JP4715186B2 - Thickener and detergent composition for surfactant - Google Patents

Description

  The present invention relates to a surfactant thickener and a detergent composition containing the same, and in particular, exhibits an excellent thickening effect on surfactants, particularly acylamino acid type anionic surfactants or alkyls. The present invention relates to a surfactant thickener effective for thickening an iminodicarboxylate-type amphoteric surfactant, and a detergent composition that has excellent foam quality and does not cause a slimy feeling.

  Traditionally, surfactants are used in a wide variety of industrial fields for a variety of applications and products. However, an aqueous solution containing a surfactant does not have an appropriate viscosity. For this reason, when the surfactant is used for a cleaning agent or the like, the surfactant is used in a mixture with various viscosity modifiers in a solvent such as water for the purpose of imparting an appropriate viscosity.

  Known thickeners for surfactant solutions include inorganic salts such as sodium chloride, water-soluble polymers such as hydroxyethyl cellulose and xanthan gum, and fatty acid alkanolamides. Of these, fatty acid alkanolamides have been widely used because not only a thickening effect but also a foam increasing effect can be obtained by combining with a surfactant such as an alkyl ether sulfate surfactant.

  However, fatty acid alkanolamide has a small thickening effect, and when combined with an acylamino acid type anionic surfactant or an alkyliminodicarboxylate type amphoteric surfactant, it is difficult to increase the viscosity. The storage stability of the mixed solution becomes a problem. Furthermore, there is a slimy feeling when used as a cleaning agent. Therefore, a thickener for surfactants that exhibits an excellent thickening effect on surfactants and is effective for thickening surfactants is desired.

  Moreover, in the detergent composition, a thickener is used for the purpose of imparting an appropriate viscosity, and the alkyl sulfate type anionic surfactant and the alkyl ether sulfate type anionic surfactant are used because of their excellent detergency. Sulfate-type or sulfonate-type anionic surfactants such as an agent, an amide ether sulfate-type anionic surfactant, an acyl taurate-type anionic surfactant, an acyl isethionate-type anionic surfactant, Acyl glutamate type anionic surfactant, acyl-β-alaninate type anionic surfactant, acyl sarcosine type anionic surfactant, acyl glycine type anionic surfactant, etc. for reasons of excellent foaming properties Acylamino acid type anionic surfactant or alkyliminodicarboxy It is used in conjunction with over preparative type amphoteric surfactants.

  By the way, as a detergent composition using a fatty acid alkanolamide which is a thickener, a detergent composition combining an acylalkyl taurate type anionic surfactant, an amine oxide and an alkanolamide (Patent Document 1), A detergent composition comprising an acyl sarcosine-type anionic surfactant or an acylglycine-type anionic surfactant and a fatty acid alkanolamide (Patent Document 2), a higher fatty acid salt, and an acylalkyl taurate-type anionic interface Detergent composition combining an activator, an acyl isethionate type anionic surfactant or an amide ether sulfate type anionic surfactant and an alkanolamide type nonionic surfactant (Patent Document 3), etc. Is mentioned.

Examples of the detergent containing an alkylene oxide derivative include a detergent composition (Patent Document 4) containing butylene oxide and a polyalkylene glycol fatty acid ester obtained by polymerizing 6 mol or more of ethylene oxide, 1 to 5 mol of butylene oxide, and Composition of a sulfated unsaturated fatty acid or fatty acid salt containing both a polyalkylene glycol fatty acid ester added with 1 to 5 moles of ethylene oxide and a polyalkylene glycol fatty acid ester added with 1 to 5 moles of butylene oxide and 6 to 20 moles of ethylene oxide A thing (patent document 5) etc. are mentioned. However, these cleaning compositions are not always satisfactory in foam quality and slimy feeling.
JP 59-100198 A Japanese Patent Laid-Open No. 2-180811 JP-A-7-138591 JP 2001-334139 A JP 2003-226900 A

  The present invention exhibits an excellent thickening effect on surfactants, and is particularly effective for increasing the use of surfactants for thickening acylamino acid type anionic surfactants or alkyliminodicarboxylate type amphoteric surfactants. An object of the present invention is to provide a cleaning composition that is excellent in the viscosity and the foam quality containing the same and does not produce a slimy feeling.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by a surfactant thickener having a specific structure, and the present invention is based on this finding. It came to complete.

