JPH11315048A - Glyceryl-etherified polyhydric alcohol ether carboxylic acid compound, anionic surfactant and detergent composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having good product storage stability and good lathering even at low temperature, scarcely irritating skins and hairs, having good touches such as good slippery touch on rinsing and good residual touch on skins, and having excellent characteristics as a component for detergents. SOLUTION: A compound of formula I [R<1> is an aliphatic group having an average carbon atom number of 6-30; R<2> and R<3> are each H, CH3 , C2 H5 , CH2 OH or a group of formula II (R<4> is H, CH3 or CH2 COOM); G is CH2 CH(OH) CH2 O or CH2 CH(CH2 OH)O; (m) is an average addition molar number of 1-10; (n) is an average condensation molar number of 1-5; M is H or a salt-forming cation]. For example, hexadecylglyceryl pentaerythritol ether glycolic acid salt. The compound of formula I is obtained by condensing a glycidyl ether with a polyhydric alcohol in the presence of a basic catalyst and subsequently reacting the produced glyceryl-etherified polyhydric alcohol as a raw material with a halogenocarboxylic acid of the formula: XCH(R<4> )COOM (for example, monochloroacetic acid) or its salt in the presence of a basic catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to the present invention, which has good foaming properties even in acidic to weakly alkaline conditions (pH 4 to 8),
A glyceryl etherified polyhydric alcohol ether carboxylic acid compound which is also hypoallergenic to hair, and which is useful as a cleaning component excellent in use feel, such as a slimy feeling upon rinsing and a little feeling of remaining on the skin, The present invention relates to an anionic surfactant comprising the same and a detergent composition using the same.

[0002]

2. Description of the Related Art Conventionally, petroleum anionic surfactants and nonionic surfactants are widely used as components of detergents generally used in households such as clothing, tableware, hair, body, and the like. ing. Recently, surfactants used in the above applications have excellent detergency, foaming power, good foaming feeling during rinsing, a good feeling of use such as refreshing feeling after rinsing, and skin irritation. And a high performance level with multiple functions such as environmental safety. Therefore, to meet such demands,
Developments are being made from both aspects of detergent compositions and surfactants. In the case of the detergent composition, the pH is changed from weakly acidic to neutral to suppress irritation to the skin, while the surfactant can be used under the same conditions, and the cleaning performance, safety, It is selected from the viewpoint of feel and environmental safety.The constituent elements consist of carbon, hydrogen, and oxygen, and there is no problem when discharged to the environment.The terminal hydrophilic group is a carboxyl group, and it has properties similar to soap. Ether carboxylate salts having various chemical structures have been proposed as next-generation surfactants. Nakamura et al., Proceedings of the 35th Symposium on Oil Chemistry,
On page 87, surfactant properties of alkyl glyceryl ether carboxylate represented by the following general formula (2) and application to detergents are introduced.

Embedded image (Wherein, R represents a higher alkyl group, M represents hydrogen or a salt-forming cation) However, in the case of an alkyl glyceryl ether carboxylate, the skin is less irritating and less slimy during rinsing. Although it has a characteristic that it provides a refreshing feel and improves hard water resistance and foaming power as compared with soap, it has a higher kraft point than existing petroleum surfactants, and a detergent composition. In addition, when it is blended at a high concentration, it has a serious problem in practical use that, at low temperatures, not only precipitates are easily formed during long-term storage, but also the detergency decreases. Therefore, in order to be put to practical use, it is not satisfactory, and a surfactant having excellent detergency and foaming power after further improving the craft point has been demanded.

[0003]

Accordingly, the present inventors have studied in detail the relationship between the chemical structure of the ether carboxylate-based surfactant and the surface activity, Kraft point, skin irritation, and the like. By further linking a polyhydric alcohol to glycerin, which is a part of the hydrophilic group, with an ether bond, the skin and hair are less irritating, and not only the Kraft point is lowered, but also the detergency at low temperatures,
It was also found that the foaming power was improved, and the present invention was completed. That is, the present invention has good storage stability and good foaming even under low temperature, has little irritation to skin and hair, and has good feeling of use such as slimy feeling upon rinsing and residual feeling on skin. It is an object of the present invention to provide a glyceryl etherified polyhydric alcohol ether carboxylic acid compound having excellent properties as a detergent component, an anionic surfactant comprising the same, and a detergent composition containing the anionic surfactant. And

[0004]

According to the present invention, there is provided a glyceryl etherified polyhydric alcohol ether carboxylic acid compound represented by the following general formula (1).

