JP3526317B2 - N-alkylamide alkanols, method for producing the same, and surfactant composition and detergent composition containing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to N-alkylamidoalkanols which are hypoallergenic to the skin and have an excellent foaming effect on a wide range of surfactants, and a process for producing the same.
It also relates to a surfactant composition and a detergent composition containing the same.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
When a surfactant is used as a detergent and foamability is particularly required, the surfactant alone often does not provide sufficient foamability, and a foaming agent is used as a surfactant aid. Has been done. Alkanoyldiethanolamide, alkanoylmonoethanolamide, alkyldimethylamine oxide and the like are used as the foaming agent. However, while these surfactant auxiliaries are relatively inexpensive,
The foaming effect on the surfactant is still insufficient, and the versatility for various surfactants is very low. Furthermore, in recent years, it has been reported that alkanoyldiethanolamide and the like produce harmful nitrosamines upon contact with air oxygen,
Its use is limited. In addition, in some known N-alkylamidoalkanols, examples reported as foaming agents (USP 3,250,71) have already been reported.
9), its foaming effect is limited to some nonionic activators such as polyoxyethylene alkyl ether type and pluronic type, and has not been widely used. Therefore, a surfactant auxiliary agent having excellent versatility and foaming property and high safety is strongly desired.

[0003]

In view of the above-mentioned situation, the present inventors have been found to be useful as various detergent aids for washing hair, body, dishwashing, etc., excellent in versatility and foaming property, and safe. As a result of intensive studies on a surfactant auxiliary having a high activity, it was found that an N-alkylamidoalkanol derived from a long-chain primary amine or secondary amine achieves the above object, and completed the present invention.

That is, the present invention provides a foaming agent comprising an N-alkylamidoalkanol represented by the general formula (I), and a surfactant composition and a detergent composition containing the same.

[0005]

[Chemical 5]

[In the formula, R ^{1 represents a} linear or branched alkyl group having 6 to 22 carbon atoms. R ² : represents a hydrogen atom or a methyl group . R ³ : —CH ₂ CH (CH ₃ ) CH ₂ CH ₂ — has 5 carbon atoms in the branched chain.
Represents an alkylene group of or a linear alkylene group having 5 carbon atoms.
You The present invention also provides the N-a represented by the general formula (I-1).
A rukylamido alkanol and a method for producing the same
Of.

[0007]

[Chemical 6]

[0008] wherein, R ^1: shows a straight or branched chain alkyl group having a carbon number of 6 to 22 of
You R ² : represents a hydrogen atom or a methyl group. R ^{3 '} : -CH ₂ CH (CH ₃ ) CH ₂ CH _2- has 5 carbon atoms in the branched chain
Is an alkylene group. In the general formula (I) or (I-1) , R ¹ is a linear or branched alkyl group having 6 to 22 carbon atoms.
Although a group, such as octyl, decyl, dodecyl, tetradecyl group, hexadecyl group, octadecyl group, isostearyl group, 2-ethylhexyl group and the like, in terms of increasing foaming, linear carbon atoms 8 Particularly preferred are -18 alkyl groups.

R ² is preferably a hydrogen atom or a methyl group from the viewpoint of foaming property.

R ³ is preferably a straight-chain C 5 alkylene group or a branched 2-methylbutylene group represented by —CH ₂ CH (CH ₃ ) CH ₂ CH ₂ —, and particularly —CH ₂ CH (CH ₃ ) A branched chain 2-methylbutylene group represented by CH ₂ CH ₂ — has a low melting point and is preferable in terms of operability in synthesis and formulation.

As the compound represented by the general formula (I),
The compound groups shown in the following 1) to 2) are exemplified. 1) In the general formula (I), R ¹ is a linear or branched chain.
An alkyl group having 6 to 22 carbon atoms, R ² is a hydrogen atom or a methyl group, R ³ is an alkylene group of 5 carbon atoms, straight-chain N- alkylamide alkanol. 2) In the general formula (I), R ¹ is a linear or branched chain.
An alkyl group having 6 to 22 carbon atoms, wherein R ² is a hydrogen atom or
A methyl group, R ³ is _{-CH 2 CH (CH 3) CH} 2 CH 2 - is the number of carbon atoms in the branched chain represented by 5 alkylene group N- alkylamide alkanol.

