JPH0212280B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to choline surfactant compositions.
More specifically, laundry detergents, kitchen detergents, which contain trialkyl (2-hydroxyalkyl) ammonium carboxylate as an essential ingredient;
The present invention relates to a choline-based surfactant composition that has both excellent surfactant performance and high safety and can be used in a wide range of applications, including detergents for shampoos and additives for foods and cosmetics. Conventionally, anionic and nonionic surfactants such as alkylbenzene sulfonates, higher alcohol sulfates, and higher alcohol ethoxylates have been mainly used as active ingredients in various detergents. Although all of these active ingredients have good surfactant ability, they have various safety problems to varying degrees and should not be used in fields where safety is strongly required. I can't. On the other hand, surfactants that can be used in fields that require extremely high safety, mainly food additives, include propylene glycol monofatty acid ester, glycerin monofatty acid ester, soybean lecithin, sorbitan fatty acid ester, and sucrose fatty acid ester. Esters are known, but among sucrose fatty acid esters, all except those with a high monoester content are highly hydrophobic and are used exclusively as water-in-oil (W/O) emulsifiers, and are generally used as water-in-oil (W/O) emulsifiers. It cannot be used for applications such as oil (O/W) emulsifiers and cleaning agents. In recent years, as interest in the safety of surfactants has increased, surfactants have become increasingly popular not only in food additives, but also in additives for cosmetics, resins, and cleaning products such as laundry detergents, kitchen detergents, and shampoos. Currently, there is a strong demand for the development of surfactants that have both excellent surfactant ability and high safety. In view of the current situation, the present inventors focused on the fact that choline, which is one of the constituents of phospholipids, and fatty acids, which are constituents of fat, are both extremely safe and edible. As a result of various studies, it was discovered that trialkyl (2-hydroxyalkyl) ammonium carboxylate has excellent surfactant ability and high safety that can be used in a wide range of applications, leading to the completion of the present invention. It is. Next, the present invention will be explained in detail. What is the trialkyl (2-hydroxyalkyl) ammonium carboxylate used in the choline surfactant composition of the present invention? General formula RCOO [R ¹ R ² R ³ NC (R ⁴ ) (R ⁵ ) C (R ⁶ ) (R ⁷ )OH] (In the formula, RCOO is a fatty acid anion having 6 to 24 carbon atoms, R ₁ , R ² and R ³ are lower alkyl groups, R ⁴ , R ⁵ ,
R ⁶ and R ⁷ represent a hydrogen atom or a lower alkyl group. Choline constituting these trialkyl (2-hydroxyalkyl) ammonium carboxylates or its homologs include choline, namely trimethyl (2-hydroxyethyl) ammonium hydroxide, ethyl dimethyl (2-hydroxyethyl) ammonium hydroxide. , diethylmethyl(2-hydroxyethyl)ammonium hydroxide, triethyl(2-hydroxyethyl)ammonium hydroxide, isopropyldimethyl(2-hydroxyethyl)ammonium hydroxide, diisopropylmethyl(2-hydroxyethyl)ammonium hydroxide,
Triisopropyl (2-hydroxyethyl) ammonium hydroxide, tri-n-propyl (2-hydroxyethyl) ammonium hydroxide, tri-n-butyl (2-hydroxyethyl) ammonium hydroxide, trimethyl (2-hydroxypropyl) hydroxide ) ammonium, ethyldimethyl(2-hydroxypropyl)ammonium hydroxide, diethylmethyl(2-hydroxypropyl)ammonium hydroxide, triisopropyl(2-hydroxypropyl)ammonium hydroxide, tri-n hydroxide
-Butyl (2-hydroxypropyl) ammonium, trimethyl (2-hydroxybutyl) hydroxide
Typical examples include quaternary ammonium salts such as ammonium, trimethyl(2-hydroxypentyl)ammonium hydroxide, and trimethyl(2-hydroxy-1-methylethyl)ammonium hydroxide. Among them, choline is a component of lecithin in soybeans and egg yolks, and is extremely safe.Moreover, it is mass-produced by organic synthesis, so it can be obtained at low cost, making it the most advantageous for the present invention. It is one of the quaternary ammonium salts that can be used for. On the other hand, as the fatty acid constituting the trialkyl (2-hydroxyalkyl) ammonium carboxylate, a fatty acid having 6 to 24 carbon atoms is used. These fatty acids may be either saturated fatty acids or unsaturated fatty acids, and their carbon chains are not limited to linear ones, but branched ones can also be used. Note that a fatty acid having a substituent such as a hydroxyl group may also be used. Typical examples of these fatty acids include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid,
