JPS59142299A - Novel cationic surfactant - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel cationic surfactant, which aims to have low irritation to the skin, excellent softening effect on hair or fibers, moist and supple feel, and The object of the present invention is to provide a new cationic surfactant that not only has an antistatic effect but also has a cleaning effect.

After washing the fibers, we improve their antistatic performance and flexibility.
In order to give the hair a soft finish, or to provide flexibility, suppleness, moisture, and smoothness after shampooing the hair, a general softening agent containing cationic surfactants as the main ingredient, or Hair rinse is used. Compared to other surfactants such as anionic and nonionic surfactants, the cationic part of cationic surfactants has a strong adsorption power to hair and fibers. It has an adsorption function. This hydrophobic group improves the slipperiness of the surface of hair and fibers, increasing the flexibility of the hair and fibers. Among cationic surfactants, quaternary ammonium salts in particular have cationic properties at all pH levels from acidic to alkaline, and have good adsorption to hair and fibers over a wide range of pH. 1~
They have better antistatic properties than tertiary cationic surfactants, and many also have antibacterial properties, making them indispensable as fabric softeners, fabric softeners, and rinse bases. From this point of view, as fiber softening agents, for example, distearyldimethylammonium chloride, and as rinse bases, quaternary ammonium salt cationic surfactants such as distearyldimethylammonium chloride and stearyltrimethylammonium chloride are widely used. ing.

Although conventional cationic surfactants have such excellent properties, many of them are more irritating to the skin and eye mucous membranes than other surfactants such as anionic and nonionic surfactants. The current trend is to specify the amount of these cationic surfactants to be used in dry rinses and fabric softeners, and to reduce the amount of these cationic surfactants blended as much as possible. Furthermore, among cationic surfactants, distearyldimethylammonium chloride, which is essential as a main base for softeners, has poor solubility in water, so solubilizers are used to make it into a highly concentrated aqueous solution as a softener. A cationic surfactant with good solubility is desired. Furthermore, cationic surfactants generally cannot be used in combination with anionic surfactants because they form water-insoluble precipitates when mixed with 7-ionic surfactants, which significantly impairs the surface m1 activity. . For this reason, in order to increase the flexibility of fibers, the fibers are first washed with an anionic detergent, rinsed, and then a cationic fabric softener is added to achieve a soft finish. Even if your hair is dry, wash it with shampoo and then rinse it.
In either case, the method of use is troublesome and requires two steps, so it is desired to develop a fabric softener that can provide both cleaning and softening effects at the same time.

As a result of intensive investigation into a new softening agent that can be incorporated into detergents, the present inventor found that a cationic surfactant containing a certain type of cationized polyol long-chain monofatty acid ester as a main component can Compared to active agents, it has less skin irritation, has good softening effects and antistatic properties, and has good solubility in water, and even when mixed with anionic surfactants, it does not form water-insoluble precipitates. The present invention was completed by discovering the conventional features and characteristics.

That is, if the cationic surfactant of the present invention is used, for example, in a +F fabric softener or conditioner, it will cause less skin irritation than conventional products, and will have good water absorption and hygroscopicity; Ya Shampoo tco combination ssureshi t1 washing and soft 1 Elc
It is possible to provide a product that can be used for finishing, cleaning and rinsing at the same time.

The cationic surfactant in the present invention is a polyol having at least 3 hydroxyl groups in its molecule; it is partially esterified with a long chain fatty acid, and some of the remaining hydroxyl groups are 3-4 hydroxyl groups.
The active ingredient is a cationized polyol long chain fatty acid ester substituted with a nitrogen-containing group. Preferred examples of poly-7 compounds include glycerin, diglycerin, triglycerin, tetraglycerin, pentaerythritol, dipentaerythritol, pentoses such as arabinose, xylose, lipose, hexoses such as glutenose, galactose, mannose, fructose, etc. These are deoxysaccharides that are deoxylated, sugar alcohols such as etrit, ribit, madonite, mannitol, galactose, inmitol,
Examples include oligosaccharides such as sucrose, lactose, and maltose. These polyols may be mixtures and adducts of ethylene oxide and propylene oxide. The long chain fatty acids include straight chain or branched saturated or unsaturated fatty acids having 8 to 22 carbon atoms, preferably lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, coconut fatty acid, and hardened beef tallow. Examples include fatty acids. In addition, the cation moiety is a general formula hydroxyl group derived from a halogenated alkylamine or glycidylamine, R1 is hydrogen, methyl group, ethyl group, or benzyl group, and R2 and R, l are represented by a methyl group, ethyl group, or benzyl group. Examples include tertiary to quaternary nitrogen-containing groups.

