JPH0438797B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Industrial Application] The present invention relates to a liquid detergent composition that can be widely used as a laundry detergent, a dishwashing detergent, a household detergent, a hair detergent, a human body detergent, etc. In particular, the present invention relates to a liquid detergent composition that has improved coloring properties and rinsability. The present invention relates to a liquid cleaning composition containing natural fruit juice. [Conventional technology] In recent years, the cleaning performance, rinsing performance, fragrance, color,
Natural fruit juices have been added to liquid cleaning compositions in order to improve the feel on the skin and to remove bad odors from items to be cleaned.
A cleaning composition for removing fish odor (US Pat. No. 3,650,968) consisting of 30 to 80% by weight of water, 0.1 to 35% by weight of a detergent, and 0.1 to 15% by weight of citrus juice, and at least two types of surfactants. A liquid cleaning composition effective for cleaning stains that are difficult to remove, such as burnt protein and starch, consisting of 5 to 60% by weight of an organic synthetic surfactant and 5 to 50% by weight of citrus fruit juice
No. 50680) has been reported. [Problems to be solved by the invention] However, products containing natural fruit juice generally have
It is known that browning occurs during storage and its quality deteriorates significantly. The main cause of this browning is said to be the reaction between carbonyl compounds (including sugars) contained in natural fruit juices and amino compounds such as amino acids (amino-carbonyl reaction). Such browning phenomenon also occurs in cleaning compositions containing natural fruit juices as described above. Therefore, research has been carried out to prevent this browning. For example, substances that bind to the carbonyl compound that is the substrate of the amino carbonyl reaction and block the reaction (i.e., carbonyl reagent), sulfite, etc. Alternatively, a method has been proposed in which a salt thereof is added as an anti-browning agent. However, these substances also have the drawback that they are not sufficiently effective, and in detergent compositions containing pigments, the pigments significantly fade due to their reducing action. Furthermore, organic acids such as citric acid and malic acid in fruit juice have a large influence on the browning phenomenon of natural fruit juice (Kato, Sakurai, Journal of the Japanese Society of Agricultural Chemistry, Vol. 38, No. 11)
(No., p. 536-541, 1964), there was a strong desire to take measures to prevent browning in products containing natural fruit juices in which organic acids and sugars (particularly reducing sugars) coexist. On the other hand, cleaning agents that use anionic surfactants as the main cleaning base have excellent cleaning power and rich foaming power, but have the disadvantage of poor rinsing performance because they have high foaming power even at low concentrations. It was hot. Rinseability is an important performance for detergents such as laundry detergents and dishwashing detergents, and if the rinseability is poor, the rinsing time will be long, and a large amount of water will be required for rinsing, which is of course uneconomical. This may cause consumers to feel uneasy about the problem of foam in wastewater (so-called foam pollution), which could develop into a social problem. In order to solve the above problems, it is possible to add a rinsing agent, but it is possible to use long-chain fatty acid salts, sorbitan fatty acid esters, glycerin fatty acid esters, etc., which have been widely used as rinsing agents.
HLB's nonionic surfactants need to be added in relatively large amounts to be effective, and in the case of liquid detergents such as laundry detergents and dishwashing detergents, adding large amounts significantly deteriorates low-temperature stability. do. In addition, foaming not only during rinsing but also during washing was inhibited, which was not necessarily satisfactory. For this reason, there has been a strong desire to develop a cleaning agent that has excellent cleaning power, produces rich foam during cleaning, and has good rinsing properties. [Means for Solving the Problems] In order to solve the problems, the present inventors have developed a liquid detergent that does not lose its original cleaning power and foaming power, has less coloring due to storage, and has excellent rinsability. As a result of intensive research aimed at developing a surfactant composition, we found that at least one non-synthetic surfactant selected from anionic surfactants, nonionic surfactants, and amphoteric surfactants and natural fruit juice were used. By mixing a dicarboxylic acid surfactant in a specific amount in the liquid cleaning composition and maintaining the pH of the stock solution in a weakly acidic range, coloring during storage is reduced and rinsability is improved. It was discovered that a liquid cleaning composition can be obtained, and the present invention was completed. That is, the present invention provides the following components (A), (B) and (C). Synthetic surfactant 5-60% by weight (B) The following general formulas (), () and () [In the formula, R ₁ represents a linear or branched alkyl group or alkenyl group having 8 to 16 carbon atoms, R ₂ ,
R ₃ may have a branched chain -(CH ₂ -CH ₂ -O) _o
-(CH ₂ ) represents _n group (m = 1 to 5, n = 0 to 5),
M ₁ and M ₂ represent hydrogen, an alkali metal, an alkaline earth metal, or an alkanolamine] 0.05 to 5% by weight of one or more dicarboxylic acid surfactants selected from the compounds represented by (C) an organic acid and Natural fruit juice containing reducing sugars
The object of the present invention is to provide a liquid detergent composition containing 0.01 to 4.5% by weight and having a PH of 4 to 6.5 in its stock solution. Surfactants that can be used as component (A) in the present invention include the following. (1) Anionic surfactant (i) Sulfonate-based linear or branched alkyl (C ₈ - _{C 22} ) benzenesulfonate, linear or branched alkyl (C ₈ - C ₂₂ )
Sulfonates, long chain olefin (C ₈ - C ₂₂ ) sulfonates, etc. (ii) Sulfate long chain monoalkyl (C ₈ - _{C 22} ) sulfate ester salts,
Polyoxyethylene (1 to 6 mol) long chain alkyl (C ₈ to C ₂₂ ) ether sulfate salt, polyoxyethylene (1 to 6 mol) alkyl (C ₈ to C ₁₈ ) phenyl ether sulfate salt, etc. iii) Phosphates Long chain monoalkyl, dialkyl or sesquialkyl ( _C8 - _C22 ) phosphates, polyoxyethylene (1-6 mol) monoalkyl, dialkyl or sesquialkyl ( _C8 - _C22 ) phosphates etc., (iv) Others polyoxyethylene (1-7 mol) linear or branched alkyl ( _C8 - _C22 ) ether carboxylate, long-chain N-acyl ( _C8 - _C22 ) glutamate,
