JP2592580B2 - N-alkylamide alkanol sulfate, method for producing the same, and detergent composition containing the compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to N-alkylamidoalkanol sulfates which are hypoallergenic to the skin, have excellent foaming and detergency, and are widely useful as cleaning agents for hair, skin or tableware. The present invention relates to an ester salt, a method for producing the ester salt, and a detergent composition containing the compound.

[0002]

2. Description of the Related Art In recent years,
Surfactants used as detergents are required to have excellent properties such as biodegradability and safety to skin and eyes, in addition to surface activity. In order to satisfy these requirements, acylated amino acid type surfactants, imidazoline type surfactants, and sugar type surfactants such as alkyl glycosides have been widely used.

[0003] However, these surfactants are generally excellent in safety and the like, but are still insufficient in detergency and foaming power, which are particularly important as detergents, and are used alone as a component of shampoos and the like. It is rarely used, and is generally used in combination with a conventional anionic surfactant such as alkyl sulfate and alkyl ether sulfate. On the other hand, sulfates of fatty acid monoethanolamide or isethionate are surfactants excellent in both safety and foaming properties, but have a problem in chemical stability in a solution state.
For this reason, the appearance of a cleaning agent which is excellent in foaming properties and detergency, and has high safety and stability is strongly desired.

[0004]

DISCLOSURE OF THE INVENTION In view of the above situation, the present inventors have developed an interface which is useful as a cleaning agent for washing hair, body, dishes, etc., has excellent detergency, foaming power and high safety. As a result of intensive studies on the activator, it has been found that an N-alkylamidoalkanol sulfate having an amide group and a sulfate group derived from a long-chain primary amine or secondary amine achieves the above object. completed.

That is, the present invention provides an N-type compound represented by the general formula (1):
Alkyl amide alkanol sulfate, a method for producing the same, and N-alkyl amide alkanol sulfate represented by the general formula (1), which is excellent in foamability, detergency, and safety. It provides a high detergent composition.

[0006]

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(Wherein, R ¹ represents a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, R ² represents an alkyl group, alkenyl group or hydrogen atom having 1 to 22 carbon atoms, R ³ represents a linear or branched alkylene group having 1 to 5 carbon atoms; R ⁴ O represents an oxyalkylene group having 2 to 3 carbon atoms; n represents an arbitrary number of 0 to 20; ⁴ O may be the same or different, and M is a hydrogen atom, an alkali metal,
Alkaline earth metal, ammonium, alkanol ammonium having 2 to 9 carbon atoms, alkyl ammonium or alkenyl ammonium having 1 to 22 carbon atoms, 1 carbon atom
~ 18 alkyl or alkenyl substituted pyridinium,
Or a basic amino acid. In the general formula (1), R ¹ represents a straight-chain or branched-chain alkyl group or alkenyl group having 6 to 22 carbon atoms, and is represented by a straight-chain or branched-chain alkyl group or alkenyl group having 6 to 22 carbon atoms. Is a group such as hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, isostearyl, eicosyl, docosyl,
A linear or branched alkyl group having 6 to 22 carbon atoms is preferred from the viewpoint of foaming properties, and a linear alkyl group having 8 to 18 carbon atoms is particularly preferred.

R ² represents an alkyl group, alkenyl group or hydrogen atom having 1 to 22 carbon atoms. Examples of the alkyl group or alkenyl group having 1 to 22 carbon atoms include methyl, ethyl, propyl, butyl, The alkyl group or the alkenyl group exemplified for the above-mentioned R ¹ is exemplified. As R ² , a hydrogen atom or a methyl group is preferable from the viewpoints of foaming properties, safety and chemical stability.

R ³ represents a linear or branched alkylene group having 1 to 5 carbon atoms, but is preferably a methylene group, a pentylene group,
-A methylbutylene group is preferred, and a methylene group is particularly preferred in terms of foaming properties and chemical stability.

R ⁴ O represents an oxyalkylene group having 2 to 3 carbon atoms, preferably an oxyethylene group or an oxypropylene group. n represents an arbitrary number from 0 to 20;
An arbitrary number of to 10 is preferable, and n = 0 is particularly preferable. The n R ⁴ Os may be the same or different.

M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkanol ammonium having 2 to 9 carbon atoms, an alkyl ammonium or alkenyl ammonium having 1 to 22 carbon atoms, or an alkyl or alkenyl having 1 to 18 carbon atoms. The term "substituted pyridinium" or "basic amino acid" refers to ammonium, sodium, potassium, or alkanol ammonium having 2 to 9 carbon atoms in terms of foamability, and more preferable are ammonium, sodium, and triethanol ammonium.

Preferred examples of the N-alkylamide alkanol sulfate represented by the general formula (1) of the present invention are as follows.

CH ₃ (CH ₂ ) ₁₁ NHCOCH ₂ OSO ₃ NH ₄ , CH ₃ (CH ₂ ) ₁₁ NH
CO (CH ₂ ) ₅ OSO ₃ NH ₄ , CH ₃ (CH ₂ ) ₉ NHCOCH ₂ OSO ₃ NH ₄ , CH ₃ (CH ₂ )
₁₁ N (CH ₃ ) COCH ₂ OSO ₃ Na, CH ₃ (CH ₂ ) ₁₁ NHCOCH ₂ OSO ₃ Na, CH ₃ (C
H ₂ ) ₁₁ NHCO (CH ₂ ) ₂ OSO ₃ Na, CH ₃ (CH ₂ ) ₁₁ NHCO (CH ₂ ) ₃ OSO ₃ Na,
CH ₃ (CH ₂ ) ₁₁ NHCO (CH ₂ ) ₄ OSO ₃ Na, CH ₃ (CH ₂ ) ₁₁ NHCO (CH ₂ ) ₅ OSO
₃ Na, CH ₃ (CH ₂ ) ₁₁ NHCOCH ₂ CH (CH ₃ ) CH ₂ CH ₂ OSO ₃ Na, CH ₃ (CH ₂ )
₁₁ NHCOCH ₂ CH (CH ₃ ) CH ₂ CH ₂ OSO ₃ K, CH ₃ (CH ₂ ) ₁₃ NHCO (CH ₂ ) ₃ O
SO ₃ Na, CH ₃ (CH ₂ ) ₁₃ NHCO (CH ₂ ) ₃ OSO ₃ NH ₄ , CH ₃ (CH ₂ ) ₁₃ NHCO
(CH ₂ ) ₄ OSO ₃ NH ₄ , CH ₃ (CH ₂ ) ₉ NHCO (CH ₂ ) ₃ OSO ₃ Na, CH ₃ (CH ₂ ) ₉
NHCO (CH ₂ ) ₃ OSO ₃ HN (CH ₂ CH ₂ OH) ₃ , CH ₃ (CH ₂ ) ₉ NHCO (CH ₂ ) ₃ OSO
₃ H ₂ N (CH ₂ CH ₂ OH) ₂ , CH ₃ (CH ₂ ) ₉ NHCO (CH ₂ ) ₃ OSO ₃ H ₃ NCH ₂ CH ₂ O
H, CH ₃ (CH ₂ ) ₉ NHCO (CH ₂ ) ₅ OSO ₃ Na, CH ₃ (CH ₂ ) ₇ NHCO (CH ₂ ) ₄ OS
O ₃ Na, CH ₃ (CH ₂ ) ₁₁ N (CH ₃ ) CO (CH ₂ ) ₃ OSO ₃ Na, CH ₃ (CH ₂ ) ₁₃ N (C
H ₃ ) CO (CH ₂ ) ₄ OSO ₃ Na, CH ₃ (CH ₂ ) ₁₁ NHCO (CH ₂ ) ₃ OCH ₂ CH ₂ OSO ₃
Na, CH ₃ (CH ₂ ) ₁₁ NHCO (CH ₂ ) ₄ OCH ₂ CH (CH ₃ ) OSO ₃ Na, CH ₃ (CH ₂ ) ₉
NHCO (CH ₂ ) ₄ O (CH ₂ CH ₂ O) ₅ SO ₃ Na The N-alkylamidoalkanol sulfate salt represented by the general formula (1) of the present invention is prepared by the following step A, B, C or A, By performing C, or D, B, C, or D, C in this order, it can be easily manufactured. Step A General formula (2)

[0014]

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(Wherein, R ¹ and R ² have the same meanings as described above).

[0016]

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(Wherein R ³ has the same meaning as described above), and reacted with a cyclic lactone represented by the general formula (4):

[0018]

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(Wherein, R ¹ , R ² and R ³ have the same meanings as described above).

Step B : An N-alkylamide alkanol represented by the general formula (4) is reacted with an alkylene oxide in the presence of an alkali or acid catalyst to give a compound of the general formula (5)

[0021]

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(Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above, and n ′ represents a number of 1 to 20). .

Step C : The N-alkylamide alkanol represented by the general formula (4) or (5) is reacted with a sulfating agent, then neutralized with a basic substance, and then expressed by the general formula (1). Obtaining an N-alkylamide alkanol sulfate salt.

Step D The aliphatic amine represented by the general formula (2) is added to the general formula (6) HO—R ³ CO ₂ R ⁵ (6) (wherein R ³ has the same meaning as described above; R ⁵ is reacted with hydrogen or a linear or ω- hydroxy carboxylic acid or its ester represented by.) represents an alkyl group branched having 1 to 4 carbon atoms, represented by the general formula (4) A step of obtaining an N-alkylamide alkanol.

Hereinafter, each step will be described in detail. Step A In this step, a cyclic lactone represented by the general formula (3) (hereinafter referred to as a cyclic lactone (3) is added to an aliphatic amine represented by the general formula (2) (hereinafter abbreviated as aliphatic amine (2)). )) To form an N-alkylamidoalkanol (hereinafter referred to as N-alkylamidoalkanol) represented by the general formula (4).
(Abbreviated as (4)). For the aliphatic amine (2) and the cyclic lactone (3) as the raw materials, any of those produced by a known method and those commercially available may be used, but if necessary, such as recrystallization, distillation, etc. A purified product may be used.

Specific examples of the aliphatic amine (2) include octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, octylmethylamine, decylmethylamine, dodecylmethylamine, tetradecylmethylamine Octylamine, decylamine, dodecylamine, and tetradecylamine are particularly preferable.

Specific examples of the cyclic lactone (3) include β-
Propiolactone, γ-butyrolactone, δ-valerolactone, 2-methyl-δ-valerolactone, ε-caprolactone, 2-methyl-γ-butyrolactone, and the like, and 2-methyl-δ-valerolactone, ε-caprolactone. Is particularly preferred.