Preferred examples of the cation moiety include dimethylaminoethyl group, diethylaminoethyl group, dimethylaminopropyl group, trimethylammonioethyl group, 3-)
Dimethylammonio 2-71 hydroxy n-propyl group, 3-triethylammonio-2-hydroxy-
n-propyl group, 3-dimethylethylammonio-2-
Examples include 1 hydroxy 〇-propyl group and the like. or,
As the anion part, for example, CI +Br + I
-+NOB-+]/250421 CH3Co9-, and the like.

In order to obtain the cationic surfactant of the present invention, one method is to prepare a fatty acid polyol ester obtained by reacting a polyol compound with a fatty acid or a fatty acid/ride in an inert organic solvent such as N,N-dimethylformamide. The desired product can be obtained by condensation with a cationizing agent such as a logogenated alkylamine or glycidylamine using an hydride or the like (by performing 7-ionization of the hydroxyl group, and then). Another method is to react the polyol compound with a cationizing agent in an alkaline aqueous solution, and if necessary, treat the unreacted polyol compound with a cation exchange resin.
This can be removed to obtain a cationized polyol, which can then be esterified with a higher fatty acid or a higher fatty acid halide by a conventional method. Further, if necessary, heat and dissolve in methyl ethyl ketone, ethyl acetate, etc.
After the insoluble matter is once removed, a purified product of the cationized polyol long-chain monofatty acid can be obtained by precipitating the solid matter at room temperature.

The cationic surfactant of the present invention is less irritating to the skin and has better flexibility than conventional cationic surfactants, is less likely to form water-insoluble salts with anionic surfactants, and is hygroscopic. Since it has improved water solubility, it can be used not only in rinse agents, fabric softeners, emollient creams, etc., but also in laundry detergents, kitchen detergents, shampoos, etc.

Synthesis Examples and Examples will be described in more detail below, but the present invention is not limited thereto.

The N + N-dimethylformamide (DMF) used as a solvent in Synthesis Examples 1 to 8 was dehydrated by distillation.

Synthesis Example 1 (i) L-7 rubitol 92.15 f (0,
5M ) and sodium hydroxide 6.3 f! water 200
After dissolving in rag, anionization is performed by stirring at 70C for 1 hour. Glycidyltrimethylammonium chloride 37.9 F (0,25
After adding M) dropwise, the reaction mixture is stirred at 70C for 5 hours to effect etherification. The reaction solution is adsorbed onto a strongly acidic ion exchange resin (Diaion 5K-IB H type), water is flowed to elute unreacted sorbitol, and 3N hydrochloric acid aqueous solution is flowed to elute cationized sorbitol. After sufficiently concentrating and dehydrating the eluate, 200 tons of ethanol was added, and by-product salt was removed by filtration. The filtrate is concentrated to obtain a cationized sorbitol consistency 399. Cationization ■ NMR spectrum of rubitol -N(Cdans) = (
From the ratio of the proton of δ3.3) to the proton of -Cdan, -〇-, and]Cdan-〇- (δ3.4 to 4.7), the molar ratio of the cation part and the nrubitol part is 1.4: 1. Met.

(ii) This cationized sorbitol9. O? D
In addition to MF150+a/, 80. After heating and dissolving at tl',
To this, 9.1 y (o,z s M ) of pyridine is added, and 8.58 F (0,028 M) of stearic acid chloride dissolved in 50 DMF (0,028 M) is added dropwise. 6
After stirring for 3 hours at 0C, the reaction solution is concentrated to dryness. The residue was heated to dissolve in 300 dt of methyl ethyl ketone, the insoluble viscous substance was removed by decantation, and the mixture was allowed to stand at room temperature to precipitate canonized sorbitol monostearate. The precipitate is filtered and dried to obtain cationized sorbitol monostearate solid product 4.02. -N (C!
! I) protons of s (δ3.5) and -C and, -
From the plateon ratio of (δ 1.3), the molar ratio of the cation part, sorbitol part, and long chain fatty acid acyl part is 1.4:
The ratio was 1:1.1. This compound will be referred to as A hereinafter.

