JPH08104891A - Liquid detergent - Google Patents

Abstract

PURPOSE: To provide a liquid detergent for clothes, dishes, house, skin, hair, etc., having excellent detergent power and keeping high liquid stability at a low temperature, etc., by using an alkylglucoside composed of a mixture of the α- and β-steric isomers as a main component. CONSTITUTION: This liquid detergent having excellent detergent power and high liquid stability and useful as a cleaning agent for clothes, dishes and house or a skin or hair cleaning agent such as hair shampoo, body shampoo and face washing agent is composed mainly of an alkyl glucoside ester expressed by formula [Z is H or group of formula COR1 (R1 is a 5-13C alkyl, a hydroxyalkyl or an alkenyl); at least one of the groups Z is the group of formula COR1 ; X is a 1-3C alkyl] (e.g. methylglucoside caprylic acid ester). The alkylglucoside ester is a mixture containing the αand β-steric isomers at the 1-carbon atom at a weight ratio (α:β) of 8:2 to 4:6. The mixture is dissolved in water to obtain the objective liquid detergent.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is useful for clothes, tableware, household and hair shampoos having excellent detergency and good liquid stability, and for skins and hairs such as body shampoo and face wash. Liquid cleaning agent.

[0002]

2. Description of the Related Art Conventional liquid detergents are mainly composed of widely used anionic surfactants such as LAS, AOS, AES, and soap, and polyoxyethylene-based nonionic surfactants. In most cases, these surfactants are used for the purpose of improving detergency, foaming property, mildness and the like.

However, in recent years, milder surfactants have been favored for the environment and the human body, and sugar-based nonionics have been used as the main component of liquid detergents for dishes, skin and hair. Surfactants have come into the limelight. Among sugar-based nonionic surfactants, those having a monosaccharide as a hydrophilic part generally have a slightly larger cmc than polyoxyethylene-based nonionic surfactants, but have a low surface activity, especially a decrease in interfacial tension to oil. It is expected to be the main component of liquid detergents that have excellent detergency and high detergency.

Among the nonionic surfactants having a monosaccharide as a hydrophilic part, the alkyl glucoside ester having the highest surface activity is a liquid detergent composition (for example, JP-A-3-174497, JP-A-3-174984, Same 3-1
85094, 3-223398, 3-25502.
1, JP-A-5-255694) and shampoo compositions (for example, JP-A-3-197415 and JP-A-3-19741).
6, No. 4-266812, No. 5-92913) and the like.

On the other hand, many of these sugar-based nonionic surfactants have higher Kraft points than polyoxyethylene-based nonionic surfactants (for example, ethylene oxide 6 mol adduct of octyl alcohol and lauryl alcohol). The Kraft point of the ethylene oxide 6 mol adduct is 0 ° C. or lower, whereas α-methylglucoside caprate, which is a monosaccharide sugar-based nonionic surfactant, is 27 ° C., β-methylglucoside caprate is 40 ° C., decyl glucoside is 23 ° C., and N-methyldecyl glucamide is 21 ° C.), and many are practically restricted in terms of liquid stability of a liquid detergent containing them.

Since the Kraft point of the above-mentioned alkyl glucoside ester also greatly increases as the number of carbon atoms of the ester increases, the alkyl glucoside ester having a large number of carbon atoms of the ester is used in order to enhance the surface activity of the liquid detergent. If a large amount of is used, the liquid properties of the liquid detergent, especially the liquid stability at low temperatures, tend to be impaired.

Therefore, in the past, α-forms having relatively low Kraft points among alkyl glucoside esters having a large number of carbon atoms of the ester have been used so far, in order to further secure practically good liquid properties, particularly liquid stability at low temperature. In addition, the α-alkyl glucoside ester was mixed with an ester having a small number of carbon atoms of the ester and a low Kraft point (JP-A-4-3373).
No. 96). However, since such an alkyl glucoside ester having a low Kraft point has low surface activity,
The liquid detergent containing this within the range where the liquid stability is secured has a limited surface activity, and such a liquid detergent sufficiently brings out the characteristic of the alkyl glucoside ester that the surface activity is excellent. It wasn't a liquid cleaner.

