JP2014062226A - Thickener composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thickener which imparts a practical viscosity without changing use feeling of an anionic surfactant and is excellent in handleability allowing construction of a stable formulation even at low temperatures.SOLUTION: The thickener comprises a compound represented by the general formula (1). [In the formula, Rrepresents a linear or branched C6-C14 alkyl group; X represents a methylene group or an oxygen atom; and Rand Rrepresent a methyl group, an ethyl group, a hydroxyethyl group or a hydroxypropyl group and may be identical or different.]

Description

  The present invention relates to a thickener that builds a viscosity by being used in combination with an anionic surfactant.

  In particular, it is difficult to increase the practical viscosity by adding it to a cleaning agent containing as a main base a non-thickening anionic surfactant such as an N-acylamino acid surfactant, which is considered difficult to increase in viscosity. The present invention relates to a thickening agent that can be realized without changing the feeling of use of an anionic surfactant, and further includes a liquid detergent composition excellent in foaming, foam quality, and viscosity stability containing the thickening agent and an anionic surfactant. About.

  Liquid detergent compositions based on anionic surfactants that do not provide the necessary thickening effect alone are generally hypoallergenic, but they give the appropriate viscosity required for their use. It was difficult.

  In order to obtain the target viscosity, a method of using a difficult-thickening anionic surfactant and a sulfate-type anionic surfactant that is relatively easy to thicken has been tried, but in this case, the irritation increases. Neither method was satisfactory.

  In the N-acylamino acid surfactant which is an example of a difficultly thickening anionic surfactant, even when thickening in combination with a polymer thickener such as hydroxyethyl cellulose or cationized guar which is often used for thickening, When a polymer thickener is added until the viscosity of 300 to 2000 mPa · s, which is usually useful as a viscosity of a liquid detergent composition, the feeling of use of the N-acylamino acid surfactant is not expressed, and it is high when used for shampoos and the like. This may cause inconveniences such as part of the molecular thickener adsorbed on the hair or loss of luster of the hair after washing.

  For this reason, various techniques have been disclosed so far for the purpose of building the viscosity of the slightly thickening anionic surfactant.

  Prior art relating to viscosity construction of N-acylamino acid surfactants will be described as an example of a hardly thickening anionic surfactant.

  A weakly acidic liquid detergent formulation in which fatty acid diethanolamide and a water-soluble inorganic salt are blended with an N-acylamino acid surfactant is disclosed (Patent Document 1). According to this technology, it is possible to increase the viscosity of the detergent composition without impairing the feeling of use of the N-acylamino acid-based surfactant. The low-temperature stability of the detergent composition in the portion close to was not sufficient.

  In order to reduce the amount of water-soluble inorganic salt and build viscosity, amphoteric surfactants, semipolar surfactants and cationic surfactants that have a cation center or pseudo-cation center in the molecule are included. A liquid detergent formulation used in combination is disclosed (Patent Document 2). Although improvement in low-temperature stability can be seen, it is not satisfactory because inorganic salts are essential components and it becomes difficult to use a conditioning agent in combination.

  On the other hand, hydroxyalkyl tertiary amine is disclosed as an emulsifier for cationic asphalt (Patent Document 3), and as applications, sterilizing, disinfecting and antiseptic compositions (Patent Document 4), for thermosetting powder coatings It is used for compositions (Patent Document 5) and the like, and in recent years, application development as a conditioning agent has been carried out (Patent Document 6).

  However, there is no description regarding the thickening effect due to the addition to the liquid detergent composition mainly composed of anions, particularly hardly thickening anionic surfactants (particularly N-acylamino acid surfactants).

  Although it is disclosed that the amine derivative described in Patent Document 7 is a composition suitable for cosmetics having a pearly luster, there is no description regarding addition to the liquid cleaning composition, and description of the thickening effect. No (Patent Document 7).

Japanese Examined Patent Publication No. 2-54400 JP 2003-147399 A Japanese Patent Laid-Open No. 49-034520 JP 51-098324 A Japanese Patent Laid-Open No. 52-069937 JP 2008-019253 A JP-A-6-263615

  In the prior art relating to the construction of the viscosity of the hardly thickening anionic surfactant, there are problems of feeling of use, thickening and compatibility of the conditioning agent, and no means for solving these problems has been found.

  As a result of studying a method for solving the viscosity building problem of an anionic surfactant, the present inventors have found that the above-mentioned problems can be solved by using the thickener of the present invention, and to complete the present invention. It came.