  That is, the gist of the present invention is as follows.

The present invention is a surfactant thickener represented by the following general formula (2):
R ¹ O (BO) _y H (2)
(In the formula, R ¹ represents a group selected from an alkyl group having 8 to 14 carbon atoms, an alkenyl group, and an acyl group, BO represents a butylene oxide group, and y represents an average addition mole number, and 1 ≦ y ≦ 3).

  The present invention contains 0.5 to 10% by mass of the surfactant thickener and 2 to 40% by mass of the surfactant, and the content ratio between the surfactant thickener and the surfactant. Provides a detergent composition having a mass ratio of 1/30 to 1/2.

  In a preferred embodiment, the surfactant is a sulfate-type anionic surfactant, a sulfonate-type anionic surfactant, an acylamino acid-type anionic surfactant, and an alkyliminodicarboxylate-type amphoteric surfactant. It is at least one selected from the group consisting of agents.

  The surfactant thickener of the present invention exhibits an excellent thickening effect on surfactants, and in particular, thickening of acylamino acid type anionic surfactants or alkyliminodicarboxylate type amphoteric surfactants. It is effective for. Moreover, the detergent composition containing the surfactant thickener of the present invention is excellent in foam quality and does not produce a slimy feeling. The cleaning composition of the present invention is also not irritating to the skin.

The surfactant thickener of the present invention has the following general formula (1):
R ¹ O (EO) _x (BO) _y (EO) _z H (1)
(In the formula, R ¹ represents a group selected from an alkyl group having 8 to 14 carbon atoms, an alkenyl group, and an acyl group, EO represents an ethylene oxide group, BO represents a butylene oxide group, and x, y, and z represent averages, respectively. Indicates the number of added moles, 0 ≦ x ≦ 3, 1 ≦ y ≦ 3, 0 ≦ z ≦ 3, 0 ≦ x + z ≦ 3)
It is represented by

In the general formula (1), the alkyl group represented by R ¹ includes octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, isoundecyl, dodecyl, isododecyl, tridecyl, isotridecyl Group, tetradecyl group, isotetradecyl group and the like. Examples of the alkenyl group for R ¹ include a tetradecenyl group. Examples of the acyl group for R ¹ include an octanoyl group, a decanoyl group, a dodecanoyl group, and a tetradecanoyl group. R ¹ is preferably a group selected from an alkyl group having 8 to 12 carbon atoms, an alkenyl group, and an acyl group, and more preferably an acyl group having 8 to 12 carbon atoms.

When the carbon number of R ¹ is 8 or more, a surfactant thickener having an excellent thickening effect is obtained, and the foam quality of the cleaning composition containing the thickener is good. Further, when the number of carbon atoms is 14 or less, the obtained thickener for a surfactant can exhibit an excellent thickening effect without deteriorating the compatibility with the surfactant solution. Moreover, the cleaning composition containing the thickener does not give a slimy feeling.

  In the said General formula (1), y which is the average addition mole number of a butylene oxide group is 1-3, Preferably it is 1-2. When y is 1 to 3, a thickener having an excellent thickening effect is obtained, and the foam quality of the cleaning composition containing the thickener is good. The average added mole number of ethylene oxide group x and z is 0 ≦ x ≦ 3, 0 ≦ z ≦ 3, 0 ≦ x + z ≦ 3, more preferably 0 ≦ x ≦ 2, 0 ≦ z ≦ 2, 0 ≦ x + z ≦ 2, more preferably x = z = 0. When x + z is 3 or less, a thickener having an excellent thickening effect is obtained, and the cleaning composition containing the thickener does not give a slimy feeling.

