JPH0749402B2 - Novel ammonium salt and surfactant composition containing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel ammonium salt, and more particularly, an ammonium salt capable of imparting excellent flexibility to fibers and excellent flexibility and smoothness to hair, and an ammonium salt containing the same. It relates to a surfactant composition.

[0002]

2. Description of the Related Art Currently,
Most of the commercially available products as a softening agent for fibers or a hair treatment agent are quaternary ammonium having two long-chain alkyl groups in one molecule as represented by di (cured tallow alkyl) dimethylammonium chloride. It is a composition whose main component is salt. The reason for this is that the quaternary ammonium salt has a good softening effect or smoothing effect on various fibers or hair in a small amount. However, although the above quaternary ammonium salt has a remarkable softening effect on cotton, it is acrylic, polyester,
It is hard to say that the effect is sufficient for synthetic fibers such as polyamide-based fibers, and if the treatment is carried out at a higher concentration, the elasticity of clothing may be reduced and the texture may be impaired.

Further, since the above quaternary ammonium salt has a strong hydrophobicity, when it is poured into rinsing water when the stirring force is weak, the dispersibility in water is poor and, therefore, there is a possibility that the garment may be uneven. Further, particularly when it is stored for a long period of time at a low temperature, it may thicken, form a gel, or separate. Conventionally, a commercially available softener for textiles contains polyoxyethylene-based nonionic surfactant, an additive such as an electrolyte and a solvent in addition to the above quaternary ammonium salt, and dispersibility in water and long-term Although it improved storage stability, its effect was still insufficient.

Further, liquid softening finishes having various amines as softening bases have been conventionally known. For example, Japanese Patent Laid-Open No. 52-
59796 discloses a composition for imparting flexibility to a fiber containing a long-chain alkylamine such as methyldi (cured tallow alkyl) amine, and JP-A-58-6070 discloses an acylated alkanolamine, a water-soluble compound. A fiber material finishing agent that imparts smoothness and comfortable feel to a fiber containing a quaternary ammonium salt and a fatty acid ester is disclosed in JP-A-61-167083. Quaternary ammonium compound, higher fatty acid and hydroxy lower alkyl polyamine. A softening agent containing a condensation reaction product with an alkylamine polyglycol ether and having good dispersibility is disclosed in JP-A-61-275474 for treating fibers containing a di (higher alkyl) cyclic amine and a Bronsted acid. A stable aqueous dispersion of JP-A-64-85368 discloses a di-long chain alkylamine-anionic surfactant ionic complex, a non-silicone wax and JP-A-2-6662 discloses a fabric conditioning composition containing an amine such as a condensate of hydroxy lower alkylalkylene diamine and a higher fatty acid and an amphoteric fabric conditioning agent. 2-14076 describes a fabric conditioning composition containing a dilong-chain alkylamine-polyfunctional carboxylic acid complex, which imparts flexibility and antistatic properties. Furthermore, JP-A-52-5394
The publication describes a fabric conditioning composition containing a mono or dialkyl alkylenediamine static suppressant and a quaternary ammonium softener. However, the softening agents containing these amines have relatively good dispersibility and storage stability as compared with the softening agents containing the quaternary ammonium salt, but the softening performance was not sufficient.

Furthermore, in general, a hair treatment agent uses a cationic active agent in the form of an aqueous solution or suspension together with a nonionic emulsifier or an aliphatic alcohol, and after the application to the hair, the hair and the hair or the hair are treated. It improves combability when wet by reducing friction between the brushes and also enhances a series of special properties such as gloss, antistatic and combability when dry. To this end, dilong-chain alkyl ammonium salts,
For example, distearyl dimethyl ammonium chloride,
Di (hardened tallow alkyl) dimethylammonium salt and the like have been used. However, none of these quaternary ammonium salts satisfies the softness, smoothness, and oily feel of the hair both during washing and drying.

Therefore, an object of the present invention is to provide an ammonium salt that imparts extremely good flexibility to fibers and extremely good flexibility and smoothness to hair, and a surfactant containing the same. To provide a composition.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a novel specific ammonium salt has excellent flexibility for fibers and elasticity for clothing ( It has been found that it can impart a fluffy feeling to the hair, and that it imparts sufficient flexibility to hair during drying and smoothness during washing and drying. That is, the present invention provides an ammonium salt represented by the following general formula (A), and a surfactant composition containing the same.