That is, the present invention
(1) General formula (1)

[Wherein R ¹ is a linear or branched alkyl group having 6 to 14 carbon atoms, X is a methylene group or oxygen atom, R ² and R ³ are methyl group, ethyl group, hydroxyethyl group or hydroxy group. A propyl group, which may be the same or different; ]
A thickener comprising a compound represented by

(2) A liquid detergent composition comprising the thickener according to (1) above,

(3) A liquid detergent composition comprising: (A) a hard-viscosity anionic surfactant; and (B) a thickener comprising the compound represented by the general formula (1) described in item 1. Is a thing,

(4) The liquid detergent composition according to (3) above, wherein the hardly thickening anionic surfactant is an N-acylamino acid surfactant.

(5) (A) N-acylamino acid surfactant (B) A thickener comprising the compound represented by the general formula (1) described in item 1, and (C) an interface having a cation center in the molecule. It is a liquid detergent composition characterized by containing an active agent.

  According to the present invention, a practical viscosity construction can be realized without changing the feeling of use of the anionic surfactant without impairing the low temperature stability.

  Hereinafter, embodiments of the present invention will be described.

The thickener of the present invention has a structure represented by the general formula (1). R ₁ in the formula represents a linear or branched alkyl group or a carbon number of 6 to 14, preferably 8 to 12. If the number of carbon atoms is smaller than 6, it is not preferable because the interaction with the hardly thickening anionic surfactant is poor and it is difficult to construct the viscosity. If it is larger than 14, the melting point becomes high and the handling property is insufficient, which is not preferable.

  Preferred examples of the thickener of the present invention include 2-hydroxyethyloctyldimethylamine, 2-hydroxyethyldecyldimethylamine, 2-hydroxyethyldodecyldimethylamine, and 2-hydroxyethyltetradecyldimethylamine in terms of handling properties and performance. 2-hydroxyethyloctyl-N-methylethanolamine, 2-hydroxyethyldecyl-N-methylethanolamine, 2-hydroxyethyldodecyl-N-methylethanolamine, 2-hydroxyethyltetradecyl-N-methylethanolamine 2-hydroxyethyloctyldiethanolamine, 2-hydroxyethyldecyldiethanolamine, 2-hydroxyethyldodecyldiethanolamine, 2-hydroxyethyltetradecyldiethanolamine, 1- (Bismethylamino) -3- (octyloxy) -2-propanol, 1- (bismethylamino) -3- (decyloxy) -2-propanol, 1- (bismethylamino) -3- (dodecyloxy)- 2-propanol, 1- (bismethylamino) -3- (tetradecyloxy) -2-propanol, 1-((2-hydroxyethyl) (methyl) amino) -3- (octyloxy) -2-propanol, 1-((2-hydroxyethyl) (methyl) amino) -3- (decyloxy) -2-propanol, 1-((2-hydroxyethyl) (methyl) amino) -3- (dodecyloxy) -2-propanol 1-((2-hydroxyethyl) (methyl) amino) -3- (tetradecyloxy) -2-propanol, 1- (bishydroxyethylamino) -3- (octyloxy) -2-propanol, 1- (Bishydr Loxyethylamino) -3- (decyloxy) -2-propanol, 1- (bishydroxyethylamino) -3- (dodecyloxy) -2-propanol, 1- (bishydroxyethylamino) -3- (tetradecyloxy) ) -2-propanol and the like.

  Although the manufacturing method of the thickener in this invention is not specifically limited, For example, the method obtained by making epoxyalkane and alkylglycidyl ether of specific chain length react with a secondary amine can be used.

  Examples of the secondary amine include dimethylamine, N-methylethanolamine, and diethanolamine.

  Examples of the epoxy alkane having the specific chain length include 1,2-epoxydecane, 1,2-epoxydodecane, and 1,2-epoxytetradecane.

  Examples of the alkyl glycidyl ether having a specific chain length include octyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, and tetradecyl glycidyl ether.

  Since the state of the thickener of the present invention is liquid at room temperature, it is excellent in handling properties.

  The thickener of the present invention is added in a low concentration compared to known thickeners such as thickeners used in other similar uses, such as fatty acid monoethanolamide, fatty acid diethanolamide, and polyethylene glycol fatty acid ester. And practical viscosity construction is possible.

  The liquid cleaning composition of the present invention contains the thickener in this invention. A liquid cleaning composition is a composition for the purpose of cleaning human bodies, clothes, dishes, machines, and the like. Examples of the liquid cleaning composition include shampoos, body shampoos, body soaps, clothing cleaners, kitchen cleaners, and car wash cleaners.