The surfactant thickener of the present invention can obtain a further excellent thickening effect especially when x = z = 0, and is a composition that does not give a slimy feeling when blended in a cleaning composition. Obtainable. This surfactant thickener is represented by the following general formula (2):
R ¹ O (BO) _y H (2)
(Wherein R ¹ , BO and y are the same as those defined in the general formula (1)).

  The method for producing the surfactant thickener of the present invention is not particularly limited, but a method of esterifying a fatty acid and polyoxybutylene polyoxyethylene glycol, a quaternary onium salt, a Lewis acid or an alkali catalyst is present. A production method such as a method in which 1,2-butylene oxide and ethylene oxide are subjected to an addition reaction with alcohol or fatty acid can be employed.

  The detergent composition of the present invention comprises a surfactant thickener (hereinafter sometimes referred to as component (a)) of the above general formula (1) or (2) and a surfactant (hereinafter referred to as component (b). In some cases).

  In the cleaning composition of the present invention, the content of the component (a) is 0.5 to 10% by mass, preferably 1 to 8% by weight. When the content of the component (a) is in the range of 0.5% by mass to 10% by mass, the detergent composition is imparted with an appropriate viscosity, does not have good foam quality and slimy feeling, and further has skin irritation. No detergent composition is obtained.

  In the cleaning composition of the present invention, the content of the component (b) is 2 to 40% by mass, preferably 5 to 30% by mass. When the content of the component (b) is 2% by mass or more, a detergent composition having good foam quality is obtained, and when it is 40% by mass or less, a good detergent composition that does not cause a slimy feeling. Things are obtained.

  The content ratio (a) / (b) of the component (a) and the component (b) in the cleaning composition is 1/30 to 1/2, preferably 1/20 to 1/4 in mass ratio. . When (a) / (b) is 1/30 or more, a detergent composition having good foam quality is obtained, and when it is 1/2 or less, excellent foam quality and good cleaning that does not give a feeling of sliminess An agent composition is obtained.

  The surfactant (component (b)) contained in the cleaning composition of the present invention is not particularly limited, but is a sulfate type anionic surfactant, a sulfonate type anionic surfactant, an acylamino acid type anion. And a surfactant composition that is at least one selected from the group consisting of an ionic surfactant and an alkyliminodicarboxylate type amphoteric surfactant can provide a better cleaning composition that is superior in foam quality and does not produce a slimy feeling. This is preferable. The surfactant can be an alkali metal salt, alkaline earth metal salt, ammonium salt, organic ammonium salt, etc., for example, lithium, sodium, potassium, 1/2 calcium, 1/2 magnesium, ammonium, triethanolammonium , Salts of diethanolammonium, monoethanolammonium and the like. These surfactants preferably have an alkyl group or acyl group having 8 to 22 carbon atoms, such as lauryl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, oleoyl group, coconut oil fatty acid residue, Examples include palm kernel oil fatty acid residues and beef tallow fatty acid residues. The use of a surfactant having 8 to 22 carbon atoms is preferable in that a detergent composition that is excellent in foam quality and does not produce a slimy feeling can be obtained.

  Examples of the sulfate type anionic surfactant include an alkyl sulfate type anionic surfactant, an alkyl ether sulfate type anionic surfactant, and an amide ether sulfate type anionic surfactant.

  Examples of the sulfonate type anionic surfactant include an acyl alkyl taurate type anionic surfactant, an acyl isethionate type anionic surfactant, a dialkyl sulfosuccinic acid type anionic surfactant, and an alkyl sulfone. Type anionic surfactants and amidosulfonic acid type anionic surfactants. An acylalkyl taurate type anionic surfactant and an acyl isethionate type anionic surfactant are preferred.

  Examples of the acyl amino acid type anionic surfactant include an acyl glutamate type anionic surfactant, an acyl-β-alaninate type anionic surfactant, an acyl sarcosine type anionic surfactant, and an acyl glycine type anionic surfactant. Examples thereof include ionic surfactants and acyl asparagated anionic surfactants. Preferred are an acyl glutamate type anionic surfactant, an acyl-β-alaninate type anionic surfactant, an acyl sarcosine type anionic surfactant, and an acyl glycine type anionic surfactant.

