JPH03169846A - Alkenyl or alkylsinnamic acid anhydride containing sulfonic acid, amide and carboxyl groups in one molecule and salt thereof, cleaner composition containing the same - Google Patents

Abstract

NEW MATERIAL:Alkenyl or alkylsinnamic acid anhydride derivatives containing sulfone, amide and carboxyl groups in the molecule and represented by formula I and II (R is alkenyl or alkyl; R' is H or hydrocarbon) and salts thereof. EXAMPLE:The reaction product of n-tetradecenylsinnamic acid anhydride with N-methyltaurine sodium salt. USE:Cleansing agents which are low irritative and have excellent surface-active performance. PREPARATION:For example, a compound of formula III is made to react with a compound of formula IV to prepare the compounds of formulas I and II, which are, if desired, converted into salts of formula V and/or VI.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to novel alkenyl or alkyl succinic anhydride derivatives and salts thereof that are less irritating and have excellent surfactant ability, and detergent compositions containing the same. [Prior Art] Conventionally, alkyl sulfates (AS), alkyl ether sulfates (AES), a-olefin sulfonates (AOS), etc. have been used as surfactant base materials for shampoos, body shampoos, lotions, etc. However, recently, new products have been developed that not only have foaming and cleansing properties, but also have a natural texture and conditioning effect, are less irritating to the skin and hair, and do not irritate the skin or damage the hair even when used repeatedly. Demand for mild cleaning agents is increasing. In connection with this, N-acyl amino acid type surfactants, sulfosuccinate type surfactants, N-acyl taurine type surfactants, etc. have come to be used. [Problems to be solved by the invention] However, although N-acyl amino acid type surfactants cause less irritation to the skin and have a mild effect, they have insufficient surface activity and poor foaming properties under weak acids. However, the presence of divalent or higher valent metal salts results in insolubility in water, resulting in insufficient hard water resistance, as well as poor odor and color. Although sulfosuccinate type surfactants are hypoallergenic and stable under weak acidity, they have the disadvantage of being susceptible to hydrolysis. N-acyl taurine type surfactants are hypoallergenic and have good hard water resistance, acid resistance, and alkali resistance, but they have the disadvantages of slightly inferior foaming properties, and are very expensive and uncommon. are doing. Furthermore, although the above surfactants are less irritating than conventionally used anionic surfactants, they are still insufficient, and there is a need for surfactants that are even less irritating and have higher surfactant ability. It is being [Means for Solving the Problems] The present inventors have developed a surfactant that has excellent surfactant ability, has a mild effect on the skin and hair, is not subject to any restrictions in use, and is also economically efficient. As a result of intensive research, they discovered that alkenylsuccinic anhydride and aminoethanesulfonic acids easily react and bond through an amide bond, leading to the completion of the present invention. That is, the present invention provides novel alkenyl or alkyl succinic anhydride derivatives and salts thereof represented by the following general formulas (1) and (It) useful as hypoallergenic surfactants, and cleaning agents containing the same. A composition is provided. R R゜l R-CHCONCH2CH2SO,Na ・・・・・・
・ (■) ZeCH, COOH (in the formula, R represents an alkyl group or alkenyl group having 8 to 30 carbon atoms, and R' represents hydrogen or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms) Compound of the present invention (1
) and (II) are produced, for example, by the following reaction. (m) (IV) R゜l R-CHCONCH, CH, So, Na bow CH, COOH (II) R-C}ICOOM 1 base --→ CH, GONCH, CH, So, Na■ R' (v) and R゜1 R-CHCONCH. CH, So, Na1 0H, COOM (Vl) (In the formula, R and R゜ have the above-mentioned meanings, and M is an alkali metal, ammonium, or hydroxyammonium having a hydroxyalkyl group having 2 to 3 carbon atoms, or lower The compound represented by the formula (III), which is a starting material, can be obtained, for example, by subjecting an α-olefin and maleic anhydride to an ene reaction in an inert gas atmosphere by a known method. That is, when dodecene is used as the α-olefin, dodecenylsuccinic anhydride is obtained, and when octadecene is used, octadecenylsuccinic anhydride is obtained. Furthermore, by using an alkylsuccinic anhydride obtained by hydrogenating the above alkenylsuccinic anhydride by a known method, the hue and odor can be improved. That is, dodecenyl succinic anhydride can be obtained by hydrogenating dodecenyl succinic anhydride, and octadecyl succinic anhydride can be obtained by hydrogenating ocdadecenyl succinic anhydride. Further, the compound represented by formula (IV) can be obtained, for example, by reacting sodium oxyethanesulfonate with an alkylamine. That is, when methylamine is used as the alkylamine, sodium N-methylsulfoethylamine (sodium methyltaurate) is obtained, and when n-butylamine is used, sodium n-butyltaurate is obtained. In general, R in these compounds has 12 to 1 carbon atoms.
6 is preferably an alkyl group or an alkenyl group, and R' is preferably a hydrogen or methyl group. The reaction between compound (II[) and (IV)] can also be carried out by bulk charging, but a preferred method is to disperse compound (IV) in a solvent at 70 to 120°C.