  The liquid cleaning composition in this invention has a viscosity of 300 to 20,000 mPa · s at room temperature by including the thickener of the present invention. Viscosity can be measured by B-type viscosity.

  Although the quantity of the thickener contained in the liquid cleaning composition of this invention is suitably determined by a composition, it can contain in the ratio of 0.1-10 mass%. If the content of the thickener of the present invention in the liquid cleaning composition is less than the lower limit, a practical viscosity cannot be obtained, and if it exceeds the upper limit, gelation or phase separation occurs, which is not preferable.

  In addition to the thickener of the present invention, the liquid cleaning composition of the present invention may contain a hardly thickening anionic surfactant.

  The difficult-thickening anionic surfactant refers to an anionic surfactant that cannot build a practical viscosity in common anionic surfactants such as salt and fatty acid diethanolamide. .

Examples of the hardly thickening anionic surfactants include the following anionic surfactants.
(A-1) Fatty acid salt (A-2) N-acyl neutral amino acid salt (A-3) N-acyl acidic amino acid salt (A-4) Alkyl ether carboxylate (A-5) Amido ether carboxylate (A-6) Polyoxyethylene alkyl sulfosuccinate (A-7) Polyoxyethylene amide ether sulfosuccinate

(A-1) Fatty acid salt The fatty acid salt is represented by the general formula (2).

[Wherein, R ⁴ represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, and M ¹ represents an alkali metal or an alkanolamine. ]
And more preferably laurate, myristate, palmitate, stearate, oleate, palm oil fatty acid salt, palm kernel fatty acid salt, palm oil fatty acid salt , Etc., and mixtures thereof are also used, and examples of the salt thereof include sodium salt, potassium salt, triethanolamine salt and the like.

(A-2) N-acyl neutral amino acid salt The N-acyl neutral amino acid salt has the general formula (3)

[Wherein R ⁵ represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, R ⁶ represents a hydrogen atom or a methyl group, Z ⁻ represents a —COO ^— group or a —SO ₃ ^— group, M ² Represents a counter ion of the Z ⁻ group and represents an alkali metal or alkanolamine, and a represents an integer of 1 or 2. ]
And an N-lauroyl sarcosine salt, an N-coconut oil fatty acid sarcosine salt, an N-lauroyl-N-methyl-β-alanine salt, an N-coconut oil fatty acid-N— Examples thereof include methyl-β-alanine salt, lauroyl-N-methyltaurine, coconut oil fatty acid-N-methyltaurine, and the salt includes sodium salt, potassium salt, triethanolamine salt and the like.

(A-3) N-acyl acidic amino acid salt The N-acyl acidic amino acid salt has the general formula (4)

[Wherein, R ⁷ represents an alkyl group or alkenyl group having ⁷ to 21 carbon atoms, and M ³ and M ⁴ are the same or different and each represents a hydrogen atom, an alkali metal, or an alkanolamine. However, M ³ and M ⁴ are not both hydrogen atoms. b is represented by an integer of 1 or 2. ]
And preferably N-lauroyl-L-glutamate, N-coconut oil fatty acid-L-glutamate, N-lauroyl aspartate, N-coconut oil fatty acid asparagine Examples of the salt include sodium salt, potassium salt, and triethanolamine salt.

(A-4) Alkyl ether carboxylate The alkyl ether carboxylate has the general formula (5)

[Wherein, R ⁸ represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and M ⁵ represents an alkali metal or an alkanolamine. c shows 1-10. ]
Preferably, poly (1-10) oxyethylene lauryl ether acetate, poly (1-10) oxyethylene coconut oil alkyl ether acetate, poly (1-10) oxy Examples thereof include ethylene tridecyl ether acetate, and examples of the salt include sodium salt, potassium salt, and triethanolamine salt.

(A-5) Amide ether carboxylate The amide ether carboxylate has the general formula (6)

[Wherein, R ⁹ represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M ⁶ represents an alkali metal or an alkanolamine. d shows 1-10. ]
Preferably, poly (1-10) oxyethylene lauroyl ethanolamide ether acetate, poly (1-10) oxyethylene coconut oil fatty acid ethanolamide ether acetate, poly (1 -10) N-methyl-lauroyl ethanolamide ether acetate, poly (1-10) N-ethyl-lauroyl ethanolamide ether acetate, poly (1-10) oxyethylene N-methyl-coconut oil fatty acid ethanolamide ether acetate Salt, poly (1-10) oxyethylene N-ethyl-coconut oil fatty acid ethanolamide ether acetate, and the like, and the salt includes sodium salt, potassium salt, triethanolamine salt, and the like.