The present invention has been made in view of the above circumstances and is mainly composed of a mild sugar-based nonionic surfactant, an alkyl glucoside ester, and has not only excellent detergency but also excellent liquid stability particularly at low temperature. It is an object of the present invention to provide a liquid detergent having

[0009]

Means and Actions for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventor has found that the stereoisomer of the 1-position carbon of the alkyl glucoside ester represented by the following general formula (1) is obtained. By mixing the α-form and the β-form, the liquid detergent of the aqueous solution of the surfactant, particularly the liquid stability at low temperature, and the liquid detergent having higher detergency than ever can be obtained. I found a thing.

[0010]

Embedded image (However, in the formula, Z represents a hydrogen atom or a —COR ₁ group, and at least one of the groups represented by Z is a —COR ₁ group. R ₁ is a straight chain or branched chain having 5 to 13 carbon atoms. It represents an alkyl group, a hydroxyalkyl group or an alkenyl group, and X represents an alkyl group having 1 to 3 carbon atoms.)

For example, the Kraft point of α-methylglucoside capric acid ester is as high as 27 ° C., and the Kraft point of β-methylglucoside capric acid ester is as high as 40 ° C. When these are used alone as a liquid detergent, they are stored at low temperature. Turbidity, solid precipitation, etc. are observed, and the stability of the liquid deteriorates. On the other hand, when these α-forms and β-forms are mixed and used, especially when they are mixed in a ratio of 8: 2 to 4: 6, both form a eutectic mixture, and the Kraft point is greatly lowered. . In the case of this methyl glucoside capric acid ester, for example, when mixed with α-form: β-form = 6: 4, the Kraft point of the mixture is lowered to 15 ° C. Therefore, it is necessary to prepare a liquid detergent showing practically good liquid stability You can

Also in the case of alkyl glucoside esters having other ester carbon numbers, the α-form and the β-form are mixed in the same manner, and particularly, the mixing ratio of α-form: β-form is 8: 2.
Mixing at 4: 6 greatly reduces the Kraft point of the mixture. Therefore, even if a large amount of alkyl glucoside ester having a long carbon chain length and high surface-active ability is used by mixing the α-form and the β-form, particularly by mixing in the ratio of the above-mentioned predetermined range, a liquid detergent The liquid stability at low temperature is not impaired, and it is found that a liquid detergent having not only excellent detergency but also good liquid stability at low temperature can be obtained, and forms the present invention. Came to.

That is, the present invention relates to a liquid detergent containing an alkyl glucoside ester represented by the following general formula (1) as a main component, wherein the alkyl glucoside ester is a stereoisomer of the carbon at the 1-position α-form. And a liquid detergent characterized by using a mixture of β-forms, particularly a liquid detergent in which α-form and β-form are used together in a weight ratio of α-form: β-form = 8: 2 to 4: 6. provide.

[0014]

Embedded image (However, in the formula, Z represents a hydrogen atom or a —COR ₁ group, and at least one of the groups represented by Z is a —COR ₁ group. R ₁ has 5 to 13 carbon atoms, preferably 9 to 11 carbon atoms. A linear or branched alkyl group, a hydroxyalkyl group or an alkenyl group is shown, and X is an alkyl group having 1 to 3 carbon atoms.)

The present invention will be described in more detail below. The alkyl glucoside ester used in the present invention is represented by the above general formula (1). The number of esterified hydroxyl groups in this alkyl glucoside ester and the position of esterification are arbitrary, but in particular, a monoester in which the 6-position hydroxyl group is esterified, a diester in which the 3,6-position hydroxyl group is esterified And mixtures of both are preferably used. Especially, a monoester in which the hydroxyl group at the 6-position is esterified is more preferably used.