, and dropwise add compound (m), or conversely, add compound (m) to
) was dissolved in a solvent and heated to 70-120°C to form a compound (
IV) is added dropwise and reacted. The solvents used in this reaction include alcohols, esters, ketones, glycol ethers, cyclic ethers, and glycols because lipophilic solvents such as aliphatic or aromatic solvents have poor affinity with the reaction products. Hydrophilic solvents such as diethers are preferred, and alkylene glycol dialkyl ethers having no polar group are preferred. After the reaction is completed, the solvent is removed from the reaction mixture by a known method such as drying under reduced pressure to obtain compounds (I) and (■) of the present invention. (1) and (I[) are readily soluble in water, and are neutralized with a known base or an aqueous solution thereof, leading to their salts. The bases used in this case include inorganic bases such as potassium hydroxide, sodium hydroxide, calcium hydroxide, lithium hydroxide, and ammonia, lower alkylamines such as monoalkylamines, dialkylamines, and trialkylamines, and monoethanol. Examples include alkanolamines such as amine, diethanolamine, and triethanolamine, and among them, alkanolamines such as triethanolamine are preferred. [Action] Compounds (1) and (II) of the present invention and their salts have excellent surface activity, are hypoallergenic, have mild effects on the skin and hair, and are resistant to acids, alkalis, and hard water. The reason for this is thought to be as follows. As is clear from the structure of the compound of the present invention, -CO
Since it has an N bond and a -〇〇〇H group and an amino acid skeleton, it has a mild effect on the skin and hair, and has a hair effect. Furthermore, just this amino acid skeleton <-
Since it has So,H groups, it has improved hard water resistance compared to amino acid surfactants with only 1000H groups. On the other hand, it is a sulfosuccinic acid type with 1000H groups and -So, Na groups, and is hypoallergenic and stable even on the weakly acidic side, and does not have an ester bond, so hydrolysis does not occur. Excellent acid and alkali resistance. Furthermore, when used in combination with quaternary nitrogen-containing water-soluble polymers, sulfosuccinic acid forms a complex salt with these polymers, and this complex salt easily precipitates on the hair surface and has a high affinity with the hair, so it is not harmful to the hair. It is easily adsorbed and has the ability to shine and condition hair. [Effects] Compounds (1) and (It) of the present invention and their salts are hypoallergenic and have excellent surfactant ability, have mild effects on the skin and mucous membranes, and have a protective effect on hair. Furthermore, it has excellent hygroscopicity and is useful as a humectant. Therefore, it is suitably used in daily shampoos, body shampoos, hair and skin cleansers for infants, kitchen cleansers for housewives who tend to get rough hands, lotions, moisturizers, and the like. Furthermore, the effect is maintained not only when using tap water but also when using water with high hardness such as ground water, hot spring water, sea water, etc. [Example] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. [Example 1] Diethylene glycol dimethyl ether 600g% N-methyltaurine soda 9 was added to a 2Q three-necked flask.1.
1 g of n-hexadecylsuccinic anhydride was heated to 80°C and mixed with 50 g of n-hexadecylsuccinic anhydride while stirring thoroughly.
The mixture was added dropwise over time and further aged for 2 hours. After the reaction, the solvent was removed by drying under reduced pressure at 80° C. or lower to obtain 240 g of the reactant. The saponification value of the obtained reaction product was 110.3 (theoretical value 1 1 6.1). According to the determination results of the infrared absorption spectrum of this reactant,
The absorption of 1865an-', which corresponds to the carbonyl group of n-hexadecylsuccinic anhydride, and the absorption by the amino group of N-methyltaurine soda disappear, and the reaction results in -○○OH and 100N groups. Equivalent 1720an-'
Absorption of 1650 an-' appeared. Therefore, it was confirmed that this compound has the following formulas (1l) and (II.). l CH, ...... (■,) The obtained reaction product was dissolved in water to a concentration of 50%, further adjusted to pH = 7.0 with triethanolamine, and finally Water was added to adjust the solid content to 40% to obtain an aqueous salt solution. [Example 2] A 2Q three-neck flask was charged with 500 g of diethylene glycol dimethyl ether, and 150 g of n-tetradecenyl succinic anhydride was dissolved therein. This solution was heated to 80° C., and 100 g of N-methyltaurine soda was gradually added dropwise over 3.0 hours. After the addition, the mixture was further aged for 3 hours. After the reaction, the solvent was removed by drying under reduced pressure at 80° C. or lower to obtain a pale yellow reaction product. The saponification value of the obtained reactant was 117.2 (theoretical value 123
．． 2). As in Example 1, it was confirmed from the IR measurement results that the compounds obtained were of the following formulas (I,) and (■,). CH, (CH,),, (?; H=CH-CH, -CHC
OOH1 CH, GONCH, CH, So, Na l CH, ...... (Iyo) CH, ■ ...... (■,) In the same manner as in Example 1, an aqueous solution of triethanolamine salt (solid 40% type content, pH=7.3) was obtained.

