JPH05230001A - New ammonium salt and surfactant composition containing the salt - Google Patents

Abstract

PURPOSE:To provide a new ammonium salt capable of imparting fibers with sufficient softness, antistaticity and excellent elasticity and hairs with softness, smoothness and moistness free from oily feeling in shampooed state as well as in dried state. CONSTITUTION:A compound of formula I or II (R<1> is 1-4C alkyl or hydroxyalkyl; R<2> and R<3> are 11-21C straight or branched-chain alkyl or alkenyl; R<4> is H or 1-4C alkyl excluding the case that both of two R<4> groups in the formula II are H; R<5> is 12-22C straight or branched-chain alkyl or alkenyl; (m) is integer of 2-9; X is halogen, sulfate or 1-4C alkylsulfate), e.g. the compound of formula IV. The compound can be produced from the compounds of formula V to formula VII by conventional method, e.g. by quaternarizing the compound of the formula R<4>-Y (Y is halogen) or (R<4>)2SO4 or by neutralizing with a hydrohalogenic acid or sulfuric acid. A surfactant composition containing the compound exhibits the above effects and is useful as a soft-finishing agent for textile and hair-treating agent.

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 to 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. Prior Art and Problems to be Solved by the Invention
Most of the commercially available products as a fabric softening agent or a hair treatment agent are quaternary ammonium having two long-chain alkyl groups in one molecule as typified by di (cured tallow alkyl) dimethylammonium chloride. It is a composition whose main component is salt. The reason 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, acrylic, polyester,
It cannot be said that the effect is sufficient for synthetic fibers such as polyamide-based fibers, and if the treatment is performed at a higher concentration, the elasticity of the clothing may be reduced and the texture may be impaired.

Further, since the above quaternary ammonium salt has strong hydrophobicity, when it is poured into rinsing water when the stirring force is weak, the dispersibility in water is poor, and there is a possibility that it may be uneven on the clothing. Further, particularly when it is stored for a long 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 (hardened tallow alkyl) amine, and JP-A-58-6070 discloses an acylated alkanolamine, a water-soluble composition. 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, which is for treating a fiber containing a di (higher alkyl) cyclic amine and a Bronsted acid. Stable aqueous dispersions of JP-A-64-85368 disclose di-long chain alkylamine-anionic surfactant ionic complexes, non-silicone waxes and JP-A-2-6662 discloses a fabric conditioning composition containing an amine such as a condensate of a hydroxy lower alkyl alkylenediamine and a higher fatty acid and an amphoteric fabric conditioning agent. JP-A 2-14076 describes a fabric conditioning composition containing a dilong-chain alkylamine-polyfunctional carboxylic acid complex and imparting flexibility and antistatic properties. Furthermore, JP-A-52-5394
The publication describes a fabric conditioning composition containing a mono or dialkyl alkylenediamine static inhibitor 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.

Further, 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 with each other. 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 which 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 ( The present invention has been completed, and it has been found that hair can be imparted with a fluffy feeling, 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 any one of the following general formulas (A), (B) and (C), and a surfactant composition containing the same.

[0008]

[Chemical 2]

[In the formula, R ¹ represents an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms. R ² and R ³ are linear or branched alkyl or alkenyl groups having 11 to 21 carbon atoms. Represent H or an alkyl group having 1 to 4 carbon atoms; R ^4. However, in the general formula (B), the case where two R ^{4 s} are both H is excluded. R ⁵ represents a linear or branched alkyl group or alkenyl group having 12 to 22 carbon atoms. 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
The tertiary amines represented by (A ') to (C') can be prepared by a conventional method, that is, R ⁴ -Y (wherein Y represents a halogen atom) or (R
⁴ ) It can be obtained by quaternization with ₂ SO ₄ or neutralization with hydrohalic acid or sulfuric acid.