Embedded image Further, according to the present invention, there is provided an anionic surfactant comprising the glyceryl etherified polyhydric alcohol ether carboxylic acid compound. Further, according to the present invention, there is provided a detergent composition containing at least one kind of the anionic surfactant.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (1), R ¹
Represents 6 to 30 aliphatic groups, which may contain hydroxyl groups. In the aliphatic group R ¹ ,
It contains a linear or branched alkyl group, alkenyl group, or hydroxyalkyl group. The optimal carbon chain length is greatly affected by the type of the terminal carboxyl group, the pH of the washing solution, and the like. Preferably, from the viewpoint of foaming power and foam stability, an aliphatic group having 10 to 24 carbon atoms, for example, Decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, undecyl, 2-hexyldecyl, 2-octylundecyl, 2-decyltetradecyl, 2-hydroxydecyl, 2-hydroxy A dodecyl group, a 2-hydroxytetradecyl group, a 2-hydroxyhexadecyl group, a 2-hydroxyoctadecyl group and the like are used. These aliphatic groups can be used alone or as a mixture.

R ² and R ³ are H, CH ₃ , C ₂ H ₅ , CH ₂
OH or CH ₂ OCH (R ⁴ ) COOM. The following general formula (3) in the general formula (1)

Embedded image The divalent group represented by represents a polyhydric alcohol residue, in which R ² and R ³ are H, CH ₃ , C ₂ H ₅ or CH ₂ OH, neomethylolpropane, 3 shows polyhydric alcohol residues derived from polyhydric alcohols such as trimethylolethane, trimethylolpropane, and pentaerythritol. Oxyacid derivative group [-CH ₂ OC
H (R ⁴ ) COOM] is obtained when the above-mentioned polyhydric alcohol is reacted with the oxyacid halide [XCH (R ⁴ ) COOM] in a molar ratio of 2 to 3 times. In addition, the oxyacid [HO
CH (R ⁴ ) COOM] includes glycolic acid, lactic acid and malic acid.

G is a glycerin residue, CH ₂ CH
(OH) CH ₂ O or CH ₂ CH (CH ₂ OH) O is shown. m is the average number of condensed glycerin residues G, and represents a number of 1 to 10. Preferably, in terms of detergency and foaming power, 1
３3. n is the average condensation number of the polyhydric alcohol, and represents the number of 1 to 5. The preferred average condensation number is selected depending on the type of the polyhydric alcohol residue, and in the case of a polyhydric alcohol residue derived from relatively less hydrophilic neomethylolpropane, trimethylolethane, and trimethylolpropane, It is 2-3 in terms of detergency and foaming power below, and 1-2 in the case of polyhydric alcohol residues derived from pentaerythritol having relatively high hydrophilicity. R ⁴ is hydrogen, a methyl group or CH ₂ C
Indicates OOM. The oxyacid residue [—CH (R ⁴ ) CO
OM] is a hydrophilic group obtained by removing the hydroxyl group from glycolic acid, lactic acid or malic acid. The type of the oxyacid residue is selected according to the conditions of use and the purpose of use. Anionic surfactants having any oxyacid residue are also excellent in foaming power in a wide pH range from acidic to weakly alkaline, excellent in use feeling such as slimy feeling upon rinsing, feeling of remaining on the skin, It has excellent irritation to hair and skin, especially
Foaming power in high-hardness hard water is excellent in the presence of lactic acid and malic acid as residues, and has a foaming power in acidity of pH 4 to 6, and a builder by having chelating power with alkaline earth metals. The effect is excellent when malic acid is used as the residue.