N- represented by the general formula (I) of the present invention
Specific examples of the alkylamidoalkanol include the compounds shown below.

[0013]

[Chemical 7]

Examples of the method for producing the N-alkylamidoalkanol of the present invention represented by the above general formula (I) include the following methods.

General formula (II)

[0016]

[Chemical 8]

(In the formula, R ¹ and R ² have the above-mentioned meanings.)
An amine represented by the general formula (III)

[0018]

[Chemical 9]

A method of reacting with a lactone represented by the formula (wherein R ³ has the above-mentioned meaning).

As the amine represented by the general formula (II),
Examples thereof include N-long chain primary or secondary amines such as octylamine, decylamine, dodecylamine, tetradecylamine, coconut alkylamine, and N-methyldodecylamine.

Examples of the lactone represented by the general formula (III) include β-methyl-δ-valerolactone and ε-caprolactone .

The amine represented by the general formula (II) and the general formula (I
The reaction temperature with the lactone represented by II) is preferably in the range of 0 to 200 ° C, and the reaction time is preferably 1 to 24 hours.

N- represented by the general formula (I) of the present invention
The alkylamidoalkanol has an excellent foaming effect on the coexisting surfactant, and the surfactant composition containing such a compound has excellent foaming properties and low irritation and high safety. It can be suitably used not only as a cleaning agent for the body and dishes, but also as various cleaning agents such as a face wash and a household detergent.

The surfactant composition of the present invention contains the N-alkylamidoalkanol represented by the above general formula (I) as an essential component, and the content thereof is 0.1-.
90% by weight is preferable, and 0.1 to 50% by weight is more preferable.

As the surfactant used in the surfactant composition of the present invention, a general anionic surfactant (alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, alkylbenzene sulfonate,
Higher fatty acid salt, α-olefin sulfonate, alkyl sulfonate, N-alkylamide alkanol sulfate ester salt, N-alkanoylethanolamide sulfate ester salt, fatty acid glyceride sulfate salt, alkyl glyceryl ether sulfate salt, taurine-based surfactant , Sarcosinate-based surfactant, isethionate-based surfactant, N-
Acylated acidic amino acid type surfactants, etc .; Amphoteric surfactants (alkyl betaine type surfactants, amidopropyl betaine type surfactants, imidazolinium betaine type surfactants, sulfobetaine type surfactants, phosphobetaine type surfactants) Surfactants and amino acid type surfactants such as sodium laurylaminopropionate); nonionic surfactants (polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, fatty acid monoglycerides,
Fatty acid sorbitan ester, alkyl polyglycoside, etc .; cationic surfactant (alkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride,
Ethanol sulfate lanolin fatty acid aminopropylethyldimethylammonium etc.) and the like. These surfactants may be used alone or as a mixture of several kinds.

The detergent composition of the present invention contains the N-alkylamide alkanol represented by the general formula (I) and a surfactant as essential components. The content of N-alkylamidoalkanol in the cleaning composition of the present invention is
The amount is preferably 0.1 to 90% by weight, more preferably 0.1 to 50% by weight.

In the detergent composition of the present invention, components used in conventional detergents for hair, body, dishware and the like can be used in combination as long as the effects of the present invention are not impaired. Examples of such concomitant components include humectants such as glycerin, propylene glycol, and ethylene glycol, other bactericides, emulsifiers, and fragrances.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 N-decyl-4-hydroxy-2-methylpentaneami
Synthesis of de- decylamine 1210.08g (7.6928mo) in a 2-liter-4 neck flask equipped with a stirrer, condenser, thermometer and dropping funnel.
l) was charged and heated to 100 ° C. with stirring. Β-Methyl-δ-valerolactone (Kuraray: MVL) 87
8.79 g (7.6992 mol) was added dropwise over 1 hour and 30 minutes. Then, stirring was continued while maintaining the system temperature at 100 ° C., and the residual amount of decylamine in the system was traced by the total amine value. as a result,
The reaction rate reached 97.8% by carrying out the reaction aging for 4 hours and 30 minutes, so the reaction was terminated. The reaction-completed product was cooled to 70 ° C., and then poured into 3 liters of hexane with stirring. The obtained white crystallized product was collected by filtration and dried,
1885.5 g of the compound represented by the following formula (1) as colorless powder
(Yield: 90.3%) was obtained.