[0013]

[Chemical 5]

[In the formula, R ^{1 to} R ⁵ and m have the same meanings as described above. Among the above compounds, the compound represented by the formula (A ′) can be obtained by hydrogenation reaction after cyanoethylation reaction of dialkanolamine such as N-lower alkylalkanolamine or diethanolamine, or an alkylenehalohydrin (for example, 9 −
(Bromo-1-nonanol) and N-lower alkylamine obtained by reacting N-alkyl-N-alkanol with cyanoethylation reaction, followed by hydrogenation reaction
(A-1)

[0015]

[Chemical 6]

[In the formula, R ¹ and m have the same meanings as described above. ] It can be obtained by reacting a compound represented by the following with a fatty acid having 12 to 22 carbon atoms. Further, the compound represented by the formula (B ′) is a compound represented by the following formula (B-1) obtained by an intramolecular dehydration cyclization reaction of N-lower alkyldiethanolamine.

[0017]

[Chemical 7]

[In the formula, R ⁴ has the same meaning as described above. ] The compound represented by the above can be obtained by subjecting the compound to a ring-opening amidation reaction with an aliphatic amine and then reacting the reaction product with a fatty acid halide having 12 to 22 carbon atoms. Further formula
The compound represented by (C ′) is obtained by the intramolecular dehydration cyclization reaction of N-long-chain alkyl or alkenyldiethanolamine.

[0019]

[Chemical 8]

[In the formula, R ⁵ has the same meaning as described above. ] After reacting a compound represented by
It can be obtained by reacting the reaction product with a fatty acid halide having 12 to 22 carbon atoms. Formula (A '), (B') or from the compound represented by (C ') of the present invention (A), (B) or
In order to obtain the ammonium salt represented by (C), a known method using a lower alkyl halide or di-lower alkyl sulfuric acid can be used. Further, the neutralized product is the formula (A '),
The compound represented by (B ′) or (C ′) can be obtained by adding it to an aqueous acid solution, or to water together with the acid.

When commercializing a softening agent for fibers 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. Further, the 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 or dimethylpolysiloxane partially modified with an amino group or a polyoxyalkylene group, particularly preferably a partially polyoxyalkylene group is used. 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 the conventionally widely used di (cured tallow alkyl) dimethylammonium chloride, but surprisingly has elasticity. It turns out that some 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. .. 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, as compared with the hair treatment agent using the 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 within a range that does not impair the effects of the novel ammonium salt of the present invention.

[0025]

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 adduct of N-methylethanolamine and acrylonitrile [J. Org. Chem., 26 , 3409, (1960)].
N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine 66g and stearic acid 284g
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 press-fitted. 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.

[0027]

[Chemical 9]

IR spectrum (KBr tablets) 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-necked flask equipped with a stirrer, thermometer and dehydration tube. -Hydroxyethyl) -N-methyl-1,3-propylenediamine (66 g) was charged and the temperature was 180 ° C.
The temperature was raised to. It was heated at that temperature for 3 hours while distilling off the produced water. Next, add 170 g 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 in an autoclave equipped with a stirrer, a thermometer and a pressure gauge, and 28 g of methyl chloride was added.
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.

[0029]

[Chemical 10]

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

[0031]

[Chemical 11]

[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 obtained product, and 1500 g of water in advance,
35 g of hydrochloric acid (49 g) was added dropwise to a 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.

[0033]

[Chemical 12]

[0034] 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 a 48% sodium hydroxide aqueous solution was press-fitted at that temperature over 6 hours, followed by aging 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 is distilled off and distilled to give 9- (N-methylamino) nonanol.
25 g were obtained. An autoclave equipped with a stirrer, a thermometer, a pressure gauge and a dropping funnel was charged with 120 g of 9- (N-methylamino) nonanol, 36.8 g of acrylonitrile was added dropwise at 70 ° C., and then aged 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 produced. 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.

[0035]

[Chemical 13]

IR spectrum (KBr tablet) 1731 cm ^-1 , 1640 cm ^-1 , 1466 cm ^-1 , 1188 cm ^-1 Example 6 Synthesis of N-methylmorpholone using the method of Example 2 of Japanese Patent Application No. 3-20709 I went. That is, as a catalyst
Using a catalyst having a composition of Cu: Ni: Pd = 5: 1: 0.01, N-methyldiethanolamine was subjected to a dehydration cyclization reaction to obtain N-methylmorpholone which was a target substance. A 4-necked flask equipped with a stirrer and a thermometer was charged with 115 g of N-methylmorpholone and 269 g of stearylamine and heated to 100 ° C.
The reaction was carried out at that temperature for 2 hours. Further, 350 g of acetone was added to the obtained product, and 303.5 g of stearic acid chloride was added dropwise with stirring. The white precipitate is the target compound represented by the following structural formula (6), and acetone was removed by filtration to obtain 560 g after drying. The following structures were confirmed from NMR and IR spectra.