Long-chain N-acyl ( _C8 - _C22 ) sarcosinate, straight-chain or branched dialkyl ( _C6 - _C14 ) sulfosuccinate, etc. The counter ions (cations) of each of the above anionic surfactants include sodium, potassium, It may be any of alkali metal or alkaline earth metal ions such as magnesium, and alkanolamine ions such as monoethanolamine, diethanolamine, and triethanolamine. (2) Nonionic surfactant Polyoxyethylene (1 to 20 mol) long chain alkyl (C ₈ to C ₂₂ ) ether, polyoxyethylene (1 to 20 mol) alkyl (C ₈ to C ₁₈ ) phenyl ether , polyoxyethylene polyoxypropylene block polymer, higher fatty acid alkanolamide or its alkylene oxide adduct, linear or branched alkyl (C ₁₀ - _{C 15} ) tertiary amine oxide, etc. (3) Ampholytic surfactant Amino acid type amphoteric Surfactants, betaine-type amphoteric surfactants such as alkyl sulfobetaines, alkyl acetate betaines, imidazoline-type amphoteric surfactants, etc., including the typical examples listed above, can be used alone as component (A). You can also use
Component (A) can also be a combination of two or more types.
The amount of surfactant to be blended is in the range of 5 to 60% by weight, preferably 10 to 40% by weight of the cleaning composition. If the amount is less than 5% by weight, the detergency and foaming power exerted by the surfactant will not be sufficient, whereas if the amount exceeds 60% by weight, an exceptional improvement in detergency is expected. In fact, it is not preferable because it causes bubble breakage, deteriorates rinsability, and is difficult to handle during production due to its high viscosity. As the dicarboxylic acid type surfactant of component (B) of the present invention, any of the compounds represented by the general formula (), (), or () can be used; however, from the viewpoint of composition stability, the general formula () Particularly preferred are dicarboxylic acid surfactants represented by: Component (B) is 0.05 to 5% by weight based on the composition, especially
It is preferably added in an amount of 0.1 to 3% by weight. If it is outside this range, the desired effects of improving coloring properties and rinsability cannot be expected. Examples of the natural fruit juice containing an organic acid and reducing sugar as component (C) used in the present invention include the following. (b) Temperate fruits Grape (Vitis vinifera), 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), grapefruit (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. The natural fruit juice of the present invention has an acid-sugar ratio (ratio of sugar content to organic acid content: sugar content/organic acid content) of 0.1 to 25.
This is preferable from the viewpoint of the feel on the hands when using the cleaning composition. If it is less than 0.1, the feeling of creaking in the hand will increase, and if it exceeds 25, the sticky feeling will increase, which is not preferable. In addition, the amount of natural fruit juice added is 0.01% of the cleaning composition.
-4.5% by weight, preferably 0.1-3% by weight. If this amount is less than 0.01% by weight, the desired improvement in rinsability will be insufficient, while if it exceeds 4.5% by weight, the coloring properties and low-temperature stability of the cleaning composition will deteriorate, which is not preferred. The PH range of the stock solution of the liquid cleaning composition of the present invention is 4.
-6.5 is preferable, and PH5-6 is especially preferable. Further, other optional components can be added to the cleaning composition of the present invention within a range that does not impair the separation stability, cleaning performance, and foaming performance of the composition. For example, lower aliphatic alcohols such as ethyl alcohol, solubilizers such as sodium and potassium salts of toluenesulfonic acid and xylenesulfonic acid, and urea, viscosity modifiers such as clay minerals and water-soluble polymer substances, calcite, and silica. , water-insoluble abrasives such as calcium phosphate, zeolite, polyethylene, nylon, and polystyrene; humectants such as glycerin and sorbitol; feel improvers such as cationized cellulose;
Other enzymes, fragrances, pigments, preservatives/antifungal agents, etc. can be added. [Effects of the Invention] The cleaning composition of the present invention can be used in laundry detergents, dishwashing detergents, household detergents, hair detergents, human body detergents, etc. without impairing their original functions, that is, cleaning power and foaming power. , is a liquid detergent composition of high practical value that shows extremely little color change during storage and has excellent rinsability after washing. [Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Test method and evaluation criteria (1) Foaming power test The foaming power is measured when 0.1% by weight of commercially available butter is added as a staining ingredient to a detergent solution with a detergent concentration of 0.5% by weight. The measurement method is to put 40 ml of the above detergent solution containing butter into a glass cylinder with a diameter of 5 cm, rotate and stir for 10 minutes, and measure the foam height immediately after stopping. (2) Cleaning power test Sudan (red pigment) was added to beef tallow as an indicator.
Add 0.1% by weight and place 3g of this in a porcelain dish (diameter 25
cm) is rubbed with a sponge soaked in 10 g of detergent and 20 g of water, and the number of plates washed until the tallow can no longer be removed from the plates is shown. (3) Rinseability: Concentration 0.25 in a vat with a diameter of 30 cm and a height of 12 cm.
% sample solution 3 for 10 minutes, then open the pot attached to the bottom of the vat to drain only the liquid. Next, add tap water 3 and perform similar rotational stirring for 10 minutes to drain the liquid. This operation is repeated by changing the tap water until no bubbles are observed in the vat, and the evaluation is based on the number of times the tap water is replaced. (4) Colorability Fill a 300ml transparent polyester bottle with the cleaning composition and leave it in a constant temperature room at 50°C for 20 days.
After standing, the degree of coloring is observed with the naked eye. (Evaluation criteria) 0: Not colored 1: Slightly colored 2: Significantly colored 3: Significantly colored 4: Very significantly colored (5) Low temperature stability The cleaning composition was filled into a 300ml transparent polyester bottle. , and leave it in a constant temperature room at -5℃ for 10 days.
After standing, visually observe the condition of the liquid inside. (Evaluation criteria) A: No change at all B: Slightly cloudy C: Significantly cloudy Example 1 The liquid cleaning composition shown in Table 1 was prepared and the cleaning power, foaming power, coloring property, rinsability, and low temperature stability were evaluated. We conducted an evaluation. The results are shown in Table 1.

