine residue.

3. The liquid detergent composition as claimed in Claim 2, wherein the component (B) is a dicarboxylic-acid-type surfactant represented by the following general formula (I):

wherein R1 means a straight-chain or branched alkyl or alkenyl group having 8-16 carbon atoms, and M1 and M2 are individually a hydrogen, alkali metal or alkaline earth metal atom or an alkanol amine residue.

4. The liquid detergent composition as claimed in Claim 1, wherein the sugar/acid ratio of the component (C) is 0.1-25.

5. A liquid detergent composition subftartially as described in the Examples.