  Examples of the alkyliminodicarboxylate type amphoteric surfactants include alkyliminodiacetate type amphoteric surfactants and alkyliminodiproprionate type amphoteric surfactants. An alkyliminodiacetate type amphoteric surfactant is preferred.

  The cleaning composition of the present invention usually contains water in the remainder other than the components (a) and (b). Furthermore, the component and additive normally used for a cleaning composition can be mix | blended as needed. Specifically, for example, higher alcohols such as cetanol and stearyl alcohol; polyhydric alcohols such as glycerin and ethylene glycol; hydrocarbon oils such as squalane and paraffin; ester oils such as jojoba oil and octyldodecyl myristate; cationic Cationic polymer compounds such as polyvinylpyrrolidone derivatives, copolymers of dimethyldiallylammonium chloride and acrylic acid amides; Silicone derivatives such as dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymers; sodium sulfate, potassium carbonate, etc. Inorganic salts of: organic acids such as glutamine and aspartic acid and salts thereof; preservatives such as paraoxybenzoic acid ester and phenoxyethanol; tonic agents such as 5-methyl-2-isopropylcyclohexanol and red pepper tincture; Diamine tetraacetate, citric acid, chelating agents such as nitrilotriacetic acid trisodium, benzophenone derivatives, UV absorbers such as benzotriazole derivatives; dyes; and the like and perfumes.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

(Preparation Example 1: Production of thickener for surfactant)
1600 g (8 mol) of dodecanoic acid and 1 part by mass of tetramethylammonium chloride (16 g) with respect to 100 parts by mass of dodecanoic acid were weighed in an autoclave having a volume of 5 liters, heated to 125 ° C. and heated to 749 g (10 .4 mol) was added and reacted at a maximum pressure of 0.45 MPa and aged for 5 hours. Next, degassing was performed at 75 ° C. under reduced pressure, and washing with 2 kg of 10% brine, dehydration, and filtration were performed to obtain butylene glycol monododecanoic acid ester (A-1) (hydroxyl value 204 mgKOH / g, butylene oxide average) Number of moles added 1.0). The yield was 2046g. Table 1 shows the structure of A-1.

(Preparation Example 2: Production of thickener for surfactant)
1152 g (8 mol) of octanoic acid and 5 parts by mass of potassium hydroxide (58 g) with respect to 100 parts by mass of octanoic acid were weighed in an autoclave having a volume of 5 liters, heated to 125 ° C. and 749 g (10. 4 mol) was added at 0.49 MPa for reaction and aged for 2 hours. Next, degassing was performed at 75 ° C. under reduced pressure, and water washing, dehydration, and filtration were performed with 2 kg of 10% bow nitric acid water to obtain butylene glycol monooctanoic acid ester (A-2) having a structure shown in Table 1 (hydroxyl value). 244 mg KOH / g, butylene oxide average addition mole number 1.2). The yield was 1708 g.

(Preparation Examples 3 to 5: Production of thickener for surfactant)
In Preparation Example 2, 1670 g (7.3 mol) of tetradecanoic acid, 760 g (3.8 mol) of dodecanoic acid, and 1250 g (6.7 mol) of dodecyl alcohol were used instead of 1152 g (8 mol) of octanoic acid. Except that the butylene glycol monotetradecanoic acid ester (A-3), butylene glycol monododecanoic acid ester (A-4), butylene glycol monododecyl ether (A) having the structure shown in Table 1 was prepared in the same manner as in Preparation Example 2. -5) was obtained.

(Comparative Preparation Examples 1 to 4)
In Preparation Example 2, instead of 1152 g (8 mol) of octanoic acid, 590 g (6.7 mol) of butanoic acid (Comparative Preparation Example 1), 2080 g (7.3 mol) of octadecanoic acid (Comparative Preparation Example 2), dodecane, respectively Comparative components C-1 to C-3 having the structures shown in Table 2 were obtained in the same manner as in Preparation Example 2, except that 300 g (1.5 mol) of acid (Comparative Preparation Example 3) was used. Further, in Preparation Example 2, 1600 g (8 mol) of dodecanoic acid was used instead of 1152 g (8 mol) of octanoic acid, and 460 g (10.5 mol) of ethylene oxide was substituted for 749 g (10.4 mol) of butylene oxide. A comparative component C-4 having the structure shown in Table 2 was obtained in the same manner as in Preparation Example 2 except that it was used (Comparative Preparation Example 4).