[0030]

[Chemical 10]

<Fat and oil analysis> Acid value: 0.70, hydroxyl value: 207.8, volatile matter (%): 2.1 <mass spectrometry (FAB-MASS ionization method> 272 (M + 1, base), 254, 226, 158 <IR Analysis (KBr method)> 3295, 2927, 2855, 1639, 1564, 1467 cm ^-1 <NMR analysis (200MHz, CDCl ₃ )> 5.87 (t, 1H), 3.53 (t, 2H), 3.12 (q, 2H) , 2.82 (b, 1H), 2.
15-1.80 (m, 4H), 1.50-1.30 (m, 3H), 1.15 (b, 14H), 0.85 (d, 3H), 0.74 (t, 3
H) ppm Example 2 N-dodecyl-4-hydroxy-2-methylpentana
Synthesis of Mido Dodecylamine 344.10g (1.8564mo) in a 1-liter-4 neck flask equipped with a stirrer, condenser, thermometer, and dropping funnel.
l) was charged and heated to 70 ° C. with stirring. Β there
Methyl-δ-valerolactone (Kuraray: MVL) 213.90
g (1.8740 mol) was added dropwise in 20 minutes. After that, set the system temperature to 1
The temperature was raised to 20 ° C. and stirring was continued, and the residual amount of dodecylamine in the system was monitored by the total amine value. As a result, the reaction rate reached 97.0% by carrying out the reaction aging for 5 hours, so the reaction was terminated. After cooling the reaction-terminated product to 70 ℃, use hexane
It was poured into 1.5 liter with stirring. The obtained white crystallized product was collected by filtration and dried to obtain 481.72 g (yield: 85.8%) of a compound represented by the following formula (2) as a colorless powder.

[0032]

[Chemical 11]

<Fat and oil analysis> Acid value: 0.20, hydroxyl value: 188.4, volatile matter (%): 0.28 <mass spectrometry (FAB-MASS ionization method> 300 (M + 1, base), 282, 254, 186 <IR Analysis (KBr method)> 3292, 2926, 2854, 1638, 1563, 1467 cm ^-1 <NMR analysis (200MHz, CDCl ₃ )> 5.75 (t, 1H), 3.52 (t, 2H), 3.08 (q, 2H) , 2.12-1.84 (m, 4
H), 1.49-1.25 (m, 3H), 1.10 (b, 18H), 0.83 (d, 3H), 0.72 (t, 3
H) ppm Example 3 N-tetradecyl-4-hydroxy-2-methylpenta
Synthesis of N- amide Tetradecylamine 698.77g (3.27g) in a 2-liter-4 neck flask equipped with a stirrer, condenser, thermometer and dropping funnel.
(43 mol) was charged and heated to 100 ° C. with stirring. There β-methyl-δ-valerolactone (Kuraray: MVL)
374.10 g (3.2776 mol) was added dropwise over 1 hour. Then, the temperature in the system was raised to 120 ° C. and stirring was continued, and the remaining amount of tetradecylamine in the system was traced by the total amine value. As a result, the reaction rate reached 95.9% by carrying out the reaction aging for 5 hours, so the reaction was terminated. The reaction-completed product was cooled to 75 ° C., and then poured into 3.0 liters of hexane with stirring.
The obtained white crystallized product was collected by filtration and dried to obtain 938.21 g (yield: 87.5%) of a compound represented by the following formula (3) as a colorless powder.