[Example 3] In the same manner as in Example 1, a pale yellow reaction product was obtained from n-dodecenylsuccinic anhydride and N-methyltaurine soda.
The saponification value of this compound is 124.7 (theoretical value 131.1
')Met. As in Example 1, it was confirmed from the IR measurement results that this compound had the following formulas (I3) and (■.). CH, ...... (I,) and CH, CH, (CH,), CH=CH-CH, -CH-C
ON-CH, CH, So, NaCH, COOH ...... (■,) An aqueous solution of triethanolamine salt (solid content 40%, pH = 7.2) was obtained in the same manner as in Example 1. Ta. [Example 4] In the same manner as in Example 1 except that 1,3 dioxane was used as a solvent, n-hexadecylsuccinic anhydride and N-methyltaurisodium were reacted to obtain a white compound. The saponification value of this compound was 109.9 (theoretical value 115.6). Similar to Example 1, the compound has the following formulas (■4) and (■,
). CH. ．． (CH.). ．． CH. -CH-C○OHr CH, -CON-CH, CH, So, NaI H (I4) and H CH. (CH.). 4CH, -CHCON-CH. CH
, So, NaCH, COOH (■4) In the same manner as in Example 1, an aqueous solution of triethanolamine salt (solid content 40%, pH=7, Q) was obtained. [Example 5] Foaming power of a triethanolamine salt aqueous solution of the reaction product of the alganyl or alkyl succinic anhydride obtained in Examples 1 to 4 and N-methyl taurine soda was evaluated. Method: Ross Miles method Concentration: 0.25% (solid content) Value: 9 stitches of strain $2: Disodium lauryl polyoxyethylene sulfosuccinate (EOI mole) [Example 6: Shampoo] (Formulation) Example Compound of 15 parts betaine
3 Coconut fatty acid diethanolamide 4 Cationized cellulose 0.2 Water
Total remaining 100.0 parts (evaluation) (i) Foaming power evaluated by Ross Miles method at a concentration of 0.25% (solid content)○... Good (200 mQ or more) Δ...・・・
Normal (150-200mQ) ×・・・Poor (L5
0 mQ or less) (if) Detergent power test Reaction rate 30-34 prepared according to the Oil and Fat Chemistry Association provisional standards
% contaminated cloth, Terg-0-Tometer
The reflectance after cleaning was measured and the cleaning effect was calculated using the following formula. ○: Good Cleaning efficiency 80% or more Δ: Average Cleaning efficiency 60-80% ×: Poor Cleaning efficiency 60% or less ( iff) Skin irritation A manual immersion test was conducted by 10 panelists, and the condition of the skin after the test was visually observed. (Conditions) Sample: Cleaning liquid composition 5% (35°C) Immersion: Conducted twice a day for 20 minutes (Evaluation) O: Good, rough skin, 2 or less people Δ: Fair 〃 3-6 people ×: 7 or more people failed Comparative Example 1: Sodium lauryl ether sulfate (
Comparative Example 2: Sodium lauryl polyoxyethylene sulfosuccinate (EOI moles) [Example 7: Body shampoo] (Formulation) Parts Compound of the present invention 20 Sodium lauryl ether sulfate 11 Coconut fatty acid diethanolamide 4.5 100 parts water (Evaluation) As in Example 6, the body shampoo with the above formulation was evaluated for foaming power, cleansing power, and skin irritation. The results are shown in Table 3. Book 2: Borioxyethylene snolephosuccinate laurinole disodium

Claims (2)

[Claims] (1) The following formulas (I) and (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・(
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・(I
I) One molecule represented by (wherein R represents an alkenyl group or alkyl group having 8 to 30 carbon atoms, and R' represents hydrogen or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms) Alkenyl or alkyl succinic anhydride derivatives containing sulfonic, amide, or carboxyl groups and salts thereof (2) The following formulas (I) and (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula R represents an alkenyl group or an alkyl group having 8 to 30 carbon atoms, and R' represents hydrogen or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms. A cleaning composition containing an alkenyl or alkyl succinic anhydride derivative containing a carboxyl group or a carboxyl group, and a salt thereof.