The counter ion M of the carboxyl group represents hydrogen or a salt-forming cation. Salt-forming cations include alkali metal ions such as sodium, potassium and lithium;
Ions of alkaline earth metals such as calcium and magnesium; ammonium ions; alkylamines, alkanolamines (mono, di, tri-ethanolamine, n-,
Organic ammonium ions derived from organic amines such as iso-propanolamine.

The anionic surfactant represented by the general formula (1) according to the present invention is obtained by using a glyceryl etherified polyhydric alcohol produced by condensing glycidyl ether and a polyhydric alcohol in the presence of a basic catalyst as a raw material. And a halogenocarboxylic acid or a salt thereof in the presence of a basic catalyst. In the reaction of glycidyl ether and polyhydric alcohol, for example,
As shown in the following reaction formula, a polyhydric alcohol is added to the oxirane ring to obtain a formula or a compound of the formula, any of which can be used as a raw material of the anionic surfactant of the present invention. .

Embedded image

A halogenocarboxylic acid or a salt thereof [XCH
(R ⁴ ) COOM] includes monochloroacetic acid, monobromoacetic acid, α-chloropropionic acid, α-bromopropionic acid, monochlorosuccinic acid, monobromosuccinic acid, and salts thereof. Preferably, monochloroacetic acid, α-chloropropionic acid, monochlorosuccinic acid and salts thereof are advantageously used from the viewpoint of economy and reactivity.

The reaction between the halogenocarboxylic acid or its salt and the glyceryl etherified polyhydric alcohol is carried out by heating a mixture of the halogenocarboxylic acid salt and the glyceryl etherified polyhydric alcohol, and gradually adding the basic catalyst aqueous solution under reduced pressure. A method of dropping, a method of heating the mixture of both raw materials and the solid basic catalyst, and reacting the mixture under reduced pressure, to the glyceryl etherified polyhydric alcohol, under heating and reduced pressure conditions,
Any method such as a reaction method in which a halogenocarboxylic acid or an aqueous solution thereof and an aqueous solution of a basic catalyst are gradually dropped can be used.

Examples of the basic catalyst include alkali metal alkoxide, alkali hydroxide, alkali carbonate and the like.
It is selected from the reaction method and the like. Preferably, sodium hydroxide or potassium hydroxide is used in terms of economy and handling. The amount of the basic catalyst to be used is from equimolar to 1.5 moles relative to the halogenocarboxylic acid. The pH during the reaction is preferably maintained at 7 to 13. The reaction can be carried out without a solvent, but in order to reduce the product viscosity in the latter half of the reaction and to evaporate water and make the reaction proceed smoothly, from the beginning of the reaction or from the latter half, hexane is used. , Toluene, xylene, chloroform,
Solvents such as carbon tetrachloride, dioxane, tetrahydrofuran, dimethylformamide, and dimethylacetamide can also be used. The amount of the glyceryl etherified polyhydric alcohol is from 1.0 to 5.
0 is appropriate. The reaction molar ratio of the halogenocarboxylic acid to the glyceryl etherified polyhydric alcohol is selected from the amount of the glyceryl etherified polyhydric alcohol remaining as an unreacted product, the number of moles of the halogenocarboxylic acid added and their reactivity, 0.1 to 2.0 in molar ratio,
Preferably, from the viewpoint of foaming power, reactivity and the like, 0.2 to 1.5.
It is. The reaction temperature is 50 to 120 ° C, especially 60 to 1
It is preferable to carry out in the range of 00 ° C. When the reaction temperature is lower than 50 ° C., the reaction rate is low, and when the reaction temperature is higher than 120 ° C., the product is undesirably colored. The reaction time varies depending on the reaction method and the reaction reagent, but is 1 to 10 hours, preferably 2 to 10 hours.
6 hours.