[0008]

[Chemical 2]

[In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. R ² and R ³ represent a linear or branched alkyl group or alkenyl group having 11 to 21 carbon atoms. Shows the H or an alkyl group having 1 to 4 carbon atoms; R ^4. m: An integer of 2 to 9 is shown. X represents a halogen atom, a sulfate or an alkyl sulfate having 1 to 4 carbon atoms. In the ammonium salt provided by the present invention, specific examples include the following compounds.

[0010]

[Chemical 3]

[0011]

[Chemical 4]

These compounds are precursors of the following formula
Usual way a tertiary amine represented by (A '), i.e. R ⁴ -
Y (wherein Y represents a halogen atom) or (R ⁴ ) ₂ SO ₄
It can be obtained by quaternization with or by neutralization with hydrohalic acid or sulfuric acid.

[0013]

[Chemical 5]

[In the formula, R ¹ to R ³ and m have the same meanings as described above. ] Above following formula (A ') a compound represented by the, N - lower After cyanoethylation reaction of dialkanolamines such as an alkyl alkanolamine and diethanolamine, or obtained by the hydrogenation reaction, the alkylene halohydrin (e.g. 9-bromo -1-
Nonanol) and obtained by reacting an N- lower alkylamine N- alkyl -N - alkanol amine cyanoethylated reaction, then the following equation obtained by the hydrogenation reaction (A-1)

[0015]

[Chemical 6]

[In the formula, R ¹ and m have the same meanings as described above. The compound represented by] Ru can be obtained by reacting a fatty acid having 12 to 22 carbon atoms. In order to obtain the ammonium salt represented by the formula (A) of the present invention from the compound represented by the formula (A ′) , a known method using a lower alkyl halide or dilower alkylsulfate can be used. . The neutralized product can be obtained by adding the compound represented by the formula (A ′) to an aqueous acid solution or by adding the compound to water at the same time as the acid.

When a softening agent for fibers is manufactured using the novel ammonium salt according to the present invention, the total amount of the novel ammonium salt according to the present invention is preferably 4 to 40% by weight, considering the viscosity and handling property of the product. Is 6 to 30% by weight, particularly preferably 10 to 30% by weight. Furthermore, this novel ammonium salt may be used in combination with a conventionally known di (long-chain alkyl) quaternary ammonium salt.

Further, in the softening agent for fibers, a silicone compound such as dimethylpolysiloxane, dimethylpolysiloxane partially modified with an amino group or a polyoxyalkylene group, particularly preferably a partially polyoxyalkylene group. By blending dimethylpolysiloxane modified with, the skin feel can be further improved. These silicone compounds are preferably added in an amount of 0.3 to 5% by weight based on the total amount of the novel ammonium salt according to the present invention.
The softening agent for fibers using the novel ammonium salt of the present invention has almost the same softening effect as that of di (cured tallow alkyl) dimethylammonium chloride, which has been widely used in the past, but surprisingly has elasticity. It turns out that a certain softness can be obtained.

When the ammonium salt of the present invention is used as a softening agent for aqueous liquid fibers, it is desirable to add 0.05 to 0.4% by weight of an inorganic electrolyte such as sodium chloride, calcium chloride or magnesium chloride for viscosity adjustment. . Also, in order to obtain a high degree of stability during long-term storage, nonionic activators such as polyoxyethylene alkyl ether and polyoxyethylene alkylamine, ethanol, isopropanol, solvents such as propylene glycol and ethylene glycol, or urea are added. can do. Also, known esters, nonionic or cationic compounds, long-chain alcohols, etc. may be used in combination as the softening base.

When the novel ammonium salt according to the present invention is used as a hair treatment agent, the compounding amount of the novel ammonium salt according to the present invention is 4
The same amount as when using a primary ammonium compound,
The amount is preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight. When the hair treatment agent using the novel ammonium salt of the present invention is used, compared to the hair treatment agent using a quaternary ammonium salt which has been conventionally used, the hair has excellent flexibility and wetness both in wet and dry conditions. Gives a smooth, oily or moist feeling. Examples of the dosage form of the hair treatment agent using the novel ammonium salt of the present invention include hair rinse, hair conditioner, hair treatment, hair pack, hair cream, styling lotion, styling mousse, conditioning mousse, hair mousse, and hair spray. Further, as a combined component constituting these hair treatment agents, cationic activators such as conventional mono- or di (long-chain alkyl) quaternary ammonium salts, nonionic activators, higher alcohols, higher esters, hydrocarbons, etc. , Fatty acids, oils such as silicone oil, humectants such as glycerin and urea, cationic polymers, polymeric polysaccharides, polymeric substances such as polypeptide,
Solvents such as lower alcohols, propylene glycol and diethylene glycol can be used as long as the effects of the novel ammonium salt of the present invention are not impaired.