Synthesis Example 2 Cationized flubitol obtained in Synthesis Example 1 (1) 10.
5 f and viridi y 12.4 t co, + 57
M) was added in DMF 200++t/r, and dissolved by heating with SaC.

To this, 19.52 (0,064 M) of stearic acid chloride dissolved in 80 trrlf of DMF was added dropwise.
Stir at 60C for about 3 hours. The reaction solution was concentrated, and the residue was heated and dissolved in 200 ml/l of ethyl acetate, and then left overnight at room temperature to precipitate cationized sorbitol distearate. The precipitate is filtered and dried to obtain a solid substance 219 of cationized sorbitol distearate. -N(CH*)s (δ 3.
From the ratio of the proton of 5) to the proton of -CH9-(δt,a), the molar ratio of the cation part, sorbitol part, and long chain fatty acid acyl part was 1.4:1:2. This compound will be referred to as B hereinafter.

Synthesis Example 3 Glycerin monopalmitate 16.51 (0.05M
) was dissolved in DMFlooml, and this was dissolved in 50% sodium hydride6. D of o y (0,12s M)
MF80mg suspension gradually? Drip this. After dropping, when no hydrogen generation is observed, add DMF5 (
1++lt dissolved chlorcholine chloride 11.9
2 (0,075 M) dropwise and then stirred at room temperature for 1 day. After consuming unreacted sodium hydride with methanol, it is neutralized by blowing in hydrogen chloride gas. Concentrate the neutralized solution, add 80 g of ethanol, remove the by-product salt by filtration, and concentrate the filtrate. The residue was dissolved in ethyl acetate.
00 ml by heating, insoluble materials were removed by decantation, and the mixture was left to stand at room temperature overnight to precipitate cationized glycerin monopalmitate. The precipitate was filtered and dried to obtain 7.31 solids of cationized glycerol monopalmitate.

-N(CHll)8(63,5
The molar ratio of the cation moiety to the glycerin monopalmitate moiety was 1.2:1 from the ratio of the proton of -CH2-(δ1.3) to the proton of -CH2-(δ1.3). This compound will be referred to as C hereinafter.

Synthesis Example 4 Polyglycerol monostearate (rNIKKOL DGMSJ manufactured by Nikko Chemicals Co., Ltd.) 21.62 (about 0
．． 05M) was dissolved in DMF 200mH, and this was dissolved in 50qb Zodium hydride. Of (0,12
Gradually drop the solution into a suspension of 5M) in 80ml of DMF. After dropping, when hydrogen generation is no longer observed, D.
11.25 F (0,075 M) of glycidyltrimethylammonium chloride dissolved in 80 ml of MF was gradually added dropwise, and the mixture was stirred at room temperature for one day. After consuming unreacted sodium hydride with methanol, hydrogen chloride gas is blown in to neutralize it. After concentrating the reaction solution, 100 g of ethanol is added thereto, the by-product salt is removed by filtration, and the filtrate is concentrated. Residue la methyl ethyl ketone 200++
! /L heating fa Solution L-1 Insoluble matter is removed by decantation. - Leave to stand at 0AF in the evening to precipitate cationized polyglycerol monostearate. The precipitate was filtered and dried to obtain a solid substance of cationized polyglycerol monostearate i1. Obtain sy■. -N(CHII)11< in NMR spectrum
From the ratio of the proton of δ3.3) to the proton of -CH,2-(δ1.3), the molar ratio of the cation moiety to the polyglycerol monostearate moiety was 12:t. This compound will be referred to below.

Synthetic example glycerin monostearate polyoxyethylene ether (manufactured by Nikko Chemicals Co., Ltd. [NIKKOL TMG
-51-ethylene oxide 5 mole adduct) 17.9
f (approximately 0.03 M) in 200 ml of DMF, and added 3.4 ml of 50 thyridium hydride.
B y (0,075M) was gradually added dropwise to a suspension of D'MF50 waste. After dropping, when hydrogen generation is no longer observed, DMF6f) Wll! Dissolved glycidyltrimethylammonium chloride 5.92 (0
,04M) was added dropwise, and the mixture was stirred at room temperature for 1 day.