The reaction product obtained by the above-mentioned reaction contains a small amount of unreacted glyceryl etherified polyhydric alcohol, carboxylate, inorganic salt, etc. in addition to the compound of the above general formula (1). Have been. The reaction product is
By simply adjusting the pH, it can be used as an anionic surfactant with excellent foaming power.However, when using a high-purity product such as a surfactant for liquid washing, solvent extraction, silica gel column chromatography It can also be purified using a known purification method such as

The anionic surfactant of the present invention can be used in combination with existing anionic surfactants, nonionic surfactants, amphoteric surfactants and the like. In this case, the existing anionic surfactant is used for the purpose of further improving the detergency and foaming power. Examples of such anionic surfactants include alkyl sulfates, polyoxyethylene alkyl sulfates, α-sulfofatty acid ester salts, and α-sulfo fatty acid ester salts.
Olefin sulfonates, alkyl or hydroxyalkyl ether carboxylates, N-acylated taurine, N
-Acylated methyltaurine, N-acylated glycine, N
-Acylated aspartic acid, N-acylated sarcosine,
N-acylated glutamic acid, monoalkyl phosphate, alkylamide ether sulfate, fatty acid monoglyceride sulfate, alkyliminodicarboxylate, secondary amide type N-acylamino acid salt, tartaric acid alkylamide, malic acid alkylamide, And citric acid alkylamides. Nonionic surfactants, like anionic surfactants, are used for the purpose of further reducing irritation to the skin and hair, in addition to detergents and foaming power. As such, in addition to glyceryl etherified polyhydric alcohol which is a precursor of the anionic surfactant of the present invention, higher alcohol ethoxylate, higher alcohol ethoxypropoxylate, nonylphenol ethoxylate, fatty acid alkanolamide, sucrose Fatty acid ester, alkyl (poly) glycoside, polyglycerin fatty acid ester, fatty acid 2,3-dihydroxypropylamide, fatty acid polyoxyethylene amide, alkylamine oxide, alkylamidoamine oxide, polyoxyethylene fatty acid ester, methyl or ethyl glycoside, fatty acid ester , Acylglucamide and the like. Amphoteric surfactants are used for the purpose of further improving foaming power and mildness to the skin. Examples of such an amide amino acid type amphoteric surfactant, long-chain alkyldimethylcarboxymethyl betaine, sulfobetaine, imidazolium betaine, glycine type, alanine type amide acid type amphoteric surfactant, carboxybetaine, sulfobetaine, Examples include phosphobetaine, amidoamino acids, imidazolinium betaine-based surfactants, and the like.

When a mixture of the anionic surfactant (A) represented by the general formula (1) and the existing surfactant (B) is used, the mixing ratio (A) / (B) is , By weight ratio, 98/2 to 10/90, preferably 80/20 to
30/70. At a lower mixing ratio, the characteristics of the anionic surfactant of the present invention cannot be sufficiently exhibited. The amount of the anionic surfactant of the present invention in the detergent composition varies depending on the dosage form of the detergent, but in the case of a liquid, 0.5 to 50% by weight of the composition, in the case of a paste, 1-7
0% by weight, and in the case of a solid type, 1 to 80% by weight is suitable.
The pH when the detergent is dissolved in water depends on the type and use of the active agent to be blended, but the preferred range is pH 5 to 8 for shampoo, body shampoo and kitchen detergent, and 7 to 11 for clothing detergent. Is preferred. If the pH is out of the above range, it is not preferable in terms of irritation to the skin and damage to the object to be washed.

The cleaning composition of the present invention may contain, if necessary, known auxiliary components to be added to the cleaning agent. Such auxiliary ingredients include builders, humectants,
Viscosity regulators, preservatives, anti-inflammatory agents, antioxidants, ultraviolet absorbers, sequestering agents, anti-migration agents, antibacterial agents, water-soluble polymer compounds, water-soluble inorganic salts, organic and Inorganic compounds, pearlescent agents, pigments, fragrances, enzymes,
Bleaching agents and the like.

[0017]

According to the present invention, foaming is good even under acidic to weakly alkaline conditions (pH 4 to 8), hypoallergenic to the skin and hair, and furthermore, the skin feels slimy when rinsing, A novel anionic surfactant which is excellent in the feeling of use, such as low persistence, and is useful as a detergent component is provided. Therefore, the detergent composition containing the surfactant of the present invention is a dishwashing vegetable detergent, clothing detergent, shampoo,
It can be widely used as body shampoo, hand soap, cleaning agent for homes, etc.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments.