(Preparation Example 6: Production of thickener for surfactant)
1375 g (5 mol) of the A-1 component obtained in Preparation Example 1 and 5 parts by mass of potassium hydroxide (69 g) with respect to 100 parts by mass of the A-1 component were weighed into an autoclave having a volume of 5 liters, and 135 ° C. The mixture was heated to 705 g (16 mol) of ethylene oxide at a maximum pressure of 0.49 MPa, reacted, and aged for 3 hours. Next, after degassing under reduced pressure at 75 ° C., neutralization with acetic acid and filtration were performed to obtain polyoxyethylene oxybutylene glycol dodecanoate (A-6) having a structure shown in Table 1 (hydroxyl group). 139 mg KOH / g, butylene oxide average addition mole number 1.0, ethylene oxide average addition mole number 2.9). The yield was 1920 g.

(Comparative Preparation Example 5)
Comparative Example C-5 having the structure shown in Table 2 was obtained in the same manner as in Preparation Example 6 except that the amount of ethylene oxide used in Preparation Example 6 was 2420 g (55 mol).

(Preparation Example 7: Production of surfactant thickener)
1119 g (6.0 mol) of dodecyl alcohol and 5 parts by mass of potassium hydroxide (56 g) with respect to 100 parts by mass of dodecyl alcohol were weighed in an autoclave having a volume of 5 liters, heated to 125 ° C. and 467 g of butylene oxide ( 6.5 mol) was added and reacted at a maximum pressure of 0.49 MPa, followed by aging for 2 hours. After degassing at 75 ° C. under reduced pressure for 1 hour, the temperature was further raised to 135 ° C., 704 g (16 mol) of ethylene oxide was added and reacted at a maximum pressure of 0.49 MPa, and aging was performed for 3 hours. Subsequently, degassing was performed at 75 ° C. under reduced pressure for 1 hour, followed by neutralization with acetic acid and filtration to obtain polyoxyethyleneoxybutylene glycol monododecyl ether (A-7) (hydroxyl value 157 mg KOH / g). , Butylene oxide average addition mole number 1.0, and ethylene oxide average addition mole number 2.3). The yield was 1971g. Table 1 shows the structure of A-7.

(Examples 1-16 and Comparative Examples 1-11)
Thickeners for surfactants shown in Tables 1 and 2 (A-1 to A-7 and C-1 to C-5), various surfactants and water are mixed in the ratios shown in Tables 3 and 4, The viscosity of this mixture was evaluated by the following method. The evaluation results are shown in Tables 3 and 4.

(1) Viscosity Using a B-type viscometer (manufactured by Tokyo Keiki Seisakusho Co., Ltd.), the mixture was held at 25 ° C., and the viscosity was measured at a measurement time of 100 seconds.

  From Table 3, the thickener effect with respect to various surfactant was confirmed in the thickener for surfactants (A-1 to A-7) of Examples 1-16.

From Table 4, it can be seen that low thickening effect for using Comparative Example 6 short comparison component carbon atoms of the acyl group C-1 is the R ^1. In Comparative Example 7, it can be seen that the thickening effect is low because Comparative Component C-2 having a long carbon number of the acyl group as R ¹ is used. In Comparative Example 8, it can be seen that the thickening effect is low because Comparative Component C-3 having a large number of added moles of butylene oxide groups was used. In Comparative Example 9, it can be seen that the thickening effect is low because Comparative Component C-4 having no butylene oxide group added thereto was used. In Comparative Example 10, it can be seen that the thickening effect is low because Comparative Component C-5 having a large number of added moles of ethylene oxide groups was used. In Comparative Example 11, since lauric acid diethanolamide which is a fatty acid alkanolamide was used, it can be seen that the thickening effect is low.