After consumption of unreacted indium hydride with methanol? Neutralize by blowing in hydrogen chloride gas. After concentrating the reaction solution, 100 ml of ethanol is added thereto, the by-produced common salt is removed by filtration, and the filtrate is concentrated. The residue was heated and dissolved in 200 + + lr of ethyl acetate, and after decanting and removing insoluble materials, the mixture was left to stand overnight at room temperature to precipitate cationized glycerol monostearate polyoxyethylene/ether.

The precipitate was filtered and dried to obtain a solid substance of cationized glycerin monostearate boriooxyethylene ether. NMR7, hector cr)-N(CH8)8
(δ3.2) noproton and -CH, -(61,3)+7
) Based on the proton ratio, the molar ratio of the cation part and the glycerin monostearate polyoxyethylene part was 1.1N. This compound will be referred to as E hereinafter.

Synthesis Example 6 Sucrose distearate (Ryotone Yugar Ester S-570J manufactured by Ryoto Co., Ltd.) 8.6 t
(approximately 0.01 M) Dissolve ODMF 80 m/in and add 50% 0% Fujiram Hydride 1.2
0.025 M) DMF 40ffil suspension
Gradually drip E. After the dropwise addition, when no hydrogen generation was observed, glycidyltrimethylammonium chloride 3.02C0.0 was dissolved in 30ml of DMF.
2M) was gradually added dropwise and then stirred at room temperature for 1 day. After consuming unreacted sodium halide with methanol, hydrogen chloride gas is blown in to neutralize it. After concentrating the reaction solution, 50 al of ethanol was added thereto, the by-produced common salt was removed by filtration, and the filtrate was immobilized. The residue was heated to dissolve 150 mJt of methyl ethyl ketone, and after decanting and removing insoluble matter, the mixture was left to stand overnight at room temperature to precipitate cationized sucrose distearate. The precipitate was filtered and dried to obtain a solid of cationized sucrose distearate (1.22). NMR2B/) Renault-N (C
Hs)++(δ3.1) +7) Proton and -CH2
-(61,3) (from the ratio of D protons, the molar ratio of the cation part and the nuclose distearate part, S: 1
Met. This compound will be referred to as F hereinafter.

Synthesis Example 7 Sorbitan monolaurate (rNIKKOL 5L-10J manufactured by Nikko Chemicals Co., Ltd.) 13.8 F (about 0.04 M) and sodium hydroxide 2 F (0.0
5 M) in 30 ml of water (stir for 1 hour at room temperature. 1 ml of this solution was dissolved in 1 θal of water and 6.0 ml of glycidyltrimethylammonium chloride (0.04
M) was added dropwise and then stirred at 40 tZ' for 8 hours to effect cationization. The reaction solution was adjusted to pH 4 with hydrochloric acid, concentrated to dryness, added with 50 ml of ethanol, and the by-produced common salt was removed by filtration. After concentrating the filtrate, the residue was diluted with methyl ethyl ketone 1
00ml by heating and dissolving insoluble matter by decantation. The mixture is left at room temperature for a while to precipitate cationized fulvitan monolaurate. The precipitate is filtered and dried to obtain 2.82 g of solid cationized fulvitan monolaurate. NMR spectrum ■ ” (CHs) + (δ3.2) proton and -C
From the proton ratio of H2, (δ1.3), the molar ratio of the cation part and sorbitan monolaurate part is 1.2:1.
Met.

This compound will be referred to as G hereinafter.

Synthesis Example 8 Sorbitan trioleate polyoxyethylene ether (1-NIKKOLTo-3 manufactured by Nikko Chemicals Co., Ltd.
0J ethylene oxide 20 mole adduct) 282 (
Approximately 0.02 M) was dissolved in 300 liters of DMF, and this was dissolved in 1.84 f (0.04 M) of 50% sodium hydride.
Slowly drop a suspension of 50 liters of DMF.

down. After the dropwise addition, when no hydrogen generation is observed, N,N-dimethylamine ethyl chloride 2.8 F (0,026M) dissolved in DMF 30d is gradually added dropwise, and then stirred at room temperature for one day.