Examples include elaidic acid, arachidic acid, behenic acid, and lignoceric acid. Note that it is not always necessary to use choline, its homologues, or fatty acids alone, and it is also possible to use two or more types in combination. Trialkyl (2-hydroxyalkyl) ammonium carboxylate is the above-mentioned choline,
Alternatively, it can be easily produced by a method in which a homologue thereof and a fatty acid are subjected to a neutralization reaction under solvent-free conditions, preferably in the coexistence of water, an organic solvent, etc., at room temperature or under heating conditions. This can be expressed as a reaction equation as follows. [R ¹ R ² R ³ NC (R ⁴ ) (R ⁵ ) C (R ⁶ ) (R ⁷ ) OH] OH + RCOOH → RCOO [R ¹ R ² R ³ NC (R ⁴ ) (R ⁵ ) C (R ⁶ ) (R ⁷ ) OH] +H ₂ O Choline or its homologs are often commercially available in the form of choline chloride or choline phosphate, for example, in the case of choline. is treated in advance with an alkali or basic anion exchange resin to liberate choline or choline analogues, and then
A method such as a method of causing a neutralization reaction with a fatty acid may be used. The method using water as a solvent is particularly advantageous because the produced trialkyl(2-hydroxyalkyl) ammonium carboxylate can be used as it is for various purposes in the form of an aqueous solution, aqueous suspension, aqueous paste, etc. be. Furthermore, even when water or an organic solvent is used, it is also possible to isolate trialkyl(2-hydroxyalkyl)ammonium carboxylate by using any method such as evaporation concentration or crystallization. In addition, trialkyl (2-hydroxyalkyl)
Ammonium carboxylate does not necessarily need to be prepared in advance according to the method described above; for example, when emulsifying fats and oils, fatty acids are dissolved in fats and oils, while choline or its homologues are dissolved in water, and then both are dissolved. It is also possible to add choline or its homolog and fatty acid separately, such as a method in which choline or its homologue and a fatty acid are added separately, such as a method in which they are mixed and a trialkyl (2-hydroxyalkyl) ammonium carboxylate is produced in the mixture. Even when it is used, it falls under the choline surfactant composition of the present invention. Although the trialkyl (2-hydroxyalkyl) ammonium carboxylate used in the choline surfactant composition of the present invention can exhibit sufficiently excellent surfactant ability even when used alone, it is of course possible to use other types of It is also possible to optionally use a surfactant in combination. Examples of surfactants that can be used in combination include sucrose fatty acid ester, sorbitan fatty acid ester, sorbitol fatty acid ester,
Mannitan fatty acid ester, mannitol fatty acid ester, glycerin fatty acid ester, propylene glycol fatty acid ester, fatty acid alkylolamides, polyoxyethylene ether of sorbitan fatty acid ester, polyoxyethylene ether of higher alcohol, polyoxyethylene ether of alkyl phenol, polyoxyethylene ether of fatty acid Nonionic surfactants such as oxyethylene ether, polyoxyethylene ether of castor oil, polyoxyethylene ether of higher amines, polyoxyethylene ether of fatty acid alkylolamide, polyoxyethylene polyoxypropylene ether, alkylbenzene sulfonates, Higher alcohol sulfate ester salt, higher alcohol polyoxyethylene ether sulfate ester salt, α-olefin sulfonate, alkanesulfonate, sulfated oil, glycerin monofatty acid ester sulfate ester salt, N-acylglutamate, N - Anionic surfactants such as acylsarcosine salts and N-acyl-N-methyl-β-alanine salts, amphoteric surfactants such as betaine type, glycine type, alanine type, and sulfobetaine type, natural lecithin, and saponin etc. are typical examples. In addition, inorganic builders such as sodium tripolyphosphate, zeolite, trisodium imidobis sulfate, sodium carbonate, sodium sulfate, sodium silicate, sodium borate, sodium chloride, potassium chloride, and ammonium chloride, which are widely used in the relevant industrial field, Malic acid, tartaric acid, citric acid, sodium malate, sodium tartrate, sodium citrate, potassium citrate, sodium oxalate, sodium maleate, sodium succinate, sodium gluconate, sodium oxydiacetate, sodium nitrilotriacetate, ethylenediaminetetraacetic acid Organic builders such as sodium, CMC (carboxymethyl cellulose),