(A-6) Polyoxyethylene alkyl sulfosuccinate The polyoxyethylene alkyl sulfosuccinate has the general formula (7-1) or (7-2)

[Wherein, R ¹¹ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, and M ⁷ and M ⁸ may be the same or different and each represents an alkali metal or an alkanolamine. e shows 0-10. ]
A poly (0-10) oxyethylene lauryl sulfosuccinate, poly (0-10) oxyethylene coconut oil fatty acid sulfosuccinate, and the like. Examples of the salt include sodium salt, potassium salt, triethanolamine salt and the like.

(A-7) Polyoxyethylene amide ether sulfosuccinate The polyoxyethylene amide ether sulfosuccinate has the general formula (8-1) or (8-2)

[Wherein R ¹² represents an alkyl group or alkenyl group having 7 to ²¹ carbon atoms, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M ⁹ and M ¹⁰ may be the same or different. Represents an alkali metal or an alkanolamine. f shows 0-10. ]
Preferably, poly (0-10) oxyethylene lauroyl ethanolamide sulfosuccinate, poly (0-10) oxyethylene coconut oil fatty acid ethanolamide sulfosuccinate, poly (0-10) oxyethylene N-methyl-lauroylethanolamide sulfosuccinate, poly (0-10) oxyethylene N-methyl-coconut oil fatty acid ethanolamide sulfosuccinate, poly (0-10) oxyethylene N-ethyl -Lauroyl ethanolamide sulfosuccinate, poly (0-10) oxyethylene N-ethyl-coconut oil fatty acid ethanolamide sulfosuccinate, and the like, and the salt includes sodium salt, potassium salt, triethanolamine salt, etc. Can be mentioned.

  Any of the non-thickening anionic surfactants contained in the liquid cleaning composition of the present invention is effective as long as it is listed above. Among them, (A-2) N-acyl neutral amino acid salts and (A -3) N-acylamino acid surfactants of N-acyl acidic amino acid salts can be expected to have a particularly excellent thickening function. That is, (A-2) N-acyl neutral amino acid salts and (A-3) N-acyl acidic amino acid salt N-acyl amino acid surfactants were particularly difficult to build viscosity with known thickeners. However, practical viscosity construction becomes possible by using the thickener of the present invention.

  The liquid cleaning composition of the present invention has practical viscosity and low-temperature stability even when the composition contains the hardly thickening anionic activator as a main ingredient.

  The hardly thickening anionic surfactant contained in the liquid cleaning composition of the present invention is usually contained in an amount of 1 to 50% by mass, preferably 10 to 40% by mass. When the content of the anionic surfactant in the liquid cleaning composition is less than the lower limit, the foaming power and the ability as a cleaning agent are not satisfied, and when the content is higher than the upper limit, gelation and phase separation occur.

  In this case, a practical viscosity can be constructed | assembled by containing 2.5-30 mass% of the thickener of this invention with respect to a difficult-thickening anionic surfactant.

  The detergent composition of the present invention can contain a surfactant having a cation center in the molecule as the component (C) in addition to the thickener of the present invention and the hardly thickening anionic surfactant.

  The surfactant having a cation center in the molecule means a surfactant containing a nitrogen atom charged in the positive electrode in the molecule.

  The surfactant having a cation center in the molecule is generally called an amphoteric surfactant, a semipolar surfactant, or a cationic surfactant.

  As the amphoteric surfactant, a betaine type amphoteric surfactant represented by the following general formula (9) and an amidoamine type amphoteric surfactant represented by the following general formulas (10) and (11) are preferable.

[In the formula, R ¹⁴ represents an alkyl group having 7 to 19 carbon atoms, an alkenyl group, or an alkyl group containing a hydroxyl group, and R ¹⁵ and R ¹⁶ each independently represents a methyl group, an ethyl group, or a hydroxyethyl group. , R ¹⁷ represents an alkylene group having 1 to 3 carbon atoms which may contain a hydroxyl group, g represents a number of 1 to 3, h represents 1 or 0, and Z ⁻ represents a —COO group or a —SO ₃ ^— group. . ]
Preferable examples include, for example, lauryl dimethyl acetate betaine, lauryl dimethyl hydroxypropyl sulfobetaine, lauric acid amide dimethyl acetate betaine, hydroxyalkyl (C12-14) hydroxyethylmethylglycine, lauric acid amidopropyl hydroxysulfobetaine, and the like.