The alkyl glucoside ester in which the α-form and the β-form are mixed is an α-D-alkyl glucoside or β-D-
Is an alkyl glucoside reacted with a fatty acid or a fatty acid ester in the presence of an alkali catalyst (JP-A-49-3)
5318, JP-A-60-58940), or in the presence of an organic solvent, a hydrolase is caused to react to react with a fatty acid or a fatty acid ester (JP-A-4-35318, JP-A-4-35318, JP-A-4-35318).
16195, JP-A-3-76593), the α-alkyl glucoside ester and the β-alkyl glucoside ester obtained by mixing can be produced by mixing them at a predetermined ratio. Alternatively, α-mixed in a predetermined ratio in advance
A method of reacting a mixture of D-alkyl glucoside and β-D-alkyl glucoside with a fatty acid or a fatty acid ester in the same manner as above may be used.

The above-mentioned alkyl glucoside is preferably one having an alkyl group having 1 to 3 carbon atoms, and such an alkyl glucoside includes methyl glucoside,
Examples include ethyl glucoside and propyl glucoside.

The fatty acid has 6 to 1 carbon atoms.
Those having a linear or branched alkyl group, a hydroxyalkyl group or an alkenyl group of 4 are used, and examples of such fatty acids include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, and lauric acid. Acid, myristic acid, etc. are mentioned.

Further, as the above fatty acid ester,
Esters of the above fatty acids and lower alcohols such as methanol, ethanol and propanol are used. Specifically, methyl caproate, ethyl caproate, propyl caproate, methyl caprylate, ethyl caprylate, propyl caprylate, capric acid are used. Methyl, ethyl caprate, propyl caprate, methyl laurate, ethyl laurate, propyl laurate and the like can be mentioned.

The mixing ratio of α-alkyl glucoside ester and β-alkyl glucoside ester contained in the liquid detergent of the present invention is preferably in the range of 8: 2 to 4: 6 by weight ratio, and preferably 7 : 3 to 5: 5. When it is out of the above range of 8: 2 to 4: 6, the Kraft point of the mixture is not sufficiently lowered, and an alkyl glucoside ester having a large number of carbon atoms cannot be added in order to enhance the surface activity of the liquid detergent. If the liquid stability of the liquid detergent at a low temperature is ensured, the surface activity of the liquid detergent is limited, and the object of the present invention may not be sufficiently achieved. α
-The aqueous surfactant solution containing the alkyl glucoside ester and the β-alkyl glucoside ester in a mixing ratio of 7: 3 to 5: 5 has the greatest reduction in the Kraft point, and has an extremely excellent liquid property, especially at low temperature. It has excellent liquid stability.

The alkyl glucoside ester used in the conventional liquid detergent has an ester average carbon number of at most 9, whereas the liquid detergent of the present invention has an ester average carbon number higher than that. It can be prepared using an alkyl glucoside ester. Particularly preferred is an alkyl glucoside ester having an ester average carbon number of 9 to 11, which not only exhibits a high surface activity and exhibits very excellent detergency, but also does not impair the liquid stability at low temperatures. A cleaning agent can be obtained.

The alkyl glucoside ester of the present invention is more effective in detergency when used in combination of two or more kinds. Even when two or more kinds of alkyl glucoside esters are used in combination, it is more preferable that the sum of the α-forms and the sum of the β-forms fall within the above mixing ratio range.

The liquid detergent of the present invention can be prepared by an ordinary method using other components as appropriate components added to the conventional liquid detergent within a range that does not impair the effects of the present invention. For example, any anionic surfactant, cationic surfactant, nonionic surfactant other than the alkyl glucoside ester of the present invention, amphoteric surfactant, hydrotrope, diluent, fluorescent dye, fragrance, preservative, bactericide,
It may contain a dye, an ultraviolet absorber, an antioxidant, a pearling agent, an emulsifying agent, a sequestering agent, a pH adjusting agent, a protein derivative, an animal or plant extract, an inorganic or organic builder, and other polymer substances.