[0021]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 A method known from the addition product of N-methylethanolamine and acrylonitrile [J. Org. Chem., 26 , 3409, (1960)].
66 g of N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized in step 284 g of stearic acid
Was charged into a four-necked flask equipped with a stirrer, a thermometer, and a dehydration tube, and the temperature was raised to 180 ° C. It was heated at that temperature for about 10 hours while distilling off the produced water. 300 g of the obtained product was dissolved in 60 g of isopropyl alcohol, charged into an autoclave equipped with a stirrer, a thermometer, and a pressure gauge, and 28 g of methyl chloride was injected under pressure. After reacting at 100 ° C. for about 8 hours, isopropyl alcohol was distilled off under reduced pressure to obtain 320 g of a target compound represented by the following structural formula (1). The following structures were confirmed from NMR and IR spectra.

[0023]

[Chemical 7]

IR spectrum (KBr tablet) 1734 cm ^-1 , 1642 cm ^-1 , 1466 cm ^-1 , 1188 cm ^-1 Example 2 100 g of lauric acid and N- (2) in a four-neck flask equipped with a stirrer, thermometer and dehydration tube. -Hydroxyethyl) -N-methyl-1,3-propylenediamine 66g, 180 ℃
The temperature was raised to. It was heated at that temperature for 3 hours while distilling off the produced water. Next, add 170g of behenic acid and 180 ℃
And reacted for 8 hours. 280 g of the obtained product was dissolved in 55 g of isopropyl alcohol and charged into an autoclave equipped with a stirrer, a thermometer and a pressure gauge to give 28 g of methyl chloride.
Was pressed in. After reacting at 100 ° C. for 8 hours, isopropyl alcohol was distilled off under reduced pressure to obtain 300 g of a target compound represented by the following structural formula (2). The following structures were confirmed from NMR and IR spectra.

[0025]

[Chemical 8]

IR spectrum (KBr tablet) 1733 cm ^-1 , 1642 cm ^-1 , 1466 cm ^-1 , 1186 cm ^-1 Example 3 Instead of the stearic acid used in Example 1, 280 g of Emersol 875 manufactured by EMERY was used. The same operation as in Example 1 was carried out to obtain a compound represented by the following structural formula (3).

[0027]

[Chemical 9]

[In the formula, p and q each represent a number from 0 to 16, and p + q = 10 to 16. Example 4 In the same manner as in Example 1, stearic acid was reacted with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine to obtain 300 g of the product, which was previously mixed with 1500 g of water,
35 g of hydrochloric acid (49 g) was added dropwise to the four-necked flask prepared. The resulting aqueous solution was freeze-dried to remove water, and a compound represented by the following structural formula (4) was obtained. The following structures were confirmed from NMR and IR spectra.

[0029]

[Chemical 10]

[0030] IR spectrum (KBr ^{tablet) 1740cm -1, 1647cm -1, 1470cm} -1, 1167cm -1 Example 5 a stirrer, a thermometer, a pressure gauge, a 40% methylamine aqueous solution with autoclave with a pressure pump 400 g, 9 180 g of -chlorononanol was charged and the temperature was raised to 100 ° C. Next, 93 g of 48% sodium hydroxide aqueous solution was press-fitted at that temperature over 6 hours, and then aged for 1 hour. After cooling, the contents were taken out and unreacted methylamine and water were distilled off under reduced pressure. Ethanol was added and NaCl was filtered. Next, ethanol was distilled off and distilled to give 9- (N-methylamino) nonanol.
25 g were obtained. 120 g of 9- (N-methylamino) nonanol was charged into an autoclave equipped with a stirrer, a thermometer, a pressure gauge, and a dropping funnel, and 36.8 g of acrylonitrile was added dropwise at 70 ° C., followed by aging for 1 hour. Then Raney Nickel
Add 7.8g, introduce hydrogen up to 20kg / cm ² G,
The hydrogenation reaction was carried out for an hour. After cooling, the contents were taken out and distilled to obtain N- (9-hydroxynonyl) -N-methyl-
122 g of 1,3-propylenediamine were obtained. Stirrer,
Stearic acid in a 4-neck flask equipped with a thermometer and dehydration tube
284 g and N- (9-hydroxynonyl) -N-methyl-
115 g of 1,3-propylenediamine was charged and the temperature was raised to 180 ° C. It was heated at that temperature for 10 hours while distilling off the water formed. After cooling, 70 g of isopropyl alcohol was added and the temperature was raised to 60 ° C. At that temperature 62 g of dimethylsulfate 2
It dripped over time. Then, the mixture was aged for 5 hours, and isopropyl alcohol was distilled off under reduced pressure. 420 g of the target compound represented by the following structural formula (5) was obtained. The following structures were confirmed from NMR and IR spectra.