[Wherein R ¹⁸ is an alkyl group or alkenyl group having 7 to 19 carbon atoms, u is an integer of 2 to 3, v and w are each independently an integer of 1 to 3, M ¹¹ is an alkali metal, an alkaline earth metal Represents an alkanolamine, and y represents an integer of 1 or 2. ]

  These include a group of surfactants commonly referred to as imidazolinium betaine type surfactants. It has been clarified that an imidazolinium betaine-type surfactant has a structure of the above general formula (10) or (11) due to hydrolysis of an imidazoline ring at an intermediate stage of the synthesis route (for example, Japanese Patent Publication No. Sho) 59-51532, Japanese Patent Publication No. 35-4762, and Cosmetics & Toiletries, Vol. 95, No. 11, p45-48, 1980).

  Suitable examples of these amidoamine type amphoteric surfactants include, for example, 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, N-lauroyl-N′-carboxymethyl-N′-hydroxyethylethylenediamine sodium, N-coconut fatty acid acyl-N′-carboxyethyl-N′-hydroxyethylethylenediamine sodium and the like are used.

  As said semipolar surfactant, what is shown by following General formula (12) is preferable.

[In the formula, R ¹⁹ represents an alkyl or alkenyl group having 7 to ¹⁹ carbon atoms, R ²⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxyethyl group, s represents an integer of 1 to 3, and t represents 1 or 0 is shown. ]

  The semipolar surfactant has a nitrogen atom charged to δ + in the molecule, which is presumed to act as a cation center. Preferable examples of the semipolar surfactant include ralyl dimethylamine oxide, lauric acid amide propyl amine oxide, myristyl dimethyl amine oxide, myristic amide propyl amine oxide, coconut alkyl dimethyl amine oxide, coconut fatty acid amide propyl amine oxide and the like. Is mentioned.

  As said cationic surfactant, what is shown by following General formula (13) is preferable.

[In the formula, R ²¹ represents an alkyl group or alkenyl group having 7 to 19 carbon atoms, s represents an integer of 1 to 3, and t represents 1 or 0. R ²² , R ²³ and R ²⁴ are each an alkyl group having 1 to 3 carbon atoms or a compound represented by the formula (14)

And B ⁻ represents a counter ion for a cation group such as chlorine ion or bromine ion. ]

  Preferable examples include dilauryl dimethyl ammonium chloride, stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, distearyl dimethyl ammonium chloride, ethyl lanolin sulfate fatty acid aminopropylethyl dimethyl ammonium, and the like.

  The surfactant having a cation center in the molecule may contain only one kind or a mixture of two or more kinds.

  By including the surfactant having a cation center in the molecule as the component (C) in the liquid cleaning composition of the present invention, the ultimate viscosity and the effect of adding a thickener are improved.

  The blending amount of the surfactant having a cation center in the molecule contained in the liquid detergent composition of the present invention is preferably 0.5 to 30% by mass in the liquid detergent composition. Furthermore, the compounding amount of the surfactant having a cation center in the molecule is 9: 1 to 1: 1 by mass ratio with respect to the hardly-thickening anionic surfactant component of the component (A) blended in the detergent composition. More preferably, it is in the range of 8: 2 to 6: 4.

  When the amount of the surfactant having a cation center in the molecule per detergent composition is less than the lower limit, the addition effect does not appear, and when the upper limit is exceeded, the feeling of use of the detergent composition is Problems such as damage and an increase in the texture of bubbles occur, which is not preferable.

  When blended as a shampoo composition, the liquid detergent composition of the present invention is excellent in the blending characteristics of the conditioning agent.

  A preferred conditioning agent is a cationic cellulose having a molecular weight of 400,000 to 1,500,000 and a cationic nitrogen content of 1 to 2.5% (mass%).

  Commercially available products include, for example, Poise C-H60 (molecular weight 600,000, N content 2.2%), Poise C-M80 (molecular weight 800,000, N content 1.5%), Poise C-L150 (molecular weight 1,500,000, N Content 1.3%) (above, manufactured by Kao Corporation); Polymer JR400 (molecular weight 400,000, N content 1.7%) (manufactured by Union Carbide); Katchinal LC-100 (molecular weight 400,000, N content 1.0 %), Kachinal HC-100K (molecular weight 400,000, N content 2.0%), kachinal LC-200 (molecular weight 1.5 million, N content 1.2%) (above, manufactured by Toho Chemical Co., Ltd.). The blending amount of the conditioning agent is 0.1 to 1.0% by weight, preferably 0.3 to 0.6% by weight, based on the entire composition. If the blending amount is less than 0.1% by weight, a sufficient conditioning effect cannot be obtained, and if it exceeds 1.0% by weight, the feeling of use may be deteriorated after washing the hair, which is not preferable.