Specifically, examples of the anionic surfactant include alkylbenzene sulfonate, α-olefin sulfonate, α-sulfofatty acid alkyl ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl sulfate ester salt, Sulfosuccinic acid mono (di) alkyl (alkenyl) ester-based surfactants, alkyl phosphate ester-based surfactants, amino acid-based surfactants, taurate-based surfactants, higher fatty acid salts, etc. other than the alkyl glucoside ester of the present invention As the nonionic surfactant, for example, alkyl alkylene oxylate, fatty acid polyalkylene oxide ester, alkylphenol alkylene oxylate, alkylene oxide copolymer, alkyl polyglycerin ether, fatty acid polyglycerin ester, Examples of amphoteric surfactants such as alkyl glycosides and N-alkanoyl-N-alkanoylglycamides include betaine surfactants and imidazoline surfactants.

Among the fragrances, the solubilizing ability of the alkyl glucoside ester is high, so that the fragrance may be difficult to attain. Therefore, vapor pressure 0.01 to 100 mmH
It is desirable to use a fragrance containing 30% or more of the fragrance component of g (20 ° C.) in the fragrance composition.

[0026]

According to the present invention, when an alkyl glucoside ester, which is a mild sugar-based nonionic surfactant, is used as the main component of a liquid detergent, the α-form and β-form of the alkyl glucoside ester are mixed. As a result, even if a large amount of alkyl glucoside ester with a long carbon chain length and high surface activity is used, the liquid stability of the liquid detergent at low temperature is not impaired, and it has superior detergency. In addition, it is possible to obtain a liquid detergent having good liquid stability at low temperatures.

[0027]

EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples 1 to 5 and Comparative Examples 1 to 5] Liquid detergents having the compositions shown in Table 1 were prepared to obtain liquid detergents of Examples 1 to 5 and Comparative Examples 1 to 5. The detergency and liquid stability of each liquid detergent were evaluated by the following methods. The results are also shown in Table 1. Detergency evaluation method A leanut test method using a polypropylene cup was adopted for evaluation of detergency.

That is, on the inner wall of a polypropylene cup having a capacity of 200 ml, leanut dirt [beef tallow / soybean oil = 5/5
(Weight ratio), about 0.15 g] was attached, and 180 ml of a solution prepared by diluting each liquid detergent into a 2% aqueous surfactant solution was added to each polypropylene cup, and the rotary vanes were polypropylene with a temperature condition of 25 ° C. The inside of the polypropylene cup was washed by rotating in the cup for 5 minutes. The detergency of each liquid cleaning agent is ⊚ when the value of the cleaning rate (%) calculated by the following formula is more than 40%, and 30 to 40% is ∘.
-30 (less than)% was evaluated as Δ, and less than 10% was evaluated as x.

[0030]

[Equation 1]

Liquid Stability Evaluation Method In order to evaluate the liquid stability of each liquid detergent under low temperature conditions, the following freeze-restoration stability test was conducted.

That is, each liquid cleaning agent was allowed to stand for 12 hours under the temperature condition of -20 ° C to be frozen, and then allowed to stand for 12 hours under the temperature condition of 0 ° C to restore it, which was repeated 6 times. The liquid stability of each liquid cleaning liquid was evaluated by visual observation. The evaluation was as follows: good liquid properties (uniform transparency, low viscosity) after 6 freeze-recovery operations were evaluated as ◯, and precipitation of solids, turbidity and the like were observed, and liquid properties were impaired. did.

[0033]

[Table 1]

From the results shown in Table 1, it is recognized that the liquid detergent of the present invention has excellent detergency and liquid stability under low temperature conditions. On the other hand, the liquid detergents containing the α-form or the β-form of Comparative Examples 1 to 5 respectively are:
It is recognized that the alkyl glucoside ester having a small number of carbon atoms does not have excellent detergency, and the larger the number of carbon atoms, the worse the liquid stability.