[0037]

[Chemical 14]

IR spectrum (KBr tablet) 1745 cm ⁻¹ , 1675 cm ⁻¹ , 1475 cm ⁻¹ , 1158 cm ⁻¹ Example 7 In the same manner as in Example 6, N-stearyl diethanolamine was used as a raw material, and N-stearyl morphoform was used. Got Ron. 353 g of N-stearylmorpholone and 73 g of butylamine were charged into an autoclave equipped with a stirrer, a thermometer and a pressure gauge, the temperature was raised to 100 ° C., and the reaction was carried out at that temperature for 2 hours. 400 g of the product in a four-necked flask equipped with a stirrer, a thermometer, and a condenser, and 800 g of acetone as a solvent.
Was charged. The temperature was raised to 50 ° C., and 285 g of stearyl chloride and 78 g of 48% NaOH were simultaneously added dropwise thereto to carry out a reaction.
After aging at this temperature for 3 hours, the produced NaCl was removed by filtration, the remaining product was transferred to an autoclave, and 57 g of methyl chloride was injected under pressure. After reacting at 100 ℃ for about 8 hours,
I took it out. The white precipitate was filtered and dried to obtain 605 g of the target compound represented by the following structural formula (7). NMR,
The following structure was confirmed from the IR spectrum.

[0039]

[Chemical 15]

IR spectrum (KBr tablet) 1735 cm ^-1 , 1673 cm ^-1 , 1473 cm ^-1 , 1160 cm ^-1 Test Example 1 Softening agent for fibers Softness and elasticity of the novel ammonium salt of the present invention are evaluated by the following methods. I went.

<Evaluation of flexibility and elasticity> (1) Treatment method 2 kg of a commercially available cotton towel and 1 kg of an acrylic jersey at 3.5 °
Repeatedly wash 5 times (30 liters washing machine) with a commercially available detergent attack (Kao Corporation, registered trademark) with DH hard water,
After removing the fiber treatment agent attached to each fiber, 1.5 g of the compounded composition of Table 1 was added as an active ingredient, and the mixture was 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 for 24 hours at a constant temperature and a constant humidity of 25 ° C. and 65% RH. 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 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 or less elastic than the control -2; more 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

[0043]

[Chemical 16]

[0044]

[Table 1]

As shown in Table 1, by using the compound of the present invention, the results of 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 examined with the following composition. <Composition> Ammonium salt 1% (ammonium salt of the present invention or reference compound (D)) Octadecyltrimethylammonium chloride 1% Cetyl alcohol 3% Water balance The hair rinse composition having the above composition is applied to each hair bundle.
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 and towel-dried to evaluate the hair at WET. 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 hands and evaluated according to the following criteria. The results are summarized in Table 2.

<Flexibility> 3: Feeling soft 2: Lacking softness 1: Lacking softness <Smoothness> 3: Smooth 2: No smoothness 1: Non-smooth <Moisture> 3: Moisture Yes 2: Slightly moist 1: No moist <oiliness> 3: No stickiness 2: Slightly sticky 1: Sticky

[0048]

[Table 2]

As described above, when the ammonium salt of the present invention is used, it has an extremely excellent effect on all of the softness, smoothness, moisturizing feel and oily feel both during washing and drying of hair. Was found to show.

[0050]

INDUSTRIAL APPLICABILITY 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), (B) or (C). [Chemical 1] Wherein, R ^1; represents an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms. R ² and R ³ are linear or branched alkyl or alkenyl groups having 11 to 21 carbon atoms. Represent H or an alkyl group having 1 to 4 carbon atoms; R ^4. However, in the general formula (B), the case where two R ^{4 s} are both H is excluded. R ⁵ represents a linear or branched alkyl group or alkenyl group having 12 to 22 carbon atoms. 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.