It is also possible to optionally add bleaching agents, fluorescent dyes, enzymes, fragrances, skin protectants, sugars, and solubilizers (hydrotropes) such as ethyl alcohol, propylene glycol, glycerin, and urea. Other surfactants that can be used in combination with the above-mentioned trialkyl (2-hydroxyalkyl) ammonium carboxylate of the present invention, inorganic builders and organic builders widely used in the relevant industrial field,
The amount of various additives such as CMC and solubilizers used is not particularly limited, and the optimal amount used varies depending on the type of additive and the purpose of use, but usually trialkyl (2-hydroxy 0 to 1000000% by weight based on alkyl) ammonium carboxylate,
More preferably, it is generally used in a range of 0 to 100,000% by weight. The choline surfactant composition of the present invention is in powder form,
It may be prepared and used in any form such as granules, solids, pastes, and aqueous solutions. The choline surfactant composition of the present invention is a completely new type of interface that has excellent foaming power, detergent power, surface tension lowering ability, solubilizing power, dispersing power, oil-in-water (O/W) emulsifying power, etc. Since it is an active agent and is composed of highly safe choline or its analogues and fatty acids, there is no need to worry about safety at all. Additionally, in general, anionic surfactants such as alkali metal salts, ammonium salts, and organic amine salts of fatty acids, especially saturated fatty acids having 16 or more carbon atoms, have low solubility in water at low temperatures to room temperature, and have poor foaming power. Since the detergency also decreases, it is preferable to use it at a temperature of around 40℃, but the choline surfactant of the present invention has a considerably higher solubility in water than the above ones even at low temperatures to room temperature, and has excellent Demonstrates foaming power, etc. Therefore, kitchen detergents for tableware, fruits, vegetables, etc., seafood detergents, laundry detergents, solid soaps, shampoos, body shampoos for infants, oral cleansers,
It can be used in a wide range of applications, including the field of cleaning agents such as industrial detergents, the field of additives such as emulsification, dispersion, and solubilization of foods, medicines, cosmetics, etc., and modification of resins. As detailed above, the choline surfactant composition of the present invention has both excellent surfactant ability and high safety that can be used in a wide range of applications, and therefore has great industrial utility value. The present invention will be explained in more detail below using production examples and examples. Production Example 1 22.8 g (0.1 mol) of myristic acid and 118.5 g of water were added to 24.2 g (0.1 mol) of a 50% by weight aqueous solution of choline, and the mixture was stirred at 30° C. for 1 hour to perform a neutralization reaction. At the beginning of stirring, the entire mixture was cloudy due to the presence of water-insoluble myristic acid, but
The aqueous solution of trimethyl (2-hydroxyethyl) ammonium myristate gradually becomes transparent as the neutralization reaction progresses, and finally becomes completely transparent165.5
g was obtained. As a result of concentrating this aqueous solution under reduced pressure, 32.8 g of white crystals were obtained (yield 99.1%). As a result of elemental analysis, C68.70%, H12.62
%, N4.35% (calculated value as C ₁₉ H ₄₁ NO ₃ :
C68.83%, H12.46%, N4.22%). or,
Infrared absorption spectrum (KBr tablet method) and nuclear magnetic resonance spectrum ('HNMR, 60MHz, solvent
The measurement results of CD ₃ OD, internal standard TMS) were
It is shown in Fig. 2. Production Example 2 Add 50% of choline to a mixture of 28.4 g (0.1 mol) of stearic acid and 100 ml of isopropanol at room temperature.