After consumption of unreacted sodium hydride with methanol? Neutralize by blowing in hydrogen chloride gas.

After concentrating the reaction solution, 100 m/ml of ethanol was added thereto, the by-product salt was removed by filtration, and the filtrate was concentrated. The residue was heated and dissolved in 200 ml of methyl ethyl ketone, and after removing the insoluble matter by decantation, it was left to stand at room temperature overnight to precipitate cationized sorbinone-oleate polyoxyethylene ether hydrochloride. The precipitate is filtered and dried to obtain a solid substance 12.31 of cationized rubitan trioleate polyoxyethylene ether hydrochloride. -N-(CH3)2 (δ2.3)nopro) and -C in NMR spectrum
From the proton ratio of H,-(δ1.3), the molar ratio of the cation part and the sorbitan trioleate polyoxyethylene ether part was 1.1:1. Below, this compound H
shall be.

Example 1 The cationized polyol fatty acid ester A-Ht obtained in Synthesis Examples 1 to 8 was used alone, and the solubility in water in a mixed system of this and a commercially available anionic surfactant was expressed. Shown in 1. All amounts below are expressed in weight%.

〔Measurement condition〕

(1) Water-soluble surfactant 1 in a single system
% aqueous solution at 25c.

(2) Aqueous solution of water-soluble cationic surfactant 1 and anionic surfactant 1 in a mixed system with a commercially available anionic surfactant
% aqueous solution in equal amounts and shaken, tf>F'S property at 25C is shown.

Abbreviations in the table S: Dissolved sH: Slightly cloudy H: Cloudy Table 1 * Commercially available anionic surfactants ■ Dodecylbenzenesulfone fiNa salt ■ Polyoxyethylene (3) lauryl ether sulfate Na salt III AO3 (Kao Detergent 95) ■ Lauryl Ether sulfate Na salt VN-lauroylglutamic acid mono-Na salt ※※Control product 1 Distearyldimethylammonium chloride 2 Stearyltrimethylammonium chloride Example 2 Each compound of A-H obtained in Synthesis Examples 1 to 8 and a commercially available cationic surfactant Table 2 shows a comparison of the skin irritation test results conducted by V-Kotsui.

〔experimental method〕

0.1rrt of a 10% aqueous solution of the test compound was included in a batch test bandage, and this was applied to 14 subjects (10 males,
It was attached to the upper arm flexor key of 4 women for 24 hours.

Judgment: The following criteria r after 1 hour and 24 hours of batch removal
I went from there.

m: No reaction ±: Erythema that can be removed as normal +: Erythema -1+: Erythema J edema Table 2 Skin irritation test results *Control: Stearyldimethylbenzyl/monium chloride Example 3 Synthesis Examples 1 to 8 The flexibility of the fibers and the antistatic performance for the fibers and each resin were measured when each of the obtained A-H compounds was used alone and when used in combination with a commercially available anifone-based detergent. . These results are shown in Table 3 and Table 41.
This is shown.

〔Measurement condition〕

(1) Flexibility of fibers A commercially available towel was soaked in an aqueous solution of 3-thiosulfuric acid for one day and washed with water, then washed with a 0.05% nonionic surfactant (polyoxyethylene alkylaryl ether) aqueous solution, washed with water, and then air-dried to make it sticky. I used it as a wet towel.

(i) Wash the above-mentioned single-liner towel with a 0.2% dodecylbenzenesulfonic acid (LAS) aqueous solution 20 times vertically and horizontally, followed by 3 spring washes 10 times vertically and horizontally.
Washed with water repeatedly. This towel was immersed in a 0.017% cationic surfactant test aqueous solution for 3 minutes at 401Z' and then air-dried to obtain a test towel.

(11) Combination system with anionic surfactant 0.017
% cationic surfactant and 0.05% LAS blended aqueous solution V
It was washed and washed with water in the same manner as trowel (1), and then air-dried to obtain a test towel.

Using 15 experienced panelists, the flexibility of the LAS-washed cloth was given a score of 2, and the flexibility of the cloth treated with distearyldimethylammonium and muchloride was given a score of 7. The flexibility of the test cloth was determined based on the average score.