In this step, the aliphatic amine (2) and 1
To 1.5-fold molar of the cyclic lactone (3) in the absence of a solvent or in a solvent such as toluene, xylene, dioxane or DMF if necessary, at 0 to 180 ° C, preferably 70 to 150 ° C, particularly preferably 80 to 130 ° C. By reacting at an appropriate temperature for 1 to 100 hours, preferably 1 to 20 hours, N-alkylamidoalkanol (4) can be obtained. If the reaction temperature exceeds 180 ° C., side reactions such as polymerization of the raw material lactone (3) become remarkable, which is not preferable.

The N-alkylamidoalkanol (4) obtained in this step can be used as it is in the next step, but if necessary, hexane, methanol, ethanol,
It can be recrystallized in a solvent such as acetone or chloroform to obtain a highly purified product.

Step B In this step, the N-alkylamide alkanol (4) obtained in Step A or Step D is reacted with an alkylene oxide in the presence of an alkali or acid catalyst, and is represented by the general formula (5). In this step, N-alkylamide alkanol (hereinafter abbreviated as N-alkylamide alkanol (5)) is obtained.

Examples of the alkali catalyst include alkali metal hydroxides, alkali metal carbonates, organic amines, metal oxides, alkoxylates and the like.
KOH. As acid catalysts, boron trifluoride (BF ₃ ),
Examples thereof include Lewis acids and metal oxides such as tin tetrachloride (SnCl ₄ ), antimony pentachloride (SbCl ₅ ), magnesium oxide (MgO), and aluminum oxide (Al ₂ O ₃ ), and preferably boron trifluoride. , Magnesium oxide. Examples of the alkylene oxide include ethylene oxide and propylene oxide, preferably ethylene oxide.

In this step, a desired amount of alkylene oxide is added to N-alkylamidoalkanol (4) in an amount of 0.5.
120 to 1 mol% in the presence of an acid or alkali catalyst
By reacting at a temperature of 80 ° C. for 1 to 10 hours, N-alkylamidoalkanol (5) can be obtained. If the reaction temperature exceeds 180 ° C., various by-products such as aldehydes and peroxides, which cause coloring or odor, are not preferred. To neutralize the acid or alkali catalyst, NaOH, KOH, or phosphoric acid, acetic acid, lactic acid, or the like may be added. Is also good.

Step C This step is carried out using N-alkylamidoalkanol (4) or N-alkylamide
The alkylamide alkanol (5) is reacted with a sulfating agent and then neutralized with a basic substance, and the N-alkylamide alkanol sulfate (hereinafter referred to as N-alkylamide alkanol sulfate) represented by the general formula (1) is used.
(Abbreviated as (1)). Examples of the sulfating agent include chlorosulfonic acid, sulfuric anhydride, fuming sulfuric acid, concentrated sulfuric acid, sulfamic acid, and the like, and chlorosulfonic acid, sulfuric anhydride, and sulfamic acid are preferable in terms of reaction yield.

As the basic substance, hydroxides, carbonates or bicarbonates of alkali metals or alkaline earth metals, ammonia, alkanolamines having 2 to 9 carbon atoms, alkylamines having 1 to 22 carbon atoms or Alkenylamine, alkyl or alkenyl-substituted pyridine having 1 to 18 carbon atoms, or basic amino acids, specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium hydrogen carbonate, sodium carbonate , Inorganic alkalis such as potassium carbonate, or ammonia, monoethanolamine, diethanolamine,
Triethanolamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, basic amino acids, and the like.
Preferred are ammonia, sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine and triethanolamine. These are subjected to neutralization of the sulfate as an aqueous solution or an alcohol solution. The degree of neutralization can be set arbitrarily.

In this step, N-alkylamidoalkanol (4) or N-alkylamidoalkanol
(5), using a 1 to 1.5 times mol of a sulfating agent, 0 to 10 times the amount of a solvent such as dichloromethane, chloroform, 1,2-dichloroethane, dimethylformamide, dimethylsulfoxide, dioxane, etc. ° C, preferably-
If the reaction is carried out at 30 to 50 ° C. for 1 to 20 hours, the corresponding sulfated ester is obtained.

It is necessary to purify the solvent so that water and alcohol are not substantially contained. Although the present sulfation can be carried out in the absence of a solvent, the viscosity is significantly increased during the reaction, so that equipment measures are required. On the other hand, if the reaction temperature exceeds 80 ° C., side reactions such as cleavage of the amide group proceed, which is not preferable. After the completion of the sulfation reaction, the solvent used for the reaction is distilled off, if necessary. The solvent can be distilled off after the neutralization described below.

Then, the sulfated product obtained in the above reaction and 0.9 to 1.5 equivalents of a basic substance were added to water, ethanol,
A neutralization reaction is performed in a solvent such as methanol at -50 to 80 ° C for 0.1 to 1 hour to obtain an N-alkylamide alkanol sulfate (1).

The compound obtained by the above neutralization reaction contains by-products such as N-alkylamidoalkanols, lactones and amines. Depending on the application, the reaction product can be used as it is, but if necessary, it can be purified by recrystallization, column chromatography, electrodialysis, solvent extraction or the like to obtain a product with higher purity.

Step D In this step, an aliphatic amine (2) is added to an ω-hydroxycarboxylic acid or an ester thereof (hereinafter referred to as ω-
Abbreviated as hydroxycarboxylic acid or its ester (6)),
Preferably, it is a step of reacting an ω-hydroxycarboxylic acid ester to obtain an N-alkylamide alkanol (4).

As the ω-hydroxycarboxylic acid or its ester (6), specifically, lactic acid, glycolic acid,
Hydroxypropionic acid, 3-hydroxybutyric acid, 4-hydroxypentanoic acid, 4-hydroxy-3-methylpentanoic acid, 5-hydroxyhexanoic acid, and methyl, ethyl, propyl, and butyl esters thereof; and methyl glycolate , Ethyl glycolate, propyl glycolate, butyl glycolate, methyl 2-hydroxypropionate, methyl 3-hydroxybutyrate, 4-
Methyl hydroxypentanoate and methyl 5-hydroxyhexanoate are preferred, especially methyl glycolate, ethyl glycolate and 5-
Methyl hydroxyhexanoate is preferred. This ω-hydroxycarboxylic acid or its ester (6) can be produced by a known method such as hydrolysis or alcoholysis of the corresponding lactone, and a commercially available product can be used as it is or subjected to purification such as recrystallization and distillation. After use, it may be used.

In this step, 1- to 2.0-fold moles of ω-hydroxycarboxylic acid or its ester (6) is added to the aliphatic amine (2) in the absence of a solvent, if necessary, if necessary, with CH ₃ ONa, KOH, NaOH.
40 to 200 ° C, preferably 60 to 150 ° C in the presence of a base catalyst such as
Dehydration or dealcoholation under reduced pressure at 1 ° C. for 1 to 100 hours, preferably 1 to 20 hours, gives N-alkylamidoalkanol (4). The pressure during the reaction is preferably reduced to 760 to 0.1 mmHg because dehydration is necessary.

The N-alkylamide alkanol (4) thus obtained can be used as it is in the next step, but if necessary, recrystallized in a solvent such as hexane, methanol, ethanol, acetone or chloroform. ,
It can also be purified.

The N-alkylamide alkanol sulfate (1) of the present invention is a surfactant having excellent detergency and foaming power and a highly safe surfactant, such as shampoo, body cleanser and tableware. It can be suitably used for various cleaning agents such as cleaning agents. The detergent composition of the present invention contains N-alkylamide alkanol sulfate (1) as an essential component, and its content is preferably 1 to 70% by weight, more preferably 10 to 70% by weight. It is.

In the cleaning composition of the present invention, components used in conventional cleaning agents such as shampoos, body cleaning agents, dishwashing agents and the like may be used in a range not impairing the effects of the present invention. Can be. Examples of such concomitant components include silicone derivatives, cationic surfactants, water-soluble cationic polymers, anionic surfactants, nonionic surfactants, amphoteric surfactants, humectants, other bactericides, emulsifiers, fragrances, and the like. .

Examples of the silicone derivative used in the present invention include the following 1) to 9). 1) Dimethyl polysiloxane

[0046]

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2) Methylphenyl polysiloxane

[0048]

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3) Polyether-modified silicone

[0050]

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4) Epoxy-modified silicone

[0052]

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Here, x ₂ is 1 to 500 (preferably 1 to 25)
0), y ₂ represents a number of 1 to 50 (preferably 1 to 30), and R ⁶ represents an alkylene group having 1 to 3 carbon atoms. 5) Fluorine-modified silicone

[0054]

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[0055] where x ₃ is 1 to 400 (preferably 1 to 250)
Represents the number of 6) Alcohol-modified silicone

[0056]

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Here, x ₄ and y ₄ are each 1 to 500 (preferably 1
Represents the number of ~200), R ⁷ represents _{C n 'H 2n' (n} '= 0~4). 7) Alkyl-modified silicone

[0058]

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Here, x ₅ and y ₅ each represent a number of 1 to 500 (preferably 1 to 200), R ⁸ represents an alkyl group having 2 to 18 carbon atoms,
R ⁹ represents C _{n ′} H _{2n ′} (n ′ = 0 to 4), and R ¹⁰ represents an alkyl group having 10 to 16 carbon atoms. 8) Alkoxy-modified silicone

[0060]

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Here, R ¹¹ represents a methyl group or a phenyl group, l ₁ represents an integer of ₁ to 3000, and m ₂ and n ₂ represent m ₂ + n ₂ = 1 to 1.
R ¹² represents an alkyl group having 1 to 28 carbon atoms (preferably 12 to 22 carbon atoms), and k represents an integer of 0 to 6. 9) Amino-modified silicone

[0062]

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Among these, particularly preferred amino-modified silicones are those represented by the following general formula.

[0064]

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(Wherein, R ¹⁵ , m ₃ , and n ₃ have the same meanings as described above.) The representative amino-modified silicone is represented by the following general formula, and has an average molecular weight of about 3,000 to 100,000. This is the name of Amodimethicone, CTFA dictionary (US, Cosmetic Ingredient Dictionar
y) It is described in the third edition.

[0066]

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(Wherein m ₃ and n ₃ have the same meanings as above.) The above-mentioned amino-modified silicone is preferably used as an aqueous emulsion.
According to the method described in JP-A-56-38609, a cyclic diorganopolysiloxane and an organodialkoxysilane having an aminoalkyl group and a hydroxy group, a hydroxyalkyl group, an oxyalkylene group, or a polyoxyalkylene group are converted to a fourth compound. It is obtained by emulsion polymerization in the presence of a quaternary ammonium salt-based surfactant and water.
When the amino-modified silicone is used as an aqueous emulsion, the amount of the amino-modified silicone contained in the aqueous emulsion is usually 20 to 60% by weight, preferably 30 to 50% by weight. Preferred commercially available amino-modified silicone aqueous emulsions include SM 8702C (manufactured by Dow Corning Toray Silicone Co., Ltd.) and DC 929 (manufactured by Dow Corning Co., Ltd.)
Manufactured).