[Examples 6 and 7, Comparative Example 6] A liquid detergent for kitchen was prepared according to the formulation shown in Table 2 and was good in the above-mentioned leanut test method or in a plurality of dishes to which a certain amount of oil stain was adhered. When the cleaning power of each liquid cleaning agent was evaluated by the number of sheets showing different cleaning states, the liquid cleaning agents of Examples 6 and 7 were compared with Comparative Example 6.
It showed a higher detergency than that of the liquid cleaning agent. Further, when each liquid detergent was stored at -5 ° C for 1 month, the liquid detergents of Examples 6 and 7 showed no change in liquid properties such as turbidity, precipitation, or thickening, and were stable at low temperatures. The property was also good. On the other hand, the liquid detergent of Comparative Example 6 had good liquid stability at low temperatures, but the detergency was inferior to that of Examples.

The formulation amounts in Table 2 are% by weight, and the same applies to the following tables.

[0037]

[Table 2]

[Examples 8 and 9] Liquid detergents for clothes were prepared according to the formulations shown in Table 3 to obtain the liquid detergents of Examples 8 and 9. When the liquid detergents were used to wash the clothes, Both liquid cleaning agents showed high detergency without damaging clothes, and their liquid stability was good even after storage at -5 ° C for 1 month.

[0039]

[Table 3]

[Examples 10 and 11] Liquid detergents for homes were prepared according to the formulations shown in Table 4 to obtain the liquid detergents of Examples 10 and 11, and the stains adhered to walls, floors, furniture, etc. When liquid cleaning agents were used, both liquid cleaning agents removed stains by simply wiping them lightly, and were excellent in their finish. Also, the liquid stability of these liquid detergents is
In both cases, storage was good at -5 ° C for 1 month.

[0041]

[Table 4]

[Examples 12 and 13] Hair shampoos were prepared according to the formulations shown in Table 5 to obtain the liquid detergents of Examples 12 and 13, and each liquid detergent was used to wash hair. There was no creaking and it was a mild, smooth wash. The liquid stability of these liquid detergents was good even after storage at -5 ° C for 1 month.

[0043]

[Table 5]

[Examples 14 and 15] Body shampoos were prepared according to the formulations shown in Table 6 to obtain the liquid cleansing agents of Examples 14 and 15, and each liquid cleansing agent was used to cleanse the body. Shows good washing performance, and the liquid stability of these liquid detergents is -5 ° C.
Storage for one month was also good.

[0045]

[Table 6]

[Examples 16 and 17] A face wash was prepared according to the formulations shown in Table 7 to obtain the liquid detergent of Examples 16 and 17, and the face was washed with each liquid detergent. It showed excellent cleaning power even for stains that were difficult to remove with a face cleanser, and was mild to wash off. Also, the liquid stability of these liquid detergents is
Storage at 5 ° C for 1 month was also good.

[0047]

[Table 7]

As is clear from the results of Examples 1 to 17, the α- and β-forms, which are stereoisomers of the 1-position carbon of the alkyl glucoside ester, are contained, and the weight ratio is 8:
The liquid detergent of the present invention, which is contained at a ratio of 2 to 4: 6, exhibits excellent detergency and good liquid stability,
It is recognized that it is useful as a kitchen cleaner, a household cleaner, a hair shampoo, a body shampoo, a facial cleanser, and the like.

Claims (3)

[Claims] 1. The following general formula (1): (However, in the formula, Z represents a hydrogen atom or a —COR ₁ group, and at least one of the groups represented by Z is a —COR ₁ group. R ₁ is a straight chain or branched chain having 5 to 13 carbon atoms. An alkyl group, a hydroxyalkyl group or an alkenyl group, and X represents an alkyl group having 1 to 3 carbon atoms.) In a liquid detergent containing an alkyl glucoside ester as a main component, A liquid detergent characterized by using a mixture of α-form and β-form which are stereoisomers of carbon at position. 2. The liquid detergent according to claim 1, wherein the α-form and the β-form of the alkyl glucoside ester are used together in a weight ratio of α-form: β-form = 8: 2 to 4: 6. 3. The liquid detergent according to claim 1 or 2, which contains a combination of two or more kinds of the alkyl glucoside ester represented by the general formula (1).