After dropping 24.2 g (0.1 mol) of a wt% aqueous solution, the mixture was stirred for 1 hour to carry out a neutralization reaction. As a result of concentrating the reaction solution under reduced pressure, white crystals of trimethyl (2-hydroxyethyl) ammonium stearate were obtained.
g was obtained (yield 98.2%). As a result of elemental analysis, C70.98%, H12.95
%, N3.55% ( _calculated value as _{C23H49NO3 :}
C71.26%, H12.74%, N3.61%). In addition, infrared absorption spectra (KBr tablet method), nuclear magnetic resonance spectra ('HNMR, 60MHz, solvent
The measurement results of CD ₃ OD, internal standard TMS) were
It is shown in Fig. 4. Examples 1 to 9 In the choline-based surfactant compositions having the following compositions, samples were prepared in which the types of choline or its homologues and fatty acids constituting the trialkyl (2-hydroxyalkyl) ammonium carboxylate were varied. The foaming force and surface tension were measured, and a monitor test was conducted. Composition of choline surfactant composition Weight % Trialkyl (2-hydroxyalkyl) ammonium carboxylate 20 Ethanol 5 Propylene glycol 5 Water 70 Perfume A little The results are shown in Table 1. The methods for measuring the foaming force and surface tension and the method for conducting the monitor test are as follows. (1) Method for measuring foaming power Choline surfactant composition with the above composition 3.125
dilute g to 250 ml with distilled water (trialkyl (2
- 0.25% concentration as (hydroxyalkyl) ammonium carboxylate) followed by the Ross & Miles method (Japanese Industrial Standard JIS) at a temperature of 25°C.
Measure the foam height (mm) immediately after foaming and after 5 minutes using K3362). (2) Method for measuring surface tension The same sample (concentration as trialkyl (2-hydroxyalkyl) ammonium carboxylate: 0.25%) used in the measurement of foaming force in (1) was used at 25°C. Surface tension (dyn/cm) is measured by the drop volume method (Japanese Industrial Standard JIS K3362) at a temperature of . (3) Monitor test Three types of choline surfactant compositions with the above compositions were selected and each was distributed to 10 monitors to evaluate their suitability as kitchen detergents and shampoos, as well as their lathering, detergency, and skin gentleness. A monitor test was conducted with a focus on performance, rinsability, finish, etc. The evaluation results are A (excellent), B (excellent), and C.
The respondents were asked to answer in five grades: (good), D (acceptable), and E (unacceptable), and the final judgment result for each choline surfactant composition was determined by the average value of the 10 responses. Examples 10 to 15 At a temperature of 50°C, choline surfactant compositions containing various types of choline or its homologues and fatty acids constituting trialkyl (2-hydroxyalkyl) ammonium carboxylate were prepared. An oil-in-water (O/W) emulsion was produced by a method in which soybean oil was gradually added dropwise to the dissolved water and emulsified using a homomixer, and the emulsification state was evaluated. The results are shown in Table-2. Example 16 Parts by weight Stearic acid 25 Glycerin 10 Choline 1 Water A mixed solution of ~64 ~ was heated to 60~65°C, and while stirring with a homomixer, the solution heated and dissolved at about 70°C was gradually added to obtain oil-in-water (oil-in-water). An O/W) type emulsion was produced. This emulsion had suitable performance as a vanishing cream.

【table】

【table】 [Brief explanation of drawings]

Figure 1 shows trimethyl (2-hydroxyethyl)
FIG. 3 is a diagram showing an infrared absorption spectrum of ammonium myristate. Also, Figure 2 shows trimethyl (2
-Hydroxyethyl)ammonium myristate is a nuclear magnetic resonance spectrum. FIG. 3 is a diagram showing an infrared absorption spectrum of trimethyl(2-hydroxyethyl)ammonium stearate. Moreover, FIG. 4 is a diagram showing a nuclear magnetic resonance spectrum of trimethyl(2-hydroxyethyl)ammonium stearate.

Claims (1)

[Claims] 1 General formula RCOO [R ¹ R ² R ³ NC(R ⁴ )(R ⁵ )C(R ⁶ )(R ⁷ )OH] (In the formula, RCOO is a fatty acid anion having 6 to 24 carbon atoms. , R ¹ , R ² and R ³ are lower alkyl groups, R ⁴ , R ⁵ ,
R ⁶ and R ⁷ represent a hydrogen atom or a lower alkyl group) A choline-based surfactant composition comprising a trialkyl(2-hydroxyalkyl) ammonium carboxylate as an essential component. .