  Moreover, if the molecular weight of the cationized cellulose is less than 400,000, a sufficient rinse-in effect cannot be obtained, and if the cationic nitrogen content is less than 1% (mass%), the adsorptivity to hair is insufficient and a sufficient conditioning effect is obtained. This is not preferable.

  Further, other anionic surfactants, nonionic surfactants, and other components commonly used in detergents or cosmetics, such as animal, plant, fish shellfish, and microorganism-derived extractions, as long as they do not interfere with the effects of the present invention. Products, powder components, liquid fats and oils, solid fats and oils, waxes, hydrocarbons, higher alcohols, esters, silicones, humectants, water-soluble polymers, coating agents, UV absorbers, flame retardants, sequestering agents, lower alcohols, sugars , Amino acids, organic amines, synthetic resin emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, antibacterial agents, perfumes, etc. good.

The effects of the present invention will be described in further detail with reference to the following examples.
A substance related to the general formula (1) of the present invention was produced and identified by the following method.

Production Example 1 90 g (20 mol) of a 50% aqueous solution of dimethylamine and 184 g (1 mol) of 1,2-epoxydodecane were placed in a 2-hydroxydodecyldimethylamine autoclave reaction vessel. After purging with nitrogen, the temperature was raised stepwise to 160 ° C. with stirring. No pressure control was performed, and when the temperature reached 160 ° C., aging was performed overnight. The next day, the reaction was stopped and cooled to room temperature. The reaction solution was transferred to a separating funnel, the organic phase was separated, and the organic layer was dried over anhydrous sodium sulfate for 2 hours. After anhydrous sodium sulfate was removed by filtration, the organic layer was concentrated under reduced pressure to obtain 2-hydroxydodecylditylamine.

Production Example 2 A 2-hydroxytetradecyldimethylamine autoclave reaction vessel was charged with 90 g (20 mol) of a 50% aqueous dimethylamine solution and 212 g (1 mol) of 1,2-epoxytetradecane. After purging with nitrogen, the temperature was raised stepwise to 160 ° C. with stirring. No pressure control was performed, and when the temperature reached 160 ° C., aging was performed overnight. The next day, the reaction was stopped and cooled to room temperature. The reaction solution was transferred to a separating funnel, the organic phase was separated, and the organic layer was dried over anhydrous sodium sulfate for 2 hours. After anhydrous sodium sulfate was removed by filtration, the organic layer was concentrated under reduced pressure to obtain 2-hydroxytetradecylditylamine.

Production Example 3 A 2-hydroxyhexadecyldimethylamine autoclave reaction vessel was charged with 90 g (20 mol) of a 50% aqueous dimethylamine solution and 240 g (1 mol) of 1,2-epoxyhexadecane. After purging with nitrogen, the temperature was raised stepwise to 160 ° C. with stirring. No pressure control was performed, and when the temperature reached 160 ° C., aging was performed overnight. The next day, the reaction was stopped and cooled to room temperature. The reaction solution was transferred to a separating funnel, the organic phase was separated, and the organic layer was dried over anhydrous sodium sulfate for 2 hours. After anhydrous sodium sulfate was removed by filtration, the organic layer was concentrated under reduced pressure to obtain 2-hydroxyhexadecyl ditylamine.

Production Example 4 2-Hydroxy Mixed Alkyl (C12 / C14) -N-Methylethanolamine In a reaction vessel, 750 g (10 mol) of N-methylethanolamine, 1,2-epoxydodecane (0.5 mol) and 1,2-epoxytetradecane 198 g of (0.5 mol) mixture was added. After purging with nitrogen, the temperature was raised stepwise to 160 ° C. with stirring. When the temperature reached 160 ° C., aging was performed overnight. The next day, the reaction was stopped and cooled to room temperature. The reaction solution was transferred to a separating funnel, the organic phase was separated, and the organic layer was dried over anhydrous sodium sulfate for 2 hours. After anhydrous sodium sulfate was removed by filtration, the organic layer was concentrated under reduced pressure to obtain 2-hydroxy mixed alkyl (C12 · C14) -N-methylethanolamine.