The above silicone derivatives 1) to 9) may be used individually as they are, when they are used as a mixture of at least two kinds in advance, or a surfactant as a commonly used emulsifier, for example, a nonionic surfactant In some cases, one or more of an agent, an anionic activator, a cationic activator, and an amphoteric activator are used in a state where the silicone derivative is microdispersed in an aqueous medium (silicone emulsion). The silicone emulsion can be obtained by a method of stirring and mixing, a method of emulsion polymerization, or the like. Examples of such a silicone emulsion include KM880, KM883, KM884, KM885, KM886, KM887 (manufactured by Shin-Etsu Chemical Co., Ltd.), TEX100, TSW831, TEX150, TEX15
4, TEX170, TEX152, TEX172, XS65-A2773, TSC930 (manufactured by Toshiba Silicone Co., Ltd.), BY22-007, BY22-029, BY22
-019. BY22-034, BY22-020, BY22-009, BY22-008, BY22
-835, SM5571, SM8705 (manufactured by Dow Corning Toray Silicone Co., Ltd.) and the like are commercially available. Such silicone derivatives are preferably present in the cleaning compositions of the present invention.
The content is 0.01 to 3% by weight, more preferably 0.1 to 0.8% by weight.

The cationic surfactant used in the present invention includes, for example, a fourth surfactant represented by the following general formula (7) or (8).
Secondary ammonium salts.

[0070]

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(Wherein at least one of R ²¹ , R ²² , R ²³ and R ²⁴ may be substituted with an alkoxy, alkenyloxy, alkanoylamino or alkenoylamino group having a total of 8 to 28 carbon atoms) It indicates an alkyl or alkenyl group and the remainder represents a benzyl group, alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms .R ²⁵ is 2 carbon atoms
Represents an alkylene group of 1 to 3, Z represents a halogen ion or an organic anion, and n ₄ represents an integer of 1 to 20) Among such cationic surfactants, a quaternary ammonium represented by the general formula (7) Salts are preferred, and further preferred as the quaternary ammonium salts represented by the general formula (7) are:
For example, branched quaternary ammonium salts represented by the following general formulas (9) to (11) can be mentioned.

[0072]

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The branched quaternary ammonium salt represented by the general formula (9) is usually synthesized from, for example, an oxo alcohol having 8 to 16 carbon atoms, and examples thereof include an alkyl derived from an oxo alcohol. Examples thereof include a dialkyldimethylammonium salt having a group, a dialkylmethylhydroxyethylammonium salt, and a dialkylmethylbenzylammonium salt.

In the present invention, the branching ratio of R ^{26 in} the formula (9) is
Usually, 10 to 100% is used, but 10 to 50% is particularly preferable. Although those total number of carbon atoms in R ²⁶ is 8 to 16 are used, preferably those having a certain distribution, it is preferable in particular with a distribution shown below. C ₈ ~C _11: 5% or less _{C 12: 10~35% C 13:} 15~40% C 14: 20~45% C 15: 5~30% C 16: 5% or less such branched quaternary ammonium Specific examples of the salt include dialkyldimethylammonium chloride having an alkyl group having 8 to 16 carbon atoms and a branching ratio of 10 to 50%.
The branched quaternary ammonium salt represented by the general formula (10) is usually a Guerbet alcohol having 8 to 28 carbon atoms.

[0075]

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Is synthesized using the above as a raw material. Preferred examples of the branched quaternary ammonium salt include an alkyltrimethylammonium salt having an alkyl group derived from Guerbet alcohol, an alkyldimethylbenzylammonium salt, a dialkyldimethylammonium salt,
Dialkylmethylhydroxyethylammonium salts, dialkylmethylbenzylammonium salts and the like. Further, as particularly preferred specific examples among these,
Examples thereof include 2-decyltetradecyltrimethylammonium chloride, 2-dodecylhexadecyltrimethylammonium chloride, di-2-hexyldecyldimethylammonium chloride, and di-2-octyldodecyldimethylammonium chloride.

A preferred example of the methyl-branched quaternary ammonium salt represented by the general formula (11) is one in which the sum of s and t is 15. In addition, the general formulas (7), (8), (9), (1
Specific examples of Z which is a counter ion of the quaternary ammonium salts represented by (0) and (11) include halogen ions such as chlorine, iodine and bromine; methosulfate, ethosulfate, methophosphate and ethophosphate. Organic anions. The above cationic surfactants can be used alone or in combination of two or more, and are preferably incorporated in the cleaning composition of the present invention in an amount of 0.05 to 10% by weight.

The water-soluble cationic polymer used in the present invention is a water-soluble cationic polymer containing an amino group or an ammonium group bonded to a polymer chain, or containing at least dimethyldiallylammonium halide as a constitutional unit. Examples include cellulose derivatives, cationic starch, cationized guar gum derivatives, diallyl quaternary ammonium salt / acrylamide copolymers, and quaternized polyvinylpyrrolidone derivatives. As the cationized cellulose derivative, for example, those represented by the following general formula (12) are preferable.

[0079]

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In the formula (12), A represents a residue of an anhydroglucose unit, f is an integer of 50 to 20,000, and each R ³⁴ is
And each represents a substituent represented by the following general formula (13).

[0081]

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In the formula (13), R ³⁵ and R ³⁶ are an alkylene group having 2 or 3 carbon atoms, g is an integer of 0 to 10, h is an integer of 0 to 3, i is
Is an integer of 0 to 10, R ³⁷ is an alkylene group or a hydroxyalkylene group having 1 to 3 carbon atoms, R ³⁸ , R ³⁹ and R ⁴⁰ are the same or different, and an alkyl group having up to 10 carbon atoms, an aryl group or It represents an aralkyl group, and may form a heterocyclic ring containing a nitrogen atom in the formula. X ₁ represents an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.). The degree of cation substitution of the cationized cellulose derivative used in the present invention is 0.01 to 1, that is, the average value of h per anhydroglucose unit is preferably 0.01 to 1, and more preferably 0.02 to 0.5. G + i
Are an average of 1 to 3. The degree of cation substitution is not sufficient if it is less than 0.01 and may be more than 1, but is preferably 1 or less from the viewpoint of reaction yield. The molecular weight of the cationized cellulose derivative used herein is preferably between about 100,000 and 3,000,000. The cationic starch is preferably represented by the following general formula (14).

[0083]

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In the formula (14), B is a starch residue, R ⁴¹ is an alkylene group or a hydroxyalkylene group, R ⁴² , R ⁴³ and R ⁴⁴ are the same or different, and have an alkyl group having 10 or less carbon atoms, an aryl group. A heterocyclic group or an aralkyl group, and may include a nitrogen atom in the formula to form a heterocyclic ring. X ₂ represents an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.), and j represents a positive integer. The cationic starch used in the present invention has a cation substitution degree of 0.01 to 1, that is, 0.01 to 1, preferably 0.02 to 0.2 per anhydroglucose unit.
Those in which five cationic groups are introduced are preferred. A degree of cation substitution of less than 0.01 is not sufficient, and may be more than 1, but is preferably 1 or less from the viewpoint of reaction yield. As the cationized guar gum derivative, one represented by the following general formula (15) is preferable.

[0085]

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In the formula (15), D is a guar gum residue, R ⁴⁵ is an alkylene group or a hydroxyalkylene group, R ⁴⁶ , R ⁴⁷ , R ⁴⁸
Are the same or different and represent an alkyl group, an aryl group or an aralkyl group having 10 or less carbon atoms, and may form a heterocyclic ring containing a nitrogen atom in the formula. X ₃ is an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate,
Phosphoric acid, nitric acid, etc.), and k represents a positive integer. The degree of cation substitution of the cationized guar gum derivative used in the present invention is preferably from 0.01 to 1, and particularly preferably from 0.02 to 0.5 cationic groups introduced into the sugar unit. This type of cationic polymer is disclosed, for example, in JP-B-58-35640,
No. 60-46158 and JP-A-58-53996,
It is marketed as Jaguar (Celanese Stein Hall). The cationic diallyl quaternary ammonium salt / acrylamide copolymer has the following general formula:
Those represented by (16) or (17) are preferred.

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In the formulas (16) and (17), R ⁴⁹ and R ⁵⁰ are the same or different, and represent hydrogen, an alkyl group (having 1 to 18 carbon atoms), a phenyl group, an aryl group, a hydroxyalkyl group, an amidoalkyl. Group, cyanoalkyl group, alkoxyalkyl group or carboalkoxyalkyl group, R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴
Are the same or different, hydrogen, a lower alkyl group (having 1 to 3 carbon atoms) or a phenyl group, X ₄ is an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, nitric acid, etc.), d is E is an integer of 0 to 50, r is 150
Indicates an integer of ~ 8000. The molecular weight of the diallyl quaternary ammonium salt / acrylamide copolymer used in the present invention is preferably about 30,000 to 2,000,000, more preferably 100,000 to 100,000.
The range is one million. As the quaternized polyvinylpyrrolidone derivative, a compound represented by the following formula (18) is preferable.

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In the formula (18), R ⁵⁵ is a hydrogen atom or a group having 1 to 1 carbon atoms.
3 alkyl groups, R ⁵⁶ , R ⁵⁷ , and R ⁵⁸ are the same or different, and include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, an amidoalkyl group, a cyanoalkyl group,
An alkoxyalkyl group or a carboalkoxyalkyl group, Y ₁ is an oxygen atom or an NH group in an amide bond, and X ₅ is an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, having 1 to 1 carbon atoms)
4, alkyl sulfuric acid, phosphoric acid, nitric acid, etc.), u represents an integer of 1 to 10, and v + w = an integer of 20 to 8000. The molecular weight of the quaternized polyvinylpyrrolidone derivative used in the present invention is preferably 10,000 to 2,000,000, and more preferably 50,000 to 1.5,000,000.

The above cationic polymers can be used alone or in combination of two or more, and are preferably 0.01 to 3% by weight, more preferably 0.1 to 0.8% by weight in the detergent composition of the present invention. Be blended.

Examples of the anionic surfactant used in the present invention include alkyl sulfate, alkyl ether sulfate, alkyl sulfonate, sulfosuccinate and the like. Examples of the nonionic surfactant used in the present invention include an alkyl glycoside represented by the following formula (19), an amine oxide, an oxyalkylene alkyl ether, a monoglyceride, a mono- and diacanolamide.

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(In the formula (19), R ⁵⁹ represents a linear or branched alkyl, alkenyl or alkylphenyl group having 8 to 18 carbon atoms, and G represents a reducing sugar residue having 5 to 6 carbon atoms. Show,
x shows the number of 0-20, y shows the number of 1-10. Examples of the amphoteric activator used in the present invention include long-chain alkyldimethylcarboxymethylbetaine. The humectant used in the present invention includes glycerin, propylene glycol, ethylene glycol and the like.