[0031]

[Chemical 11]

IR spectrum (KBr tablet) 1731 cm ^-1 , 1640 cm ^-1 , 1466 cm ^-1 , 1188 cm ^-1 Test Example 1 Softener for textiles The novel ammonium salt of the present invention was evaluated for flexibility and elasticity by the following methods. I went.

<Evaluation of flexibility and elasticity> (1) Treatment method Commercially available cotton towel 2 kg, acrylic jersey 1 kg 3.5 °
Repeatedly wash 5 times (30 liter washing machine) with commercial detergent attack (registered trademark, manufactured by Kao Corporation) with DH hard water,
After removing the fiber treating agent attached to each fiber, 1.5 g of the compounded composition of Table 1 was added as an active ingredient and treated under stirring at 25 ° C. for 1 minute. In each case, 1% by weight of polyoxyethylene-modified dimethylpolysiloxane was added to the total amount of the compounds according to the present invention.

(2) Evaluation Method The cloth treated by the above method was air-dried at room temperature, and then allowed to stand at 25 ° C. and 65% RH in a constant temperature and constant humidity for 24 hours. The softness and elasticity of these cloths were evaluated. For the evaluation of softness and elasticity, pairwise comparison was carried out by using a cloth treated with 10 cc of a softening agent containing 15% by weight of di (hardened beef tallow alkyl) dimethylammonium chloride as a control. The evaluation is expressed as follows. +2; softer or more elastic than the control +1; slightly softer or more elastic than the control 0; same as the control -1; slightly softer than the control or slightly less elastic than the control -2: the control Is softer or less elastic than the control. The compounds (D) and (E) used as comparative products are shown below. (D) ； Distearyl dimethyl ammonium chloride

[0035]

[Chemical 12]

[0036]

[Table 1]

As shown in Table 1, by using the compound of the present invention, the results satisfying both the effect of imparting flexibility and elasticity to the fiber were obtained.

Test Example 2 Hair Treatment Agent The effect of the novel ammonium salt of the present invention as a hair treatment agent was investigated with the following composition. <Composition> Ammonium salt
1% (ammonium salt of the present invention or control compound (D)) octadecyltrimethylammonium chloride
1% cetyl alcohol
3% water balance A hair rinse composition of the above composition was added to each of the hair bundles.
After applying 10% and leaving for 3 minutes after application, the hair was rinsed with warm water at 30 ° C. for a certain period of time, towel-dried, and the hair at WET was evaluated. After that, the hair bundle is dried with a dryer and DRY
The hair at that time was evaluated. Evaluation is by 10 panelists,
It was touched by the hand and evaluated according to the following criteria. The results are summarized in Table 2.

<Flexibility> 3: Soft feel 2: Lack of soft feel 1: Lack of soft feel <Smoothness> 3: Smooth 2: No smoothness 1: Non-smooth <Moist feeling> 3: Moisture Yes 2: Somewhat moist 1: No moist <oiliness> 3: No stickiness 2: Some stickiness 1: Sticky

[0040]

[Table 2]

As described above, when the ammonium salt of the present invention is used, a very excellent effect is obtained in all of the softness, smoothness, moisturizing feeling and oily feeling both during washing and drying of hair. Was found to show.

[0042]

The novel ammonium salt of the present invention, when used as a softening agent, has sufficient flexibility for each fiber,
It provides antistatic properties and excellent elasticity. Further, when used as a hair treatment agent, it imparts an extremely excellent effect in terms of flexibility, smoothness, and oily or moisturizing feeling both when washing and drying hair.

Claims (2)

[Claims] 1. An ammonium salt represented by the following general formula (A ): [Chemical 1] Wherein, R ^1; represents an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms. R ² and R ³ represent a linear or branched alkyl group or alkenyl group having 11 to 21 carbon atoms. Shows the H or an alkyl group having 1 to 4 carbon atoms; R ^4. m: An integer of 2 to 9 is shown. X represents a halogen atom, a sulfate or an alkyl sulfate having 1 to 4 carbon atoms. ] 2. A surfactant composition containing the ammonium salt according to claim 1.