Example 1 (Synthesis of hexadecylglycerylpentaerythritol ether glycolate) 5 equipped with a vacuum stirrer, a Liebig condenser and a thermometer
A 100 ml four-necked flask was charged with 100 g of hexadecylglyceryl etherified pentaerythritol and 40.2 g of sodium monochloroacetate.
Under a condition of mHg, 35.2 g of a 40 wt% NaOH aqueous solution was dropped and reacted in 2 hours with stirring to remove distilled water. Subsequently, 150 ml of dioxane was added, and the mixture was reacted and aged for 1.5 hours under the same conditions while distilling off water and dioxane. After dissolving the product in pure water, the pH was adjusted to 6.8 with 6N hydrochloric acid, and 329.8 g of a 28.0 wt% aqueous solution of sodium hexadecylglyceryl etherified pentaerythritol ether glycolate (789.8% yield,
Liquid chromatography analysis).

Example 2 (Synthesis of Tetradecylglyceryltrimethylolpropane ether glycolate) The procedure of Example 1 was repeated, except that tetradecylglyceryletherified trimethylolpropane was used instead of hexadecylglyceryletherified pentaerythritol ether. According to Example 1, a 29 wt% aqueous solution of sodium tetradecylglyceryltrimethylolpropane ether glycolate having a pH of 6.5 (yield: 80%, quantitative method is based on Example 1) was obtained.

Example 3 (Synthesis of tetradecylglyceryltrimethylolpropane ether lactate) In Example 1, sodium α-monochloropropionate was replaced with sodium α-monochloropropionate, and tetradecylglyceryl etherified pentaerythritol was used instead of sodium pentaerythritol. Using decyl glyceryl etherified trimethylol propane, a 30 wt% aqueous solution of sodium tetradecyl glyceryl trimethylol propane ether lactate having a pH of 7.5 (yield: 82%, quantitative method is based on Example 1) was obtained according to Example 1. Was.

Example 4 (Synthesis of tetradecylglyceryl trimethylolpropane ether malate) In Example 1, sodium monochlorosuccinate was replaced with sodium monochlorosuccinate, and tetradecyl glyceryl etherified pentaerythritol was used instead of sodium pentaerythritol. Using glyceryl etherified trimethylolpropane, a 25 wt% aqueous solution of sodium tetradecylglyceryltrimethylolpropaneethermalate having a pH of 6.5 (77% yield, quantification method conforming to Example 1) was obtained according to Example 1. Was.

Reference Example 1 A 0.1 wt% aqueous solution of the compound of Example 1 and the comparative compound was prepared, and the solubility was visually determined.

[0024]

[Table 1] ^* C ₁₆ H ₃₃ OCH ₂ CH (OH) CH ₂ OCH ₂ COONa The compound of the present invention was found to have a lower Krafft point and better solubility at low temperatures than the comparative compound.

Examples 5 to 8 and Comparative Examples 1 and 2 The compounds obtained in Examples 1 to 4 were evaluated for foaming power and feeling in use as follows. Table 1 shows the results. Table 1 also shows the results for sodium laurate or sodium polyoxyethylene (P = 3) lauryl ether sulfate for comparison.

(1) Detergency Dirt (tallow / soybean oil = 5/5, weight ratio, about 0.15 g) is adhered to the inner wall of a polypropylene cup having a capacity of 200 ml, and PH 6.5 to 7.5 is applied to each polypropylene cup. 5
180 ml of a 2 wt% aqueous solution (cleaning agent) of each of the sample surfactants adjusted as described above was added, and the rotating blades were rotated in a polypropylene cup for 5 minutes at a temperature of 25 ° C. to wash the inside of the polypropylene cup. The cleaning power of each cleaning agent is as follows: when the value of the cleaning rate (%) calculated by the following formula exceeds 41% (◎), 31 to 40% (○), 11 to 30 (△), 10 to 30 % Or less was evaluated as (x). (2) Foaming force Take 20 ml of a 2 wt% aqueous solution of each sample surfactant adjusted to pH 6.5 to 7.5 in an Epton tube (100 ml).
Mixed dirt (tallow / soybean oil = 5/5)
Is added by 0.2% by weight. Shake 20 times at room temperature for 10 seconds. When the interface between the aqueous solution and the bubbles becomes clear, the bubble height (m
l) was measured. The evaluation was (◎) when the foam height (ml) exceeded 81, (○) for 66 to 80, (△) for 51 to 65, and (×) for 50 or less. (3) Feeling of use 2 w of each sample surfactant adjusted to pH 6.5 to 7.5
A t% aqueous solution was prepared, the sponge was squeezed 20 times in this aqueous solution, and the sensory evaluation was performed on the feeling of sliminess when rinsed with running water and the residual feeling on the skin. The average value of five panelists was calculated, and when the average value was 2.5 or more (◎),
The case of 2.0 to 2.5 was judged as (○), the case of 1.5 to 2.0 was judged as (△), and the case of less than 1.5 was judged as (x). still,
The following criteria were used for evaluation. 3: Excellent 2: Normal 1: Inferior