[0095]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Sodium N-dodecyl- 1 -sulfoxyacetamide
Synthesis _{nC 12 H 25 NHCOCH 2 OSO 3} Na (1) N- 500 ml of capacity equipped with a synthetic stirrer and thermometer dodecyl glycolic acid amide 4-necked flask dodecylamine 181.4g (1.0mol), glycolic acid 104.1 g (1.0 mol) of ethyl and 7.5 g (40 mmol) of a methanol solution of 28% sodium methylate were charged, stirred under a stream of nitrogen, and heated to 100 ° C. The mixture was stirred for 2 hours while distilling off methanol generated at this temperature. The obtained reaction mixture was dissolved in 500 ml of ether, transferred to a separating funnel, and washed with water. The ether phase was separated and concentrated, and the remaining solid was dried under reduced pressure to obtain 182.3 g of N-dodecyl glycolamide white powder (yield: 74.9%). Its hydroxyl value was 229.4 (theoretical 230.5).
The infrared absorption spectrum and the ¹ H-NMR spectrum were as follows.

Infrared absorption spectrum (KBr tablet method) 3334 (OH stretching), 3262 (NH stretching), 2920, 2854 (CH stretching),
1638 (C = 0 stretching) cm ^{-1 1} H-NMR spectrum (δ, ppm) in _{CDCl 3 a: 0.89ppm (t,} 3H) b: 1.30ppm (m, 18H) c: 1.55ppm (m, 2H) d: 3.27 ppm (q, 2H) e: 7.02 ppm (b, 1H) f: 4.02 ppm (s, 2H) g: 5.10 ppm (b, 1H)

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(2) Synthesis of sodium N-dodecyl-1-sulfoxyacetamide 35.5 g of N-dodecylglycolic acid amide synthesized in (1)
(146 mmol) was placed in a 500 ml four-necked flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer, and dissolved in 350 ml of chloroform. Chlorosulfonic acid (17.9 g, 153 mmol) was added dropwise in about 30 minutes while stirring at room temperature under nitrogen aeration. At this time, the mixture was sometimes cooled with a water bath so that the reaction temperature did not exceed 40 ° C. After completion of the dropwise addition, the mixture was stirred at 30 ° C. for 2 hours. N-butanol containing 150 g of ice water
After pouring into 500 ml, transferring to a separatory funnel and shaking vigorously, the organic phase was separated. The organic phase was neutralized with a 10% aqueous solution of sodium hydroxide, and the solvent was distilled off under reduced pressure and dried. In this way, 39.8 g of a white powder of sodium N-dodecyl-1-sulfoxyacetamide was obtained (yield: 78.9%). Infrared absorption spectrum, ¹ H-NMR spectrum and Ma
The ss spectrum was as follows.

Infrared absorption spectrum (KBr tablet method) 3346 (NH stretching), 2926, 2854 (CH stretching), 1659 (C = 0 stretching),
1251,1070 (S = 0 stretching) cm ^{-1 1} H-NMR spectrum (δ, ppm) in _{CDCl 3 a: 0.57ppm (t,} 3H) b: 0.97ppm (m, 18H) c: 1.21ppm (m, 2H) d: 2.90 ppm (t, 2H) e: 4.15 ppm (s, 2H)

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Mass spectrum (Fab ionization method) 368: (M + Na) ⁺ , 266: (M + H-SO ₃ ) ⁺ , 226: (M-OSO ₃ Na) ⁺ Example 2 N-dodecyl-1- Sulfoxyacetamide ammonium
Beam synthesis _{nC 12 H 25 NHCOCH 2 OSO 3} NH 4 in Example 1 (1) synthesized N- dodecyl glycolic acid amide 35.5 g (146 mmol) with a stirrer, a dropping funnel, 1 liter equipped with a cooling tube and a thermometer And dissolved in 500 ml of chloroform. Chlorosulfonic acid (17.9 g, 153 mmol) was added dropwise over about 40 minutes while stirring at room temperature under nitrogen. At this time, the mixture was sometimes cooled with a water bath so that the reaction temperature did not exceed 40 ° C. After dropping, 2 at 25-30 ° C
Stirred for hours. The reaction mixture was poured into 600 ml of n-butanol containing 300 g of ice water, transferred to a separating funnel and shaken vigorously, and the organic phase was separated. The organic phase was neutralized with 10% aqueous ammonia, and the solvent was distilled off under reduced pressure and dried. Thus, 41.4 g of white powder of N-dodecyl-1-sulfoxyacetamidoammonium was obtained (yield: 83.3%). The purity of the anionic surfactant was 97.7% as determined by the Epton method. The infrared absorption spectrum was as follows.

Infrared absorption spectrum (KBr tablet method) 3340 (NH stretching), 2925, 2855 (CH stretching), 1655 (C = 0 stretching),
1245,1071 (S = O stretching) cm ^-1 Example 3 N-dodecyl-N-methyl- ¹ -sulfoxyacetamide
Synthesis of dosodium nC ₁₂ H ₂₅ N (CH ₃ ) COCH ₂ OSO ₃ Na 42.7 g (21 1) of dodecylmethylamine was added to a 200 ml four-necked flask equipped with a stirrer, a condenser and a thermometer.
4 mmol), 22.5 g (216 mmol) of ethyl glycolate and 28%
2.1 g (0.7 mmol) of methanol solution of sodium methylate
, And stirred under a stream of nitrogen to raise the temperature to 80 ° C.
The mixture was stirred for 3 hours while methanol generated at this temperature was distilled off. The obtained reaction mixture was dissolved in 300 ml of ether, transferred to a separating funnel, and washed with water. The ether phase was separated and concentrated, and the remaining liquid was dried under reduced pressure.
-Dodecyl-N-methylglycolamide was obtained. This was put into a 500 ml four-necked flask equipped with a stirrer, a dropping funnel, a cooling tube and a thermometer, and dissolved in 300 ml of chloroform. Chlorsulfonic acid (26.2 g, 225 mmol) was added dropwise in about 30 minutes while stirring at room temperature under nitrogen aeration. At this time, make sure that the reaction temperature does not exceed 30 ° C.
Sometimes cooled in a water bath. After completion of the dropwise addition, the mixture was stirred at 25 to 30 ° C for 1 hour. N-Butanol containing 200 g of ice water was added to the reaction mixture.
Pour into 00 ml, transfer to a separating funnel and shake vigorously,
The organic phase was separated. The organic phase was neutralized with a 10% aqueous solution of sodium hydroxide, and the solvent was distilled off under reduced pressure and dried. Thus, 34.0 g of a white powder of sodium N-dodecyl-N-methyl-1-sulfoxyacetamide was obtained (yield: 4).
4.1%). The purity of the anionic surfactant was 99.4% as determined by the Epton method. The infrared absorption spectrum, ¹ H-NMR spectrum and Mass spectrum were as follows.

Infrared absorption spectrum (KBr tablet method) 2926,2854 (CH stretching), 1665,1647 (C = 0 stretching), 1263,122
4,1035 (S = 0 stretching) cm ^{-1 1} H-NMR spectrum (δ, ppm) in _{CDCl 3 a: 0.59ppm (t,} 3H) b: 1.00ppm (m, 18H) c: 1.22ppm (m, 2H) d: 3.01 ppm (m, 2H) e: 2.60 ppm (s, 1.4H), 2.69 (s, 1.6H) f: 4.39 ppm (s, 2H)

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Mass spectrum (Fab ionization method) 382: (M + Na) ⁺ 280: (M + H-SO ₃ ) ⁺ 240: (M-OSO ₃ Na) ⁺ Example 4 N-dodecyl-5-sulfoxy Hexanoamide sodium
(1) Synthesis of N-dodecyl-5-hydroxyhexanamide Charge 384.20 g (2.0727 mol) of dodecylamine into a 2-liter four-necked flask equipped with a stirrer, dropping funnel, and thermometer, and heat to 90 ° C. did. Thereafter, ε-caprolactone 23
6.58 g (2.0727 mol) was added dropwise over about 0.5 hour. Meanwhile, the temperature in the system was kept between 90 ° C and 100 ° C. The reaction mixture was further stirred at 100 ° C. for 5 hours. The obtained crude product was dissolved in 2.1 liter of hexane and crystallized to obtain 509.53 g of N-dodecyl-5-hydroxyhexaneamide (82% yield). Its hydroxyl value is 182.
0 (theoretical value: 187.33), and the infrared absorption spectrum was as follows.

Infrared absorption spectrum (KBr tablet method) 3316 (OH stretching), 2926, 2854 (CH stretching), 1635 (C = O stretching) c
m ^-1 (2) Synthesis of sodium N-dodecyl-5-sulfoxyhexanamide 460.26 g (1.5368 mol) of N-dodecyl-5-hydroxyhexanamide obtained in (1) was stirred with a stirrer, a dropping funnel, a condenser, A 5 liter round bottom flask equipped with a thermometer was charged and dissolved in 2 liters of chloroform. 189 g of chlorosulfonic acid with stirring at room temperature under nitrogen aeration
(1.62 mol) was added dropwise in about 1 hour. During this time, the temperature in the system
It was kept at 10 ° C to 20 ° C. Thereafter, stirring was performed at room temperature for 1 hour. The reaction mixture was poured into 1 liter of n-butanol solution containing 300 ml of ice water, stirred for about 10 minutes, and the organic layer was extracted with a separating funnel. The organic layer was neutralized with a 30% aqueous NaOH solution to adjust the pH to 7. Butanol and chloroform were distilled off under reduced pressure, and the remaining solid was recrystallized from 2 liters of acetone to obtain 575.06 g of sodium N-dodecyl-5-sulfoxyhexanamide (93% yield). The infrared absorption spectrum, ¹ H-NMR spectrum and Mass spectrum of the obtained compound were as follows.