Production Example 5 1-((2-hydroxyethyl) (methyl) amino) -3- (octyloxy) -2-propanol 750 g (10 mol) of N-methylethanolamine was added to a reaction vessel, and 1-Chloro-3- (octyloxy) -2-propanol (0.5 mol) synthesized with reference to the example of 344701 was added. After purging with nitrogen, the temperature was raised stepwise to 160 ° C. with stirring. When the temperature reached 160 ° C., aging was performed overnight. The next day, the reaction was stopped and cooled to room temperature. The reaction solution was transferred to a separating funnel, the organic phase was separated, and the organic layer was dried over anhydrous sodium sulfate for 2 hours. After the anhydrous sodium sulfate was removed by filtration, the organic layer was concentrated under reduced pressure to obtain 1-((2-hydroxyethyl) (methyl) amino) -3- (octyloxy) -2-propanol.

Production Example 6 1-((2-Hydroxyethyl) (methyl) amino) -3- (dodecyloxy) -2-propanol 750 g (10 mol) of N-methylethanolamine was added to a reaction vessel. 1-Chloro-3- (dodecyloxy) -2-propanol (0.5 mol) synthesized with reference to the example of 344701 was added. After purging with nitrogen, the temperature was raised stepwise to 160 ° C. with stirring. When the temperature reached 160 ° C., aging was performed overnight. The next day, the reaction was stopped and cooled to room temperature. The reaction solution was transferred to a separating funnel, the organic phase was separated, and the organic layer was dried over anhydrous sodium sulfate for 2 hours. After removing anhydrous sodium sulfate by filtration, the organic layer was concentrated under reduced pressure to obtain 1-((2-hydroxyethyl) (methyl) amino) -3- (dodecyloxy) -2-propanol.

Comparative Example 750 g (10 mol) of N-methylethanolamine and 1,2-epoxyoctadecane (0.5 mol) were placed in a 2-hydroxystearyl-N-methylethanolamine reaction vessel. After purging with nitrogen, the temperature was raised stepwise to 160 ° C. with stirring. When the temperature reached 160 ° C., aging was performed overnight. The next day, the reaction was stopped and cooled to room temperature. The reaction solution was transferred to a separating funnel, the organic phase was separated, and the organic layer was dried over anhydrous sodium sulfate for 2 hours. After removing anhydrous sodium sulfate by filtration, the organic layer was concentrated under reduced pressure to obtain 2-hydroxystearyl-N-methylethanolamine .

  Samples produced in the production example and Amisole CME (palm fatty acid monoethanolamide manufactured by Kawaken Fine Chemical Co., Ltd.) and Genapol DEL (Lauric acid PEG-2 manufactured by Clariant Japan Co., Ltd.) were added to various anionic surfactants for comparison. Its performance was evaluated. As the sample adjustment method, the mixture was mixed at the blending mass ratio shown in the table and the pH was adjusted, and then the total amount was diluted with water so as to be 100 parts by mass.

The measurement conditions for the measurement items were as follows.
Viscosity measuring instrument B-type rotational viscometer model B8M manufactured by TOKIMEC
Measurement temperature 25 ℃
After each sample made for low temperature stability viscosity measurement is allowed to stand at 5 ° C. for 12 hours, the sample is taken out and observed. Evaluation was performed in the following two stages.
× White turbidity, crystal precipitation 〇 Maintaining a transparent solution form

  Table 1 shows N-acylamino acid surfactants (hardly thickening anionic surfactant (A): comparative example group (B ′)) used in hair and body cleaning compositions. This indicates that the thickening effect of each compound (B) according to the present invention is not easily increased with the thickener.

  Comparing the examples and comparative examples, the compound of the present invention enables an excellent high-viscosity construction with a small amount of addition to the N-acyl amino acid surfactant, and has a thickening effect superior to conventional thickeners. You can see that Further, the compound of the present invention showed excellent usability test results, and also had good low-temperature stability.

  Table 2 shows the results of investigations on the thickening of the compounds of the present invention with respect to the N-acylglutamic acid surfactants and N-acylmethyltaurine surfactants, which are hardly thickening anionic surfactants. It shows viscosity. In addition, (A) indicates an N-acylamino acid surfactant, (B) is a thickener comprising the compound group of the present invention, (B ′) is a thickener shown as a comparison, (C ) Refers to a surfactant having a cationic center in the molecule. The compound of the present invention also had good low temperature stability. It was found that the viscosity can be more easily constructed by blending the amphoteric surfactant betaine amphoteric into the combination of the hardly thickening anionic surfactant and the thickener of the present invention. 14 and Comparative Examples 9 and 10 are clearly compared.

  Table 3 shows the thickener (B) of the present invention for the ether sulfate surfactant (A, a surfactant that tends to thicken) frequently used in shampoo compositions and the like, and the conventional thickener ( This shows the thickening effect of B ′).

