JPH0524199B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a liquid detergent composition containing a specific anionic surfactant, a specific succinic acid derivative, and a specific sulfobetaine, and more particularly, to a liquid detergent composition containing a specific anionic surfactant, a specific succinic acid derivative, and a specific sulfobetaine, and more particularly, The present invention relates to a liquid detergent composition that has an ability to prevent formation and is extremely comfortable to use. [Prior art] Anionic surfactants are mainly used in light liquid detergents such as dishwashing detergents, shampoos, and heavy liquid detergents for clothing because of their excellent detergency and foaming power. It is used as a cleaning base.
Additives collectively called hydrotropic agents such as ethanol, p-toluenesulfonate, and urea are added to this for the purpose of improving low-temperature stability. [Problems to be Solved by the Invention] In liquid detergent compositions, hydrotropic agents added to improve low-temperature stability need to be added in a relatively large amount to improve low-temperature stability, and are flammable. may pose a risk of
This often resulted in negative effects such as the foam feeling worse and the pH increasing over time. In addition, in general, when liquid cleaning agents have a high concentration of surfactant, when used for a long period of time, moisture etc. evaporate from the liquid and form a film on the surface, which can clog the cap, which can be a problem, especially at low temperatures. This was more likely to occur during dry winters. Conventional hydrotropes such as ethanol, p-toluenesulfonate, and urea are ineffective in preventing film formation, and there is a strong demand for additives that are effective in both low-temperature stability and film formation prevention when added in small amounts. It had been. In addition, in recent years, consumers have become more aware of the feel of cleaning products, especially those that are washed directly by hand, such as dishwashing detergents. is preferred. Cleaning agents that use anionic surfactants as their main cleaning base tend to be sticky because the surfactant is highly adsorbed to the skin, which can cause your hands to slip and break dishes or cause you to feel anxious about getting your hands rough. I might give it away. For this reason, there has been a strong demand for improvement in stickiness during use. [Means for Solving the Problems] Under these circumstances, the present inventors have conducted extensive research in order to obtain a liquid cleaning agent that has excellent low-temperature stability and ability to prevent film formation, and is also pleasant to use. As a result, it was discovered that the desired liquid detergent composition can be obtained by adding a specific succinic acid derivative and sulfobetaine to a liquid detergent composition containing a specific anionic surfactant.The present invention completed. That is, the present invention comprises the following three components (a), (b) and (c) (a) polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate, alkanesulfonate,
and one or two selected from the group consisting of polyoxyethylene alkyl ether carboxylates.
More than one species of anionic surfactant 10-40% by weight (b) The following general formula () (In the formula, R ₁ represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and X and Y each represent a hydrogen atom, an alkali metal, ammonium, or an alkanolamine.) A succinic acid derivative represented by (c) General formula for () (In the formula, R ₂ represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, R ₃ and R ₄ represent an alkyl group having 1 or 2 carbon atoms, and Z represents a hydrogen atom or a hydroxyl group.) Provided is a cleaning composition containing sulfobetaine, in which [(b) + (c)] is 1 to 10% by weight, and (b)/(c) is 0.1 to 1 in weight ratio. It is something to do. Examples of the anionic surfactants that are component (a) of the present invention include polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, alkanesulfonates, and polyoxyethylene alkyl ether carboxylic acids. Any one or more anionic surfactants selected from salts can be used. Among these, polyoxyethylene alkyl sulfates are particularly preferred for their skin-friendly properties, especially those with the following general formula () R ₅ O (CH ₂ CH ₂ O) _o SO ₃ M () (where R ₅ has 10 to 10 carbon atoms). 18 alkyl or alkenyl groups, M represents an alkali metal, ammonium or alkanolamine, and n is 1 on average.
A polyoxyethylene alkyl ether sulfate represented by the following formula is preferred. In addition, in terms of both cleaning power and price, the following general formula () (In the formula, R ₆ represents an alkyl group or alkenyl group having 10 to 16 carbon atoms, and M represents the same as described above.) An alkylbenzenesulfonate represented by the following formula is preferred. The content of component (a) of the present invention is in the range of 10 to 40% by weight; if this content is less than 10% by weight, the detergency and foaming power will be insufficient, and if it exceeds 40% by weight, The low temperature stability of the composition is extremely deteriorated. A particularly preferred content is in the range of 15 to 20% by weight. The succinic acid derivative of component (b) of the present invention exhibits a remarkable effect of improving low-temperature stability and preventing film formation when combined with the above-mentioned sulfobetaine. These effects are small when the number of carbon atoms in R ₁ is less than 8,
When it exceeds 18, the solubility of the succinic acid derivative itself is significantly reduced, resulting in a worsening of low temperature stability. The particularly preferable carbon number range is 10 to
It is 14. Component (c) of the present invention is sulfobetaine represented by the general formula (). The combination of this sulfobetaine and the succinic acid derivative of component (b) exhibits a remarkable effect of improving low-temperature stability and preventing film formation, but these effects are not achieved when the number of carbon atoms in R ₂ is less than 8. If the number exceeds 18, the solubility of sulfobetaine itself will be significantly reduced, resulting in a worsening of low-temperature stability. A particularly preferred range of carbon number is 10-14. Certain succinic acid derivatives have been used as a component of cleaning agents. For example, JP-A-1987-