Infrared absorption spectrum (KBr tablet method) 3338 (NH stretching), 2925, 2855 (CH stretching), 1640 (C = O stretching), 1
200,1069 (S = O stretching) cm ^{-1 1} H-NMR spectrum (δ, ppm) D ₂ O in a: 0.93ppm (t, 3H) b: 1.40ppm (b, 18H) c: 1.50ppm (m , 2H) d: 3.18ppm (t, 2H) e: 2.30ppm (t, 2H) f: 1.68ppm (m, 6H) g: 4.09ppm (t, 2H)

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Mass spectrum (Fab ionization method) 424: (M + Na) ⁺ 322: (M + H-SO ₃ ) ⁺ 282: (M-OSO ₃ Na) ⁺ Example 5 N-dodecyl-5-sulfoxy Hexanamide ammonium
Um Synthesis Example 4 (1) synthesized N- dodecyl-5-hydroxyhexanamide 600.0 g (2.0 mol) with a stirrer, a dropping funnel, 4-necked 5-liter capacity equipped with a cooling tube and a thermometer The mixture was placed in a flask and dissolved in 2 liters of chloroform. Chlorosulfonic acid (270.4 g, 2.5 mol) was added dropwise over about 1 hour while stirring at room temperature under a stream of nitrogen. At this time, the mixture was sometimes cooled with a water bath so that the reaction temperature did not exceed 40 ° C. After completion of the dropwise addition, the mixture was stirred at 25 to 30 ° C for 2 hours. The reaction mixture was poured into 2 liters of n-butanol solution containing 1 kg of ice water, transferred to a separating funnel and shaken vigorously, and the organic phase was separated. The organic phase was neutralized with a 10% aqueous ammonia solution, and the solvent was distilled off under reduced pressure and dried. In this way, 713.2 g of white powder of N-dodecyl-5-sulfoxyhexanamidammonium was obtained (yield 90.0%). The purity of the anionic surfactant was 99.9% as determined by the Epton method. The infrared absorption spectrum was as follows.

Infrared absorption spectrum (KBr tablet method) 3334,3214 (NH stretching), 2926,2854 (CH stretching), 1641 (C = 0)
Stretch), 1209, 1065, 1044 (S = O Stretch) cm ^-1 Example 6 of sodium N-decyl-3 -sulfoxybutyroamide
Synthesis (1) Synthesis of N-decyl-3-hydroxybutyroamide 535.7 g (3.41 mol) of n-decylamine was charged into a 2 liter round bottom flask equipped with a stirrer, a dropping funnel, and a thermometer, and then subjected to nitrogen bubbling. The temperature was raised to 80 ° C. while stirring.
293.2 g (3.41 mol) of γ-butyrolactone was charged from the dropping funnel in about 1 hour. At this time, the reaction temperature is about
The temperature rose to 100 ° C. The reaction mixture was further stirred at 100 ° C. for 5 hours. The obtained crude product was dissolved in 3 liters of hexane and recrystallized to obtain 767.9 g of N-decyl-3-hydroxybutyroamide (yield: 89.2).
%). Its hydroxyl value was 228.6 (theoretical value: 230.5), and its infrared absorption spectrum and ¹ H-NMR spectrum were as follows.

Infrared absorption spectrum (KBr tablet method) 3304 (OH stretching), 3104 (NH stretching), 2924, 2856 (CH stretching), 1
642 (C = O stretching) cm ^{-1 1} H-NMR spectrum (δ, ppm) in _{CDCl 3 a: 0.72ppm (t,} 3H) b: 1.12ppm (m, 14H) c: 1.33ppm (m, 2H) d: 3.05 ppm (q, 2H) e: 6.10 ppm (b, 1H) f: 2.18 ppm (t, 2H) g: 1.70 ppm (m, 2H) h: 3.50 ppm (t, 2H) i: 3.64 ppm ( b, 1H)

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(2) Synthesis of sodium N-decyl-3-sulfoxybutyroamide 750.9 g (2.97 mol) of N-decyl-3-hydroxybutyroamide synthesized in (1) was stirred with a stirrer, a dropping funnel and a condenser. Was charged into a 5 liter round bottom flask equipped with a thermometer and dissolved in 3 liters of chloroform. 363.5 g of chlorosulfonic acid with stirring at room temperature under nitrogen aeration
(3.12 mol) was added dropwise in about 4 hours. At this time, the reaction temperature is 40
Cooled in a water bath so as not to exceed ° C. Then, at 20 ° C, 2
Stirring was continued for hours. The reaction mixture was mixed with n-
The mixture was poured into 3 liters of butanol, stirred for about 10 minutes, and the organic layer was extracted with a separating funnel. The organic layer was neutralized with 20% NaOH to adjust the pH to 7. Butanol and chloroform were distilled off under reduced pressure, and the remaining solid was recrystallized from 3 liters of ethanol to obtain 843.4 g of sodium N-decyl-3-sulfoxybutyroamide (yield: 82.2%). The infrared absorption spectrum, ¹ H-NMR spectrum and Mass spectrum of the obtained compound were as follows.

Infrared absorption spectrum (KBr tablet method) 3340 (NH stretching), 2926, 2854 (CH stretching), 1638 (C = O stretching), 1
206,1071 (S = O stretching) cm ^{-1 1} H-NMR spectrum (δ, ppm) D ₂ O in a: 0.88ppm (t, 3H) b: 1.30ppm (m, 14H) c: 1.50ppm (m , 2H) d: 3.20 ppm (t, 2H) e: 2.37 ppm (t, 2H) f: 1.96 ppm (m, 2H) g: 4.10 ppm (t, 2H)

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Mass spectrum (Fab ionization method) 368: (M + Na) ⁺ 266: (M + H-SO ₃ ) ⁺ 226: (M-OSO ₃ Na) ⁺ Example 7 N-tetradecyl-3-sulfoxy Butyroamide
(1) Synthesis of N-tetradecyl-3-hydroxybutyroamide 508.19 g (2.3813 mol) of tetradecylamine was charged into a two-liter four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, and heated at 90 ° C. Until heated. Thereafter, 208.4 g (2.421 mol) of γ-butyrolactone was added dropwise over about 0.5 hour. Meanwhile, the temperature in the system was kept between 90 ° C and 100 ° C. The reaction mixture was further stirred at 100 ° C. for 4 hours. The obtained crude product was dissolved in 2.5 liters of hexane and recrystallized to obtain 668.98 g of N-tetradecyl-3-hydroxybutyroamide (yield 94%). The hydroxyl value of this product is
190.7 (theoretical 187.33), and the infrared absorption spectrum was as follows.

Infrared absorption spectrum (KBr tablet method) 3300 (OH stretching), 3100 (NH stretching), 2920, 2855 (CH stretching), 1
642 (C = O stretching) cm ^-1 (2) Synthesis of sodium N-tetradecyl-3-sulfoxybutyroamide 401.54 g (1.3407 mol) of N-tetradecyl-3-hydroxybutyroamide obtained in (1) Was charged into a 5 liter round bottom flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer, and dissolved in 1.8 liter of chloroform. Chlorsulfonic acid 17 with stirring at room temperature under nitrogen aeration
2.5 g (1.480 mol) was added dropwise in about 1 hour. During this time, the temperature in the system was kept at 10 to 20 ° C. Thereafter, stirring was performed at room temperature for 3 hours. The reaction mixture was mixed with 1000 g of ice water and n-butanol 1
The mixture was poured into 1 liter of the mixture, stirred for about 10 minutes, and the organic layer was extracted with a separating funnel. The organic layer was neutralized with a 30% aqueous NaOH solution to adjust the pH to 7. Butanol and chloroform were distilled off under reduced pressure, and the remaining solid was recrystallized from 4 liters of acetone to obtain 511.43 g (95% yield) of sodium N-tetradecyl-3-sulfoxybutyroamide. The infrared absorption spectrum, ¹ H-NMR spectrum and Mass spectrum of the obtained compound were as follows.

Infrared absorption spectrum (KBr tablet method) 3344 (NH stretching), 2925, 2854 (CH stretching), 1635 (C = O stretching), 1
206,1070 (S = O stretching) cm ^{-1 1} H-NMR spectrum (δ, ppm) D ₂ O in a: 0.89ppm (t, 3H) b: 1.30ppm (b, 22H) c: 1.52ppm (m , 2H) d: 3.18ppm (t, 2H) e: 2.38ppm (t, 2H) f: 1.98ppm (m, 2H) g: 4.10ppm (t, 2H)

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Mass spectrum (Fab ionization method) 424: (M + Na) ⁺ 322: (M + H-SO ₃ ) ⁺ 282: (M-OSO ₃ Na) ⁺ Example 8 N-cocoyl-3-sulfoxy Butyramide ammonium
(1) Synthesis of N-cocoyl-3-hydroxybutyroamide Cocoamine alkylamine (Kamin Co., Ltd .: Farmin CS: average) was placed in a 2-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer. Molecular weight: 196.04) 777.36 g (3.9653 mol)
And heated to 90 ° C. Thereafter, 341.39 g (3.9655 mol) of γ-butyrolactone was added dropwise over about 1 hour. Meanwhile, the temperature in the system was kept between 90 ° C and 100 ° C. The reaction mixture was further stirred at 100 ° C. for 3 hours. The obtained crude product was dissolved in 4 liters of hexane and crystallized to obtain 1078.4 g of N-cocoyl-3-hydroxybutyroamide (yield: 96%). Its hydroxyl value is 202.
9 (theoretical 198.86).

(2) Synthesis of N-cocoyl-3-sulfoxybutyroamidoammonium 463.38 g (1.643 mol) of N-cocoyl-3-hydroxybutyroamide obtained in (1) was stirred with a stirrer, a dropping funnel, and cooled. A 5-liter round bottom flask equipped with a tube and a thermometer was charged and dissolved in 2 liters of chloroform. Chlorosulfonic acid 202.0 g with stirring at room temperature under nitrogen aeration
(1.734 mol) was added dropwise in about 1.5 hours. During this time, the temperature in the system was kept at 10 to 20 ° C. Thereafter, stirring was performed at room temperature for 2 hours. The reaction mixture was poured into a mixture of 1000 g of ice water and 1 liter of n-butanol, stirred for about 10 minutes, and the organic layer was extracted with a separating funnel. This organic layer was neutralized with 25% aqueous ammonia to adjust the pH to 7. Butanol and chloroform were distilled off under reduced pressure, and the remaining solid was recrystallized from 4 liters of acetone to obtain 591.91 g (95% yield) of N-cocoyl-3-sulfoxybutyroamidoammonium. The infrared absorption spectrum of the obtained compound was as follows.

Infrared absorption spectrum (KBr tablet method) 3260 (NH stretching), 2926, 2855 (CH stretching), 1634 (C = O stretching), 1
210,1085 (S = O stretch) cm ^-1 Example 9 N-dodecyl-2-methyl-4 -sulfoxypentanathan
216.6 g (1.17 m) of dodecylamine was added to a 2 liter round bottom flask equipped with a synthetic sodium stirrer, a dropping funnel, a condenser, and a thermometer.
ol) and heated to 90 ° C. under a stream of nitrogen. Next, 2-
133.4 g (1.17 mol) of methyl-δ-valerolactone was charged from the dropping funnel with stirring for about 1 hour. At this time, the reaction temperature rose to about 100 ° C. due to exotherm. The reaction mixture was further stirred at 100 ° C. for 5 hours. Subsequently, a sulfation reaction was performed without isolating the alkanolamide. That is, after the reaction product was cooled to room temperature, 1000 g of methylene chloride was charged and dissolved. At room temperature, 143.0 g (1.23 mol) of chlorosulfonic acid was added dropwise in about 1 hour. After completion of the dropwise addition, the mixture was stirred at 30 ° C. for about 2 hours, and poured into a mixture of 500 g of ice water and 500 ml of butanol. Shake vigorously with a separatory funnel, neutralize the organic layer with a 30% aqueous NaOH solution, and adjust the pH to 7.2.
Was prepared. After evaporating the solvent and water under reduced pressure, the residue was recrystallized in ethanol to obtain 417.4 g of sodium N-dodecyl-2-methyl-4-sulfoxypentanamide (yield).
88.7%). Infrared absorption spectrum of the obtained compound and
^{The 1} H-NMR spectrum was as follows.