  Comparing the Examples and Comparative Examples, the compound of the present invention can build an excellent viscosity with a small amount of addition to SLES, and compared with the conventional thickener (lauric acid PEG-2, coconut fatty acid monoethanolamide). It can be seen that it has an excellent thickening effect. Further, it can be seen that the compound of the present invention has good low-temperature stability and does not impair the usability.

Explanation of abbreviations in the table SLES: Polyoxyethylene lauryl ether sulfate sodium salt Ala. ALE: N-lauroyl-N-methyl-β-alanine sodium salt
(Made by Kawaken Fine Chemical Co., Ltd.)
Amizole CME: palm fatty acid monoethanolamide
(Made by Kawaken Fine Chemical Co., Ltd.)
Sof. LPB-R: Laminated amidopropyl betaine
(Made by Kawaken Fine Chemical Co., Ltd.)
Genapol DEL: PEG-2 laurate
(Manufactured by Clariant Japan)
AMT: Sodium cocoyl methyl taurine
(Manufactured by Nikko Chemicals Co., Ltd.)
Amisof CS22: Sodium cocoyl glutamate
(Ajinomoto Co., Inc.)
Farmin DM2098: Dimethyllaurylamine
(Manufactured by Kao Corporation)

Example 45 Shampoo Composition A formulation example of a shampoo composition using the amine of Production Example 1 is shown below. Compared with the composition which mix | blended conventional thickeners, such as Amidol CME, the prescription excellent in the higher thickening effect and low-temperature stability was obtained.
(Compounding ingredients) (wt%)
Polyoxyethylene (3) sodium lauryl ether sulfate 12.0%
Coconut oil fatty acid amidopropyl betaine 4.0%
Amine of Production Example 1 5.0%
Ethylene glycol distearate 0.5%
Cationized cellulose 0.5%
Quaternium-33 1.0%
Cetyl alcohol 0.5%
Dimethylpolysiloxane (20cs) 1.0%
Glutamic acid 5% distilled water diluted solution pH = 4.0
Preservative 0.2%
Pigment proper amount of fragrance 0.3%
Purified water residue

Example 46 Body Shampoo A formulation example of a body shampoo using the amine of Production Example 1 is shown below. Similar to Example 45, the formulation is excellent in thickening and low temperature stability.
(Compounding ingredients) (wt%)
Lauric acid 6.0%
Myristic acid 8.0%
Palmitic acid 2.0%
Potassium hydroxide 3.89%
Lauric acid amidopropyl hydroxysulfobetaine 3.0%
Lauroyl-N-methyl-β-alanine potassium 2.0%
Production Example 1 amine 3.0%
Palm oil fatty acylglycine potassium salt 0.5%
Glycerin 5.0%
Ethylene glycol distearate 1.5%
Hydroxypropyl methylcellulose 0.2%
EDTA.4 sodium 0.2%
Methylparaben 0.2%
Purified water residue

Example 47 Conditioner The following is a conditioner formulation example. By blending the amine of Production Example 1, the formulation gives the appropriate viscosity required at the time of application, and further feels the familiarity of the base with the hair and the feeling of unity after drying.
(Compounding ingredients) (wt%)
Stearyl alcohol 5.0%
Glycerin 4.0%
Stearamidopropyldimethylamine 2.0%
Dimethicone 2.0%
Amodimethicone 2.0%
Cetanol 1.0%
Amine of Production Example 1 0.8%
Isopropyl myristate 1.0%
Lactic acid 0.5%
(Hydroxystearic acid / stearic acid / rosinic acid) dipentaerythryl 1.5%
Hydroxyethyl cellulose 0.2%
Lanolin fatty acid cholesteryl 0.1%
Purified water residue

  The thickener of the present invention is suitable as a thickener because it can thicken an anionic surfactant that is difficult to thicken without impairing the feeling of use of the anionic surfactant.

Claims (5)

General formula (1)

[Wherein R ¹ is a linear or branched alkyl group having 6 to 14 carbon atoms, X is a methylene group or oxygen atom, R ² and R ³ are methyl group, ethyl group, hydroxyethyl group or hydroxy group. A propyl group, which may be the same or different; ]
A thickener comprising a compound represented by A liquid detergent composition comprising the thickener according to claim 1. A liquid detergent composition comprising (A) a hard-viscosity anionic surfactant and (B) the thickener according to claim 1.   The liquid detergent composition according to claim 3, wherein the hardly thickening anionic surfactant is an N-acylamino acid surfactant. (A) N-acylamino acid surfactant (B) A liquid detergent composition comprising the thickener according to claim 1 and (C) a surfactant having a cation center in the molecule. object.