No. 142603 describes the use of a succinic acid derivative having an alkyl group or an alkenyl group having 4 to 14 carbon atoms in combination with lower ethanol as a solubilizer in a detergent composition containing an alkaline builder. . In addition, in JP-A-58-196299 and JP-A-58-196296, a succinic acid derivative having an alkyl group or an alkenyl group having 4 to 8 carbon atoms is added to a liquid detergent composition to improve low-temperature stability. It is described that it is used for purposes such as preventing film formation. However, in these examples, a relatively short-chain succinic acid derivative is used in combination with a volatile component, or a relatively short-chain one is used alone, and as in the present invention, a relatively long-chain succinic acid derivative is used as an amphoteric surfactant. The technical concept of using sulfobetaine in combination with one type of sulfobetaine to achieve the objective by utilizing their combined effect is completely unprecedented. Considering the process of film formation of a liquid cleaning agent, first, concentration of the liquid occurs near the interface due to volatilization of volatile components such as water from the air/liquid interface. A concentrated surfactant solution often forms a liquid crystal structure or a gel structure, loses fluidity, and forms a film at the air/liquid interface. Therefore, volatile hydrotropes such as ethanol have little or no effect in preventing film formation. Since succinic acid derivatives are nonvolatile and have hydrophobic groups, they are thought to enter the association structure of surfactants, which are the main components of detergents, and form mixed micelles. It is thought that by forming a mixed micelle system in this way, it becomes difficult to form a liquid crystal structure or a gel structure when concentrated, thereby preventing film formation. For this reason, to prevent film formation, it is preferable to use a succinic acid derivative with a somewhat longer chain alkyl group or alkenyl group than the short chain succinic acid derivatives described in JP-A-58-196299 or JP-A-58-196296. Succinic acid derivatives, which themselves have strong surface activity, are more likely to form mixed micelles, are more effective, and are expected to be effective in small amounts. However, in reality, long-chain succinic acid derivatives have a limited solubility in solution, and if the solubility limit amount is exceeded during the concentration process, solids will precipitate or become cloudy, so it is not sufficient to use it alone. I couldn't say it was possible. However, in the present invention, if sulfobetaine, which is a type of amphoteric surfactant, is used in combination with a long-chain succinic acid derivative in an appropriate ratio, the compatibility of the long-chain succinic acid derivative in the composition is improved. Even when concentrated at the gas/liquid interface, solids do not precipitate, and a small amount of addition can significantly prevent film formation and improve low-temperature stability. In addition, by incorporating succinic acid derivatives and sulfobetaine into a cleaning agent whose main ingredient is anionic surfactant, the stickiness caused by the anionic surfactant is surprisingly reduced, and the feeling of use is significantly improved. be done. Therefore, in the present invention, it is necessary to use the succinic acid derivative as the component (b) and the sulfobetaine as the component (c) in combination, and the blending amount [(b)+(c)] is 1 to 1.
10% by weight, and the blending ratio (b)/(c) needs to be 0.1 to 1 by weight. When [(b)+(c)] is less than 1% by weight, the effect of preventing film formation is insufficient and the usability is also poor. If it exceeds 10% by weight, the solubility of the succinic acid derivative will be exceeded and solids will precipitate.
The viscosity of the composition increases, which is undesirable. A particularly preferred range is 2 to 5% by weight. Furthermore, if the blending ratio (b)/(c) is less than 0.1, the film formation prevention effect will be insufficient, and if it exceeds 1, the compatibility of the succinic acid derivative with the anionic surfactant will deteriorate and the solid will form. Precipitation becomes easier. A particularly preferable range is
It is 0.2-0.5. In addition to the above-mentioned essential components, the detergent composition of the present invention may optionally contain a known surfactant for liquid detergents within a range that does not impair the desired performance. Such surfactants include, for example, polyoxyethylene (average number of added moles of 3 to
20) Alkyl or alkenyl (C ₈ to C ₁₈ linear or branched) alkyl ethers, higher aliphatic (C ₈
~ _C18 ) Nonionic surfactants such as alkanolamides, anionic surfactants such as α-sulfoaliphatic ester salts, N-acylglutamates, monoalkyl phosphates, tertiary alkyl (C8 _{~ C18} )
Examples include amphoteric surfactants such as amine oxides and alkyl ( _C8 - _C18 ) betaines. Furthermore, other optional components used in ordinary liquid cleaning compositions, such as lower alcohols such as ethanol, lower alkylbenzene sulfonates such as p-toluenesulfonate, glycols such as ethylene glycol and propylene glycol. kind,
Hydrotropes such as urea, PH buffers such as citric acid and malic acid, organic or inorganic builders, natural fruit juices such as lemon and lime, hand roughness preventive agents, enzymes, protein derivatives, colorants, fragrances, clouding agents, Chelating agents, preservatives, ultraviolet absorbers, etc. can be added. [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. Example 1 The compositions shown in Table 1 were prepared, and the ability of each composition to prevent film formation and low temperature stability were examined. Each test was conducted as follows. (Film formation prevention ability) Put 50g of each composition into a 100ml beaker and leave it as is.
Leave it in a constant temperature and humidity room at 20℃ and 40% humidity for 3 days.
The condition after being left was evaluated based on the following criteria. Evaluation Details 〇: No change △: Thin film formation ×: Complete film formation (low temperature stability) The liquid cleaning agent was stored in a constant temperature room at -5°C for 10 days and evaluated. Evaluation details 〇: No change in appearance △: Slightly cloudy ×: Separation or precipitation