Infrared absorption spectrum (KBr tablet method) 3262 (NH stretching), 2926, 2854 (CH stretching), 1635 (C = O stretching), 1
209,1083 (S = O stretching) cm ^{- 11} H-NMR spectrum (δ, ppm) a, i in D ₂ O : 0.60 ppm (m, 6H) b: 0.93 ppm (m, 18H) c: 1.33 ppm (m, 2H) d, f: 2.90 ppm (m, 3H) e: 2.03 ppm (d, 2H) g: 1.74 ppm (m, 2H) h: 3.78 ppm (t, 2H)

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Example 10 N-octyl-4-sulfoxypentanamide sodium
(1) Synthesis of N-octyl-4-hydroxypentanamide In a 100 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 34.14 g (0.8641 mol) of octylamine was charged.
Heated to 90 ° C. Thereafter, 26.46 g of δ-valerolactone
(0.2643 mol) was added dropwise over about 10 minutes. Meanwhile, the temperature in the system was kept between 90 ° C and 100 ° C. The reaction mixture
The mixture was stirred at 100 ° C for 4 hours. The obtained crude product is treated with hexane
It was dissolved in 400 ml and crystallized to obtain 46.58 g of N-octyl-4-hydroxypentanamide (yield 77%). The infrared absorption spectrum of the obtained compound was as follows.

Infrared absorption spectrum (KBr tablet method) 3320 (OH stretching), 2922, 2856 (CH stretching), 1636 (C = O stretching) c
m- ¹ (2) Synthesis of sodium N-octyl-4-sulfoxypentanamide 40.29 g (0.1757 mol) of N-octyl-4-hydroxypentanamide obtained in (1) was stirred with a stirrer, a dropping funnel, a condenser, A 300 ml round bottom flask equipped with a thermometer was charged and dissolved in 160 ml of chloroform. Chlorosulfonic acid 22.5 g (0.193 mol) with stirring at room temperature under nitrogen aeration
It was dropped in 20 minutes. During this time, the temperature in the system was kept at 10 to 20 ° C. Thereafter, stirring was performed at room temperature for 1 hour. The reaction mixture was poured into a mixture of 150 g of ice water and 70 ml of n-butanol, stirred for about 10 minutes, and the organic layer was extracted with a separating funnel.
Then, the organic layer was neutralized with a 30% aqueous solution of NaOH to adjust the pH to 7%.
Was prepared. Butanol and chloroform were distilled off under reduced pressure, and the remaining solid was recrystallized from 200 ml of acetone to give 44.8% sodium N-octyl-4-sulfoxypentanamide.
4 g (77% yield) were obtained. The infrared absorption spectrum, ¹ H-NMR spectrum and Mass spectrum of the obtained compound were as follows.

Infrared absorption spectrum (KBr tablet method) 3345 (NH stretching), 2926, 2855 (CH stretching), 1640 (C = O stretching), 1
200,1077 (S = O stretching) cm ^{-1 1} H-NMR spectrum (δ, ppm) D ₂ O in a: 0.95ppm (t, 3H) b: 1.28ppm (b, 10H) c: 1.53ppm (m , 2H) d: 3.18 ppm (t, 2H) e: 2.30 ppm (t, 2H) f: 1.75 ppm (m, 4H) g: 4.10 ppm (t, 2H)

[0129]

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Mass spectrum (Fab ionization method) 354: (M + Na) ⁺ 252: (M + H-SO ₃ ) ⁺ 212: (M-OSO ₃ Na) ⁺ Example 11 N-dodecyl-4-sulfoxy Pentanamide sodium
(1) Synthesis of N-dodecyl-4-hydroxypentanamide In a 100 ml four-necked flask equipped with a stirrer, dropping funnel and thermometer, 49.77 g (0.2685 mol) of dodecylamine was charged and heated to 90 ° C. did. Then, δ-valerolactone
26.89 g (0.2686 mol) was added dropwise over about 15 minutes. Meanwhile, the temperature in the system was kept between 90 ° C and 100 ° C. The reaction mixture was further stirred at 100 ° C. for 3 hours. The obtained crude product was dissolved in 400 ml of hexane and recrystallized to obtain 57.
95 g of N-dodecyl-4-hydroxypentanamide was obtained (76% yield). Its hydroxyl value is 183.1 (theoretical value
196.54), and the infrared absorption spectrum was as follows.

Infrared absorption spectrum (KBr tablet method) 3332 (OH stretching), 2924, 2856 (CH stretching), 1636 (C = O stretching) c
m ^-1 (2) Synthesis of sodium N-dodecyl-4-sulfoxypentanamide 50.21 g (0.1759 mol) of N-dodecyl-4-hydroxypentanamide obtained in (1) was stirred with a stirrer, a dropping funnel, a condenser, A 500 ml round bottom flask equipped with a thermometer was charged and dissolved in 200 ml of chloroform. Chlorosulfonic acid (21.6 g, 0.185 mol) was added dropwise with stirring under a nitrogen atmosphere at room temperature over about 20 minutes. During this time, the temperature in the system should be between 10 ° C and 20 ° C
Kept. Thereafter, stirring was performed at room temperature for 2 hours. The reaction mixture was poured into a mixture of 100 g of ice water and 100 ml of n-butanol, stirred for about 10 minutes, and the organic layer was extracted with a separating funnel. The organic layer was neutralized with a 30% aqueous NaOH solution to adjust the pH to 7. Butanol and chloroform were distilled off under reduced pressure.
The remaining solid was recrystallized from 500 ml of acetone to obtain 51.57 g of sodium N-dodecyl-4-sulfoxypentanamide.
(76% yield). The infrared absorption spectrum, ¹ H-NMR spectrum and Mass spectrum of the obtained compound were as follows.

[0132] Infrared absorption spectrum (KBr tablet method) 3346 (NH stretch), 2926,2854 (CH stretching), 1641 (C = O stretch), 1197,1077 (S = O stretching) cm ^{-1 1} H-NMR spectrum (Δ, ppm) in D ₂ O a: 0.65 ppm (t, 3H) b: 1.05 ppm (b, 18H) c: 1.28 ppm (m, 2H) d: 2.89 ppm (t, 2H) e: 2.10 ppm ( (t, 2H) f: 1.49 ppm (m, 4H) g: 3.75 ppm (t, 2H)

[0133]

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Mass spectrum (Fab ionization method) 410: (M + Na) ⁺ 308: (M + H-SO ₃ ) ⁺ 268: (M-OSO ₃ Na) ⁺ Example 12 N-decyl-5-sulfoxy Sodium hexanamide
(1) Synthesis of N-decyl-5-hydroxyhexanamide 362.56 g (2.3049 mol) of decylamine was charged into a 1-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer, and heated to 90 ° C. Thereafter, ε-caprolactone 26
3.08 g (2.3049 mol) was added dropwise over about 30 minutes. Meanwhile, the temperature was kept between 90 ° C and 100 ° C. The reaction mixture
The mixture was stirred at 100 ° C for 5 hours. The obtained crude product was dissolved in 2 liters of hexane and crystallized to give 528.69.
g of N-decyl-5-hydroxyhexaneamide was obtained (yield 85%). Its hydroxyl value is 181.6 (theory 206.
70), and the infrared absorption spectrum was as follows.

Infrared absorption spectrum (KBr tablet method) 3321 (OH stretching), 2926, 2855 (CH stretching), 1635 (C = O stretching) c
m ^-1 (2) Synthesis of sodium N-decyl-5-sulfoxyhexanamide 467.58 g (1.7226 mol) of N-decyl-5-hydroxyhexanamide obtained in (1) was stirred, a dropping funnel, a condenser, A 5 liter round bottom flask equipped with a thermometer was charged and dissolved in 2 liters of chloroform. Chlorosulfonic acid 210.9 g while stirring under nitrogen aeration at room temperature
(1.810 mol) was added dropwise in about 1.5 hours. During this time, the temperature in the system was kept at 10 to 20 ° C. Thereafter, stirring was performed at room temperature for 2 hours. 1000 g of ice water and n-butanol 5
The mixture was poured into 00 ml of the mixture, stirred for about 10 minutes, and the organic layer was extracted with a separating funnel. The organic layer was neutralized with a 30% aqueous NaOH solution to adjust the pH to 7. Butanol and chloroform were distilled off under reduced pressure, and the remaining solid was recrystallized from 4 liters of acetone to obtain 521.16 g (81% yield) of sodium N-decyl-5-sulfoxyhexanamide. The infrared absorption spectrum, ¹ H-NMR spectrum and Mass spectrum of the obtained compound were as follows.

Infrared absorption spectrum (KBr tablet method) 3316 (NH stretching), 2926, 2854 (CH stretching), 1635 (C = O stretching), 1
206,1071 (S = O stretching) cm ^{-1 1} H-NMR spectrum (δ, ppm) D ₂ O in a: 0.92ppm (t, 3H) b: 1.38ppm (b, 14H) c: 1.50ppm (m , 2H) d: 3.19ppm (t, 2H) e: 2.29ppm (t, 2H) f: 1.71ppm (m, 6H) g: 4.07ppm (t, 2H)

[0137]

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Mass spectrum (Fab ionization method) 396: (M + Na) ⁺ 294: (M + H-SO ₃ ) ⁺ 254: (M-OSO ₃ Na) ⁺ Example 13 N-dodecyl-2-sulfoxy Propionamide sodium
(1) Synthesis of N-dodecyl-2-hydroxypropionamide In a 200 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 25.34 g (0.1367 mol) of dodecylamine and 30 g of dioxane were charged, and a transparent solution was prepared. And Thereafter, 9.85 g (0.1367 mol) of β-propiolactone was added dropwise over about 15 minutes.
Meanwhile, the temperature in the system was kept between 25 ° C and 30 ° C. The reaction mixture was further stirred at 30 ° C. for 5 hours. By pouring the obtained crude product into 100 ml of hexane and crystallizing,
28.93 g of N-dodecyl-2-hydroxypropionamide was obtained (82% yield). The infrared absorption spectrum and ¹ H-NMR spectrum of the obtained compound were as follows.