[0034]

[Chemical 12]

<Fat and oil analysis> Acid value: 0.17, hydroxyl value: 170.2, volatile matter (%): 0.37 <mass spectrometry (FAB-MASS ionization method> 328 (M + 1, base), 310, 282, 214 <IR Analysis (KBr method)> 3295, 2927, 2856, 1640, 1563, 1467 cm ^-1 <NMR analysis (200MHz, CDCl ₃ )> 5.80 (t, 1H), 3.55 (t, 2H), 3.10 (q, 2H) , 2.10-1.90 (m, 4
H), 1.61-1.32 (m, 3H), 1.13 (b, 22H), 0.80 (d, 3H), 0.71 (t, 3
H) ppm Example 4 Synthesis of N-octyl-5-hydroxyhexanamide In a 2 liter-4 neck flask equipped with a stirrer, cooling tube, thermometer, dropping funnel, 425.65 g (3.2932mo) of octylamine.
l) was charged and heated to 100 ° C. with stirring. There ε
-Caprolactone (UCC: TONE Monomer EC) 377.00g
(3.3030 mol) was added dropwise over 2 hours. After that, change the system temperature
Stirring was continued while maintaining the temperature at 100 ° C., and the residual amount of octylamine in the system was monitored by the total amine value. After aging the reaction for 3 hours, the product was cooled to 70 ° C. and poured into 2 liters of hexane with stirring. The white crystallized product obtained was collected by filtration and dried to obtain 702.10 g (yield: 87.6%) of a compound represented by the following formula (4) as a colorless powder.

[0036]

[Chemical 13]

<Fat and oil analysis> Acid value: 0.30, hydroxyl value: 229.8, volatile matter (%): 2.6 <mass spectrometry (FAB-MASS ionization method> 244 (M + 1, base), 226, 198, 130 <IR Analysis (KBr method)> 3316, 2926, 2854, 1635, 1542, 1473 cm ^-1 Example 5 Synthesis of N-decyl-5-hydroxyhexanamide 1 liter equipped with stirrer, cooling tube, thermometer, dropping funnel 362.56 g (2.3049 mol) decylamine in a 4-necked flask
Was charged and heated to 100 ° C. with stirring. There ε-
Caprolactone (UCC: TONE Monomer EC) 263.08g (2.
(3049 mol) was added dropwise in 40 minutes. After that, set the system temperature to 100 ° C.
The stirring was continued while maintaining the above value, and the residual amount of decylamine in the system was monitored by the total amine value. After aging the reaction for 3 hours, the product was cooled to 70 ° C. and poured into 2 liters of hexane with stirring. The obtained white crystallization product was collected by filtration and dried to obtain 528.69 g (yield: 84.5%) of a compound represented by the following formula (5) as a colorless powder.

[0038]

[Chemical 14]

<Fat and oil analysis> Acid value: 0.30, hydroxyl value: 203.9, volatile matter (%): 1.3 <mass spectrometry (FAB-MASS ionization method> 272 (M + 1, base), 254, 226, 158 <IR Analysis (KBr method)> 3316, 2926, 2854, 1634, 1541, 1473 cm ^-1 Test Example 1 The N-alkylamide alkanol of the present invention and a comparative product were analyzed by the following method for polyoxyethylene.
(3) The foaming effect on sodium lauryl ether sulfate was measured. As the activator pure component, a mixture of polyoxyethylene (3) sodium lauryl ether sulfate / inventive product or comparative product = 17/3 in weight ratio was used. The results are shown in Table 1.

<Foaming amount measuring method> 0.1% by weight of pure active agent and 0.3% by weight of lanolin were added to 40 ° C., 4 ° DH hard water, and the dissolved solution was stirred for 30 seconds by an inversion stirring method. The amount of bubbles was measured 10 seconds after the stirring was stopped and 120 seconds after the stirring was stopped.

[0041]

[Table 1]

Test Example 2 With respect to the N-alkylamide alkanol of the present invention and a comparative product, N-dodecyl-2-methyl-4-sulfoxypentanamide represented by the following formula (10) was used in the same manner as in Test Example 1. The foaming effect on ammonium was measured. As the activator pure content, a mixture of N-dodecyl-2-methyl-4-sulfoxypentanamide ammonium / the product of the present invention or the comparative product = 17/3 in a weight ratio was used. The results are shown in Table 2.

[0043]

[Chemical 15]

[0044]

[Table 2]

Formulation examples of the detergent 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 foamability and detergency, and was good to the touch without squeaking.