(2) Antistatic performance A sample of 125 ml of cationic surfactant was placed in a Petri dish with a diameter of 18α and 50 ml of pure water. Add and dissolve. Next, a wool cloth or various resin films of 10 X I Q crn is immersed in this solution at 25 U for 2 minutes, and then air-dried overnight at 25 U at a humidity of 50%.

Under the same conditions, the surface resistivity of the wool cloth or resin film is measured using a V-trowel surface resistor (Model 4329-A, manufactured by Yokogawa Hule Notop Card KK). Antistatic performance is expressed in surface resistivity Ω, and the smaller the value, the stronger the antistatic performance.) Table 3 Results of fiber softening effect test *Control 1, - Distearyldimethylammonium chloride 2, Stearyltrimethylammonium Chloride 3, LAS (sodium dodecylbenzenesulfonate) As shown in Table 3, among the compounds of the present invention, the diester (B+F) and triester σ0 are commercially available softening bases, distearyl dimethyl ammonium. It has a more supple and fluffy feel compared to cloth treated with chloride.

The monoesters (A, C, D, E, G) also have better flexibility than stearyltrimethylammonium chloride. It has good flexibility even when used in combination with Saranko anionic surfactant.

Table 4 Antistatic Performance Test Results D , E , G) have antistatic properties comparable to the commercially available antistatic agent stearyltrimethylammonium chloride.

Example 4 The following formulation composition was prepared, and the compound of the present invention was evaluated as a rinse base through sensory evaluation. The evaluation results are shown in Table 5.

Formulation example (Lion KK: Leoguard G) Formulation (V) Same as above distearyldimethylammonium chloride 1.5% [Evaluation method] Using a panel of 10 women in their 20s to 30s, they first washed their hair with a commercially available shampoo and trowel. , then when rinsing using a 10ml sample (finger-stickability, sliminess, etc.) and when drying (
The feel of the hair (such as dryness, suppleness, smoothness, etc.) was sensory evaluated and scored according to the following criteria, and the average score was shown.

+2 +1 0 -1 -2Table 5
As is clear from Table 5 of the rinsing sensory evaluation results, when the compound of the present invention is used as a rinsing base, a product with a good feeling of use can be obtained both during rinsing and during drying.

Example 5 Fiber softener cetyl alcohol 3.0
% Propylene Glycol 1.
0% Pigment/Fragrance Appropriate amount A fiber softener with good flexibility for cloth was obtained by blending the above components.

Example 6 Softener compounded detergent cationized sucrose distearate 5.0
% (Compound F of the present invention) Sodium lauryl sulfate salt 20.0
Attack P, o, E (31 lauryl ether sulfate Na salt
5.0% pigment/fragrance
Appropriate amount of water (total balance: 100%) By blending the above ingredients, a detergent containing a fabric softener was obtained which had a good softening effect on fabrics after washing.

Example 7 Hair rinse cetyl alcohol 3.0
% lanolin polyethylene glycol ester 3.
0% propylene glycol 1
．． 0% Pigment/Fragrance Appropriate amount Water Remaining total 10.0 The above-mentioned blended composition is easy to run your fingers through when rinsing without causing any squeaks, and when drying, the hair does not become loose and has a moist and supple texture.

Example 8 Softening hair shampoo Na lauryl sulfate salt 20.0
%Dinocol L BL-4,2' 1 '$ Citric acid 2 Chi Flavoring
appropriate amount of water
Remainder total: 100% The above composition does not cause squeaks when washing hair, does not make hair stiff when drying, and is moist and flexible.Patent applicant: Ajinomoto Co., Inc.

Claims (1)

[Claims] A polyol compound having at least three hydroxyl groups in the molecule is partially esterified with a long-chain fatty acid having 8 to 22 carbon atoms, and a portion of the remaining hydroxyl groups is represented by the following general formula. 3~
Cationic surfactant I consisting of a cationized polyol long chain 1 fatty acid ester substituted with a quaternary nitrogen-containing group as an active ingredient (wherein n'40 is an integer of 4, R is hydrogen or a hydroxyl group R1 is hydrogen, methyl group, ethyl group or