Infrared absorption spectrum (KBr tablet method) 3298 (OH stretching), 2926, 2854 (CH stretching), 1644 (C = O stretching) c
m ^{-1 1} H-NMR spectrum (δ, ppm) in _{CDCl 3 a: 0.82ppm (t,} 3H) b: 1.35ppm (b, 18H) c: 1.47ppm (m, 2H) d: 3.11ppm (q, 2H) e: 6.20 ppm (b, 2H) f: 2.30 ppm (t, 2H) g: 3.79 ppm (t, 2H) h: 5.00 ppm (b, 1H)

[0140]

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(2) Synthesis of sodium N-dodecyl-2-sulfoxypropionamide 15.34 g (0.05959 mol) of N-dodecyl-2-hydroxypropionamide obtained in (1) was added to a stirrer, a dropping funnel, a cooling tube, It was charged into a 100 ml round bottom flask equipped with a thermometer and dissolved in 100 ml of chloroform. Under nitrogen aeration,
At room temperature, with stirring, 7.67 g of chlorosulfonic acid (0.0658
mol) was added dropwise over about 10 minutes. During this time, the temperature in the system was kept at 10 to 20 ° C. Thereafter, stirring was performed at room temperature for 1 hour.
The reaction mixture was poured into 50 ml of n-butanol containing 50 g of ice water, stirred for about 10 minutes, and the organic layer was extracted with a separating funnel.
The organic layer was neutralized with a 20% aqueous NaOH solution to adjust the pH to 7. Butanol and chloroform were distilled off under reduced pressure, and the remaining solid was recrystallized from 100 ml of acetone to give N-dodecyl-
19.32 g of sodium 2-sulfoxypropionamide
(90% yield). The infrared absorption spectrum, ¹ H-NMR spectrum and Mass spectrum of the obtained compound were as follows.

Infrared absorption spectrum (KBr tablet method) 3272 (NH stretching), 2928, 2856 (CH stretching), 1636 (C = O stretching), 1
208,1084 (S = O stretching) cm ^{-1 1} H-NMR spectrum (δ, ppm) D ₂ O in a: 0.89ppm (t, 3H) b: 1.35ppm (b, 18H) c: 1.58ppm (m , 2H) d: 3.20ppm (t, 2H) e: 2.65ppm (t, 2H) f: 4.27ppm (t, 2H)

[0143]

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Mass spectrum (Fab ionization method) 382: (M + Na) ⁺ 280: (M + H-SO ₃ ) ⁺ 240: (M-OSO ₃ Na) ⁺ Example 14 N-dodecyl-2-methyl- 4-sulfoxypentana
Synthesis stirrer bromide potassium, dropping funnel, cooling tube, dodecylamine 150.0g round bottom flask of 1 liter equipped with a thermometer (0.81 m
ol) and heated to 90 ° C. under a stream of nitrogen. Next, 2-
92.4 g (0.81 mol) of methyl-δ-valerolactone was charged from the dropping funnel with stirring for about 1 hour. At this time, the reaction temperature rose to about 100 ° C. due to exotherm. The reaction mixture was further stirred at 100 ° C. for 5 hours. Subsequently, a sulfation reaction was performed without isolating the alkanolamide.
That is, after the reaction product was cooled to room temperature, 500 g of methylene chloride was charged and dissolved. At room temperature, 99.0 g (0.85 mol) of chlorosulfonic acid was added dropwise in about 1 hour. After dropping, the mixture was stirred at 30 ° C for about 2 hours, and 500 g of ice water and butanol were added.
Poured into 500 ml of the mixture. The mixture was vigorously shaken with a separating funnel, and the organic layer was neutralized with a 30% aqueous KOH solution to adjust the pH to 7.0. After evaporating the solvent and water under reduced pressure, the residue was recrystallized in ethanol to obtain 308.6 g of sodium N-dodecyl-2-methyl-4-sulfoxypentanamide (yield 91.0).
%). Infrared absorption spectrum and ¹ H of the obtained compound
-The NMR spectrum was as follows.

Infrared absorption spectrum (KBr tablet method) 3262 (NH stretching), 2926, 2854 (CH stretching), 1635 (C = O stretching), 1
210,1085 (S = O stretching) cm ^{-1 1} H-NMR spectrum (δ, ppm) D ₂ O in a, i: 0.60ppm (m, 6H) b: 0.93ppm (m, 18H) c: 1.33ppm (m, 2H) d, f: 2.90 ppm (m, 3H) e: 2.03 ppm (d, 2H) g: 1.74 ppm (m, 2H) h: 3.78 ppm (t, 2H)

[0146]

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Example 15 N-decyl-sulfoxypolyoxyethylene (EO = 5)
Synthesis of sodium loamido 252.8 g (1.0 mol) of N-decyl-3-hydroxybutyroamide synthesized in (1) of Example 6 and 2 g of sodium methylate were subjected to a closed reaction equipped with a stirrer, thermometer, and dropping funnel. After charging into a container and purging with nitrogen, the temperature was raised to 100 ° C. Charge 220.0 g (5.0 mol) of ethylene oxide, 100 ℃
For 5 hours. Next, the mixture was cooled to room temperature, and 116.5 g (1.0 mol) of chlorosulfonic acid was charged in 2 hours. The reaction mixture was stirred at 30 ° C. for another hour and poured into 300 g of ice water. The solution was neutralized with a 30% aqueous sodium hydroxide solution to adjust the pH to 7.0. The solvent and water were distilled off under reduced pressure, and 550 g of sodium N-decyl-sulfoxypolyoxyethylene (EO = 5) butyroamide to which 5 mol of ethylene oxide had been added (yield).
98.6%). The pure sulfate content of this product was measured by the Epton method and found to be 95.5%. The infrared absorption spectrum was as follows.

Infrared absorption spectrum (Nujol method) 3341 (NH stretching), 2925, 2855 (CH stretching), 1638 (C = O stretching), 1
207,1070 (S = O expansion / contraction) cm ^-1 Test Example 1 The foaming properties of the N-alkylamide alkanol sulfates of the present invention shown in Table 1 and comparative products were tested by the following method. Table 1 shows the results. <Foamability test method> Lanolin 0.3 in 40 ° C, 4 ° DH hard water
A solution in which 0.1% by weight of a surfactant and 0.1% by weight of a surfactant were added was stirred by an inverted stirring method, and the foam amount was measured 10 seconds and 120 seconds after the stirring was stopped.

[0149]

[Table 1]

Test Example 2 The N-alkylamide alkanol sulfates of the present invention shown in Table 2 and comparative products were tested for irritation to the skin by the following four times cumulative irritation test method. Table 2 shows the results. <Fourth Cumulative Irritation Test Method> An aqueous solution having a surfactant concentration of 10% by weight was applied four times to healthy skin of five guinea pigs, and the fourth reaction was evaluated according to the following criteria, and the average score was shown. Evaluation Criteria 0: No reaction observed 1 ... Faint erythema observed 2 ... Clear erythema observed 3 ... Clear erythema accompanied by edema 4 ... Clear erythema accompanied by necrosis or asphyxia

[0151]

[Table 2]

Examples of the formulation of the cleaning composition of the present invention are shown below. Formulation Example 1 A shampoo having the following composition was prepared. The obtained shampoo was excellent in foaming properties and detergency, and also had a good feel during hair washing and rinsing.

[0153]

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Lauroyldiethanolamide 3% by weight Lauryldimethylamine oxide 0.5 Hydroxyethylcellulose (SE-850K, manufactured by Daicel) 0.1 Sodium benzoate 0.3 Colorant Suitable amount Flavor Suitable amount Citric acid Suitable amount Purified water Total 100 pH 6.5 Prescription example 2 A shampoo having the following composition was prepared. The obtained shampoo was excellent in foaming properties and detergency, and also had a good feel during hair washing and rinsing.

[0155]

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Lauryl dimethylamine oxide 0.5% by weight Hydroxyethylcellulose (SE-850K, manufactured by Daicel) 0.1 Sodium benzoate 0.3 Colorant Suitable amount Perfume proper amount Citric acid proper amount Purified water Total 100 pH 6.5 Formulation Example 3 A shampoo having the following composition was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking.

[0157]

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Aminopropyl dimethyl dimethylaminoacetate betaine laurate 3% by weight Cationized cellulose (manufactured by Union Carbide, Polymer JR400) 0.5 Sodium benzoate 0.3 Colorant Suitable amount Flavor Suitable amount Citric acid Suitable amount Purified water All 100 Formulation Example 4 A shampoo having the following composition was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking.

[0159]

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Polyoxyethylene (3) lauryl sulfosuccinate 3% by weight cetyltrimethylammonium chloride 1 hydroxyethylcellulose (SE-850, manufactured by Daicel) 0.1 Cationic starch 0.3 (cationized corn starch, having a degree of cationization of 0.3) Benzo Sodium acid salt 0.3 pigment Suitable amount Fragrance suitable amount Citric acid proper amount Purified water Total 100 Formulation Example 5 A body shampoo having the following composition was prepared. The obtained body shampoo was excellent in foaming properties and detergency, and the feeling after washing was moist and good.

[0161]

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5% by weight of decyl polyglucoside (in the above formula (19), R ⁵⁹ = decyl group, G is a glucose residue, x = 0, y = 1.3) lauryl dimethylamine oxide 3 glycerin 4 sucrose fatty acid ester 1 Methylparaben 0.3 pigment Suitable amount Perfume proper amount Citric acid proper amount Purified water Total 100 Formulation Example 6 A shampoo having the following composition was prepared. The obtained shampoo was excellent in foaming properties and detergency, and also had a good feel during hair washing and rinsing.

[0163]

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Lauroyl diethanolamide 3% by weight Lauryl dimethylamine oxide 0.5 Hydroxyethylcellulose (SE-850K, manufactured by Daicel) 0.1 Sodium benzoate 0.3 Colorant Appropriate quantity Perfume Appropriate quantity Citric acid Appropriate quantity Purified water Total 100 pH 6.5 Prescription example 7 A shampoo having the following composition was prepared. The obtained shampoo was excellent in foaming properties and detergency, and also had a good feel during hair washing and rinsing.

[0165]

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Lauryl dimethylamine oxide 0.5% by weight Hydroxyethylcellulose (SE-850K, manufactured by Daicel) 0.1 Sodium benzoate 0.3 Colorant Suitable amount Perfume suitable amount Citric acid Suitable amount Purified water Total 100 pH 6.5 Formulation Example 8 The following composition Was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking.

[0167]

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Aminopropyl dimethyl dimethylaminoacetate laurate betaine 3% by weight Cationized cellulose (manufactured by Union Carbide Co., Ltd., polymer JR400) 0.5 Sodium benzoate 0.3 Colorant proper amount Flavor proper amount Citric acid proper amount Purified water 100 formulas Example 9 A shampoo having the following composition was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking.