<Shampoo Composition> Polyoxyethylene (3) lauryl ether sulfate sodium salt 15.0% by weight N-decyl-4-hydroxy-2-methylpentanamide (Compound of Example 1) 2.3 Sodium benzoate 0.5 Phosphoric acid 0.1 Dye Proper amount Perfume Proper amount Water Balance 100% by weight Formulation Example 2 A shampoo having the following composition was prepared. The obtained shampoo was excellent in foamability and detergency, and was good to the touch without squeaking.

<Shampoo composition> N-dodecyl-2-methyl-4-sulfoxypentanamide sodium 15.0% by weight N-dodecyl-4-hydroxy-2-methylpentanamide (compound of Example 2) 3.0 Sodium benzoate 0.5 Phosphoric acid 0.1 Dye Appropriate amount Fragrance Appropriate amount Water Balance 100% by weight Formulation Example 3 A shampoo having the following composition was prepared. The obtained shampoo was excellent in foamability and detergency, and was good to the touch without squeaking.

<Shampoo composition> N-decyl-5- represented by the following formula (11)       Ammonium sulfoxyhexanamide 15.0% by weight

[0050]

[Chemical 16]

N-Decyl-5-hydroxyhexanamide (Compound of Example 5) 2.3 Cationized cellulose (UCC: Polymer JR400) 0.5 Sodium benzoate 0.3 Citric acid qs Dye qs Perfume qs Water Balance 100% by weight Formulation Example 4 A dishwashing detergent having the following composition was prepared. The obtained dishwashing detergent was excellent in foamability, washability, and rinsability, and was good in terms of tactile feeling without a slimy feel.

<Detergent Composition> Palm alkyl polyglucoside 16.0% by weight Polyoxyethylene (3) lauryl ether 4.0 N-tetradecyl-4-hydroxy-2-methylpentanamide (Compound of Example 3) 2.0 Paratoluenesulfonic acid 1.0 Ethanol 1.0 Dye Appropriate amount Fragrance Appropriate amount Water Balance 100% by weight

Continuation of front page (51) Int.Cl. ⁷ identification code FI C11D 1/52 C11D 1/52 (56) References JP-A-2-24360 (JP, A) JP-A-6-73077 (JP, A) Japanese Patent Publication No. 48-13530 (JP, B1) Japanese Patent Publication No. 50-17216 (JP, B2) US Patent 3250719 (US, A) US Patent 4325973 (US, A) US Patent 3125530 (US, A) US Patent 3025323 ( US, A) West German patent application publication 2729209 (DE, A1) West German patent application publication 1920975 (DE, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 235/00 C07C 231/00 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] 1. A foaming agent comprising an N-alkylamidoalkanol represented by the general formula (I) . [Chemical 1] [In the formula, R ^{1 represents a} linear or branched alkyl group having 6 to 22 carbon atoms. R ² : represents a hydrogen atom or a methyl group . R ³ : —CH ₂ CH (CH ₃ ) CH ₂ CH ₂ — has 5 carbon atoms in the branched chain.
Represents an alkylene group of or a linear alkylene group having 5 carbon atoms.
You ] 2. The foam-increasing foam according to claim 1, wherein in the general formula (I), R ¹ is a linear alkyl group having 8 to 18 carbon atoms.
Agent . 3. A foaming agent according to claim 1 or 2 is contained.
A surfactant composition comprising: 4. A foaming agent according to claim 1 or 2 is contained.
A cleaning composition comprising: 5. N-alkyl represented by formula (I-1)
Amido alkanol. [Chemical 2] [In the formula, R ^{1 represents a} linear or branched alkyl group having 6 to 22 carbon atoms.
You R ² : represents a hydrogen atom or a methyl group. R ^{3 '} : -CH ₂ CH (CH ₃ ) CH ₂ CH _2- has 5 carbon atoms in the branched chain
Is an alkylene group. ] 6. In the general formula (I-1), R ¹ is a straight chain.
The N- according to claim 5, which is an alkyl group having 8 to 18 carbon atoms.
Alkylamido alkanol. 7. A compound represented by the general formula (II): (Wherein R ¹ and R ² have the above-mentioned meanings), and an amine represented by the general formula (III-1) : (In the formula, R ^{3 ′} has the above-mentioned meaning.) The lactone represented by the formula (9) is reacted with N-represented by the general formula (I-1) according to claim 5 or 6. Method for producing alkylamidoalkanol.