[Blend composition]

Blending ratio (wt%) Polyoxyethylene (P-=4) Sodium lauryl sulfate 20 Sodium alkane ( _C14 ) sulfonate 5 Coconut oil fatty acid diethanolamide 3 Dicarboxylic acid surfactant (see Table 2) 0-5 Grapefruit juice (Acid-sugar ratio: 5) 1 Ethanol 3 Sodium paratoluenesulfonate 2 Water Balance amount

[Blend composition]

Blending ratio (wt%) Sodium laurylbenzenesulfonate 15 Polyoxyethylene (P-=2) Sodium lauryl sulfate 5 Lauryl dimethylamine oxide 2 Monosodium octenyl succinate 1 Natural fruit juice (see Table 3) 0.005-10 Ethanol 5 Water Balance amount <Evaluation criteria for usability> A: Good feel in hand B: Slightly poor feel in hand C: Poor

【table】

【table】

Claims (1)

[Scope of Claims] 1. At least one non-containing surfactant selected from the following components (A), (B) and (C) (A): anionic surfactants, nonionic surfactants and amphoteric surfactants; Setsuken synthetic surfactant 5-60% by weight (B) Following general formulas (), () and () [In the formula, R ₁ represents a linear or branched alkyl group or alkenyl group having 8 to 16 carbon atoms, R ₂ ,
R ₃ may have a branched chain -(CH ₂ -CH ₂ -O) _o
-( _CH2 ) represents an _n group (m=1 to 5, n=0 to 5),
M ₁ and M ₂ represent hydrogen, an alkali metal, an alkali metal, or an alkanolamine] 0.05 to 5% by weight of one or more dicarboxylic acid surfactants selected from the compounds represented by (C) an organic acid and Natural fruit juice containing reducing sugars
A liquid detergent composition containing 0.01 to 4.5% by weight and having a PH of 4 to 6.5 in its stock solution. 2 (B) component is the following general formula () [In the formula, R ₁ represents a linear or branched alkyl group or alkenyl group having 8 to 16 carbon atoms, and M ₁
and _M2 represents hydrogen, an alkali metal, an alkaline earth metal, or an alkanolamine.] The liquid cleaning composition according to claim 1, which is a dicarboxylic acid surfactant represented by the following formula. 3. The liquid detergent composition according to claim 1, wherein the acid-sugar ratio of component (C) is 0.1 to 25.