【table】

[Table] ｜ ｜
_CH3OH

Example 2 Based on the following formulation composition, various succinic acid derivatives and sulfobetaine were added to prepare compositions, and the ability to prevent film formation and low-temperature stability of each composition were examined. The test results are shown in Table-2. Ingredients Compounding ratio (wt%) polyoxyethylene (4) dodecyl ether sulfate
Na 15.0 Dodecyldimethylamine oxide 3.0 Polyoxyethylene (7) dodecyl ether 5.0 Succinic acid derivative (see Table-2) 0 or 1.0 Sulfobetaine (see Table-2) 0 or 2.5 Ethanol 4.0 Tap water Balance PH (undiluted solution/25℃) ) 7.0

【table】

[Table] Example 3 The compositions shown in Table 3 were prepared, and the detergency, foaming power, viscosity, and low-temperature stability of each composition were examined.

[Table] ｜ ｜
_CH3OH

Example 4 Kitchen detergents A and B having the following combination compositions were prepared, and a blind in-home use test was conducted using the paired comparison method on 50 ordinary household housewives under the age of 49. The period of use was one week. The results are shown in Table-4.

【table】

【table】

【table】

Claims (1)

[Claims] 1. The following three components (a), (b) and (c) (a) polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, α-olefin sulfonate, alkanesulfonate, and One or more anionic surfactants selected from the group consisting of polyoxyethylene alkyl ether carboxylates 10 to 40% by weight (b) The following general formula () (In the formula, R ₁ represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and X and Y each represent a hydrogen atom, an alkali metal, ammonium, or an alkanolamine.) A succinic acid derivative represented by (c) General formula for () (In the formula, R ₂ represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, R ₃ and R ₄ represent an alkyl group having 1 or 2 carbon atoms, and Z represents a hydrogen atom or a hydroxyl group.) A liquid detergent composition containing sulfobetaine, wherein [(b)+(c)] is 1 to 10% by weight, and (b)/(c) is 0.1 to 1 in weight ratio. 2 (a) component has the following general formula () R ₅ O (CH ₂ CH ₂ O) _o SO ₃ M () (In the formula, R ₅ represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, and n is 2. The liquid cleaning composition according to claim 1, which is a polyoxyethylene alkyl ether sulfate represented by a polyoxyethylene alkyl ether sulfate having an average number of 1 to 7, and M represents an alkali metal, ammonium, or alkanolamine. 3 (a) Component is the following general formula () (In the formula, R ₆ represents an alkyl group or alkenyl group having 10 to 16 carbon atoms, and M represents the same as above.) The liquid cleaning agent according to claim 1, which is an alkylbenzenesulfonate salt represented by Composition.