(Examples 17 to 32 and Comparative Examples 12 to 20)
Surfactant thickeners (a component), surfactants (b component) and water shown in Tables 1 and 2 were mixed in the proportions shown in Tables 5 and 6 to obtain a cleaning agent. Foam quality and feeling of use were evaluated by the following methods. The evaluation results are shown in Tables 5 and 6.

(2) Foam quality 10 men and women each were panelists, and the foam quality when the body was washed with 5 g of a cleaning agent was evaluated. From the total score of 20 people, 2 points when the foam feels fine and elastic, 1 point when the foam feels slightly rough, 0 when the foam feels rough and not elastic, It was evaluated in three stages.
Foam quality is good: ○ (total score of 30 points or more)
Foam quality is slightly bad: △ (total score 20 points or more and less than 30 points)
Poor foam quality: x (total score less than 20 points)

(3) Feeling slimy Ten men and women each were panelists, and the slimy feeling when the body was washed with 5 g of a cleaning agent was evaluated. From the total of 20 people, 2 points when you did not feel slimy, 1 point when you feel slightly slimy, and 0 points when you feel that you are feeling slimy and take time to rinse, It was evaluated in three stages.
No slimy feeling: ○ (30 or more total points)
Somewhat slimy: △ (Total score 20 or more and less than 30)
Strong feeling of sliminess: × (Total score less than 20 points)

  From Table 5, it can be seen that the cleaning agents of Examples 17 to 32 of the present invention are excellent in foam quality and usability. In addition, the cleaning agents of Examples 17 to 32 had little skin irritation.

From Table 6, it can be seen that, in Comparative Example 12, the content of the component (b) is less than 2% by mass, so that the foam quality is not good. In Comparative Example 13, it can be seen that the content of the component (b) exceeds 40% by mass, so that there is a slimy feeling. In Comparative Example 14, it can be seen that (a) / (b) is larger than ½, so that the foam quality is not good. In Comparative Example 15, since Comparative Component C-1 having a short carbon number of the acyl group as R ¹ was used, it was found that the foam was inferior and slimy. In Comparative Example 16, it can be seen that since the comparative component C-2 having a long carbon number of the acyl group as R ¹ is used, the foam quality is not good. In Comparative Example 17, it is understood that the foam quality is not good because Comparative Component C-3 having a large number of added moles of butylene oxide was used. In Comparative Example 18, it can be seen that since Comparative Component C-4 to which butylene oxide was not added was used, the foam quality was inferior and slimy. In Comparative Example 19, it can be seen that the comparison component C-5 having a large number of added moles of ethylene oxide has a slimy feeling. In Comparative Example 20, since lauric acid diethanolamide, which is a fatty acid alkanolamide, was used, it was found that the feeling of sliminess was strong.

  Since the thickener of the present invention exhibits a remarkable thickening effect even when added in a small amount, it is useful as a thickener for surfactants. By using this in a detergent composition, an appropriate viscosity can be obtained. Thus, a detergent composition having excellent foam quality and no slimy feeling can be obtained.

Claims (3)

Surfactant thickener represented by the following general formula (2):
R ¹ O (BO) _y H (2)
(In the formula, R ¹ represents a group selected from an alkyl group having 8 to 14 carbon atoms, an alkenyl group, and an acyl group, BO represents a butylene oxide group, and y represents an average addition mole number, and 1 ≦ y ≦ 3). Containing 0.5 to 10% by mass of the surfactant thickener according to claim 1 and 2 to 40% by mass of the surfactant, containing the surfactant thickener and the surfactant A cleaning composition having a mass ratio of 1/30 to 1/2. The surfactant is selected from the group consisting of sulfate-type anionic surfactants, sulfonate-type anionic surfactants, acylamino acid-type anionic surfactants, and alkyliminodicarboxylate-type amphoteric surfactants. The cleaning composition according to claim 2 , wherein the cleaning composition is at least one kind.