[0169]

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Monolauryl phosphate 3% by weight Cetyltrimethylammonium chloride 1 Hydroxyethylcellulose (SE-850, manufactured by Daicel Corporation) 0.1 Cationic starch 0.3 (cationized corn starch, having a degree of cationization of 0.3) Sodium benzoate 0.3 Perfume appropriate amount Citric acid appropriate amount Purified water Total 100 Formulation Example 10 A body shampoo having the following composition was prepared. The obtained body shampoo was excellent in foaming properties and detergency, and the feeling after washing was moist and good.

[0171]

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Polyoxyethylene (3) lauryl glucoside 5% by weight lauryl dimethylamine oxide 3 glycerin 4 sucrose fatty acid ester 1 methyl paraben 0.3 pigment proper amount perfume proper amount citric acid proper amount purified water all 100 Formulation Example 11 The following composition Was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking. It also exhibited an excellent rinsing effect, and in particular, had good slipperiness during drying.

[0173]

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Lauryl polyglucoside 5% by weight (in the above general formula (19), R ⁵⁹ = lauryl group, G is a glucose residue, x = 0, y = 1.3) dimethylpolysiloxane (KF manufactured by Shin-Etsu Chemical Co., Ltd.) −96, viscosity 200 cs) 0.5 Polyoxyethylene sorbitan tristearate (160EO) 0.3 Sodium benzoate 0.3 Colorant Suitable amount Fragrance proper amount Citric acid proper amount Purified water Total 100 Formulation Example 12 Prepare a shampoo having the following composition did. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking. It also exhibited an excellent rinsing effect, and was excellent in slipperiness and flexibility during rinsing and drying.

[0175]

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Lauryl dimethylamine oxide 3% by weight Hydroxyethylcellulose (SE-850K manufactured by Daicel) 0.1 Cationized cellulose (manufactured by Union Carbide, polymer JR400) 0.3 Sodium benzoate 0.3 Colorant Appropriate perfume Appropriate citric acid Appropriate amount Purified water Total 100 Formulation Example 13 A shampoo having the following composition was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking. It also exhibited an excellent rinsing effect, and was excellent in slipperiness and flexibility during rinsing and drying.

[0177]

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Lauroyl diethanolamide 2% by weight Decanoic acid monoglyceride 3 Cationized cellulose (manufactured by Union Carbide, Polymer JR400) 0.3 Colorant Suitable amount Perfume Suitable amount Citric acid Suitable amount Purified water Total 100 Formulation Example 14 The following composition A shampoo was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking. It also exhibited an excellent rinsing effect, and was excellent in slipperiness and flexibility during rinsing and drying.

[0179]

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Polyoxyethylene (3) sodium lauryl ether sulfate 7% by weight lauroyl diethanolamide 3 cationized cellulose (manufactured by Union Carbide Co., Ltd., polymer JR400) 0.3 pigment proper amount perfume proper amount citric acid proper amount purified water all 100 formulations Example 15 A shampoo having the following composition was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking. It also exhibited an excellent rinsing effect, and was excellent in slipperiness and flexibility during rinsing and drying.

[0181]

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Polyoxyethylene (17) lauryl ether 3% by weight Laurylhydroxysulfobetaine 3 Cationic polymer (manufactured by Dow Corning Co., Ltd., MAQ-100) 0.3 Colorant Suitable amount Fragrance Suitable amount Citric acid Suitable amount Purified water Total 100 Formulation Example 16 A shampoo having the following composition was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking. It also exhibited an excellent rinsing effect, and was excellent in slipperiness and flexibility during rinsing and drying.

[0183]

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Lauroyl monoethanolamide 2% by weight Cationic starch 0.2 (cationized corn starch, having a cationization degree of 0.3) Pigment suitable amount Perfume proper amount Citric acid proper amount Purified water Total 100 Formulation Example 17 The following composition Was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking. It also exhibited an excellent rinsing effect, and was excellent in slipperiness and flexibility during rinsing and drying.

[0185]

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Polyoxyethylene (3) sodium lauryl ether sulfate 10% by weight lauroyl diethanolamide 2 dimethyl polysiloxane emulsion 4 (manufactured by Dow Corning Toray Silicone Co., Ltd., product name: SM8705) Sodium benzoate 0.5 flavor 0.4 pigment 0.0001 Purified water Total 100 Formulation Example 18 A shampoo having the following composition was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking. It also exhibited an excellent rinsing effect, and was excellent in slipperiness and flexibility during rinsing and drying.

[0187]

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Lauryl polyglucoside 5% by weight (in the above formula (19), R ⁵⁹ = lauryl group, G is a glucose residue, x = 0, y = 1.3) decanoic acid monoglyceride 2 propylene glycol 3 polyether-modified silicone 0.3 (Shin-Etsu Chemical Co., Ltd., Silicone KF-6005) Dimethyl polysiloxane emulsion 3 (Toshiba Silicone Co., Ltd., product name: XS65-A2773) Sodium benzoate 0.5 Flavor 0.4 Colorant 0.0001 Purified water All 100 Formulation examples 19 A shampoo having the following composition was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking. It also exhibited an excellent rinsing effect, and was excellent in slipperiness and flexibility during rinsing and drying.

[0189]

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Lauryl dimethylamine oxide 15% by weight Cationized cellulose 0.2 (manufactured by Union Carbide, Polymer JR-400) Dimethyl polysiloxane emulsion 5 (manufactured by Toshiba Silicone Co., Ltd., product name: TSC930) Amino-modified silicone emulsion 0.2 (Toray Co., Ltd.) Dow Corning Silicone Co., Ltd., product name: SM8702C) Sodium benzoate 0.5 Fragrance 0.4 Color element 0.0001 Purified water All 100 Formulation Example 20 A shampoo having the following composition was prepared. The shampoo thus obtained was excellent in foaming properties and detergency, and good in feeling during washing and rinsing without creaking. It also exhibited an excellent rinsing effect, and was excellent in slipperiness and flexibility during rinsing and drying.

[0191]

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Lauryl polyglucoside 10% by weight (in the above general formula (19), R ⁵⁹ = lauryl group, G is a glucose residue, x = 0, y = 1.3) Purified salt 2 Glycerin 2 Dimethyl polysiloxane emulsion 4 ( (Manufactured by Toray Dow Corning Silicone Co., Ltd., product name: BY22-835) Sodium benzoate 0.5 flavor 0.4 pigment 0.0001 purified water All 100 Formulation Examples 21 to 28 and Comparative Formulation Examples 1 to 3 Various dishwashing detergents were prepared, and the foaming property was examined by the following method. Table 3 shows the results.

<Foaming Test Method> A solution obtained by adding 0.2% by weight of butter and 5% by weight of dishwashing detergent to ion-exchanged water at 25 ° C. was stirred by an inverted stirring method, and the foam height was measured 30 seconds after the stirring was stopped. .

[0194]

[Table 3]

[0195]

The N-alkylamide alkanol sulfate (1) of the present invention has low irritancy to the skin and has excellent foaming and detergency. Therefore, the cleaning composition of the present invention containing the N-alkylamide alkanol sulfate (1) is useful as a cleaning agent for hair, skin, tableware and the like.

Claims (8)

(57) [Claims] 1. An N-alkylamide alkanol sulfate salt represented by the general formula (1). Embedded image (Wherein, R ¹ represents a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, R ² represents an alkyl group, alkenyl group or hydrogen atom having 1 to 22 carbon atoms, and R ³ represents Shows a linear or branched alkylene group having 1 to 5 carbon atoms,
R ⁴ O is an oxyalkylene group having 2 to 3 carbon atoms, and n is 0 to 20.
And n R ⁴ Os may be the same or different. M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkanol ammonium having 2 to 9 carbon atoms, an alkyl ammonium or alkenyl ammonium having 1 to 22 carbon atoms, an alkyl or alkenyl substituted pyridinium having 1 to 18 carbon atoms, Or a basic amino acid. ) 2. R ¹ is a linear or branched alkyl group having 6 to 22 carbon atoms, R ² is a hydrogen atom or a methyl group, R ³ is a linear or branched alkylene group having 1 to 5 carbon atoms, R ⁴ O
Is an oxyethylene group or an oxypropylene group, n is any number from 0 to 10, and M is ammonium, sodium, potassium or an alkanolammonium having 2 to 9 carbon atoms. salt. 3. R ¹ is a linear alkyl group having 8 to 18 carbon atoms, R ²
There hydrogen atom or a methyl group, R ³ is a straight-chain alkylene group having 1 to 5 carbon atoms, n is 0, M is ammonium, sodium or N- alkylamide alkanol sulfates of claim 1 wherein the triethanolammonium. 4. R ¹ is a linear alkyl group having 8 to 18 carbon atoms, R ²
But a hydrogen atom, R ³ is a methylene group, a pentylene group or a 2-methyl-butylene radical, n is 0, M is ammonium, sodium or N- alkylamide alkanol sulfates of claim 1 wherein the triethanolammonium. Wherein R ¹ is a linear alkyl group having 8 to 18 carbon atoms, R ²
But a hydrogen atom, R ³ is a methylene radical, n is 0, M is ammonium, sodium or N- alkylamide alkanol sulfates of claim 1 wherein the triethanolammonium. 6. The method according to claim 1, wherein the following steps A, B, C, or A, C, or D, B, C, or D, C are performed in this order. A method for producing an N-alkylamide alkanol sulfate salt according to claim 1. Step A: General formula (2) (Wherein R ¹ and R ² have the same meanings as described above) to the aliphatic amine represented by the general formula (3). (Wherein, R ³ has the same meaning as described above), and is reacted with a cyclic lactone represented by the following general formula (4). (Wherein, R ¹ , R ² and R ³ have the same meanings as described above). Step B An N-alkylamide alkanol represented by the above general formula (4) is reacted with an alkylene oxide in the presence of an alkali or acid catalyst to give a compound of the general formula (5) (Wherein R ¹ , R ² , R ³ and R ⁴ have the same meaning as described above, and n ′ represents a number of 1 to 20). Step C: A N-alkylamide alkanol represented by the general formula (4) or (5) is reacted with a sulfating agent, then neutralized with a basic substance, and the N-alkylamide alkanol represented by the general formula (1) is reacted. A step of obtaining an alkylamide alkanol sulfate salt. Step D The aliphatic amine represented by the general formula (2) is added to the general formula (6) HO-R ³ CO ₂ R ⁵ (6) (wherein R ³ has the same meaning as described above, and R ⁵ is A hydrogen atom or a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms) or an ester thereof to give an N-alkyl amide represented by the general formula (4). A step of obtaining an alkanol. 7. The method according to claim 6, wherein the sulfating agent in step C is chlorosulfonic acid, sulfuric anhydride, fuming sulfuric acid, concentrated sulfuric acid or sulfamic acid. 8. An N represented by the general formula (1) according to claim 1.
-A detergent composition comprising an alkylamide alkanol sulfate salt.