[0027]

[Table 1]

Next, examples of specific formulations using the anionic surfactant of the present invention as a detergent component will be shown.

Example 9 Detergent composition for tableware vegetables Polyoxyethylene lauryl alcohol (p = 10) 13 (% by weight) Compound of Example 12 12 Amidopropyltrimethylamine oxide laurate 3 Ethanol 5 Dye, flavor appropriate amount Purified water balance This tableware The vegetable detergent had little irritation to the skin, and had good detergency, foaming power, and feel during use.

Example 10 Detergent composition for liquid clothing Alcohol ethoxylate 15 (% by weight) (synthetic secondary alcohol, p = 8) Alcohol ethoxylate 5 (C ₁₂ alcohol, p = 12) Compound of Example 1 7.5 Triethanolamine 3 Sodium chloride 1.5 Ethanol 2 Propylene glycol 3 Purified water Balance This liquid heavy detergent was mild to the skin, and had good detergency and foaming power.

Example 11 Detergent Composition for Liquid Yarn Polyoxyethylene Lauryl Alcohol (p = 10) 10 (% by Weight) Compound of Example 1 5 Lauryl Alcohol Ethoxy Sulfate Monoethanolamine Salt 5 Ethanol 2 Color, Perfume Appropriate Purification Water Balance This yarn detergent had good detergency and foaming power.

Example 12 Shampoo composition Compound 8 of Example 3 (% by weight) N lauroylmethyltaurine Na 8 Coconut fatty acid diethanolamide 2 Alkylimidozolinium betaine 2 Propylene glycol 5 Dye, perfume Appropriate amount Purified water balance It was hypoallergenic to the skin, foamed well, had little slimy feeling during rinsing, and had a good feel upon use.

Example 13 Shampoo composition Compound of Example 4 10% by weight lauroyl N-methyltaurine Na 6 coconut fatty acid diethanolamide 22-decyltetradecyltrimethylammonium chloride 0.2 citric acid qs pigment, flavor qs Purified water Balance This shampoo was hypoallergenic to the skin, had good lathering, had little slimy feeling upon rinsing, and had a good feel to the hair after shampooing.

Example 14 Body Soap Compound of Example 4 10 (% by weight) Na lauroylglutamate 7 Coconut fatty acid diethanolamide 3 Ethylene glycol fatty acid ester 3 Ethanol 3 Propylene glycol 5 Dye, perfume Appropriate amount Purified water balance This body soap is skin There was little irritation, and there was abundant foaming during use, and there was little residual feeling on the skin during rinsing, and the feel during use was good.

Example 15 Hand Soap Compound of Example 2 15 (% by weight) Coconut fatty acid diethanolamide 4 Ethylene glycol fatty acid ester 3 Ethanol 3 Propylene glycol 5 Dye, perfume Appropriate amount Purified water balance This body soap irritates the skin When used, there was abundant bubbling, and there was little residual feeling on the skin during rinsing, and the feel during use was good.

Example 15 Hand soap Compound of Example 2 15 (wt%) Coconut fatty acid diethanolamide 4 Amidopropyl trimethylamine laurate 3 2-decyltetradecyltrimethylammonium chloride 0.3 Ethylene glycol fatty acid ester 0.7 Propylene glycol 5 Dyes, perfume Appropriate amount Purified water balance This hand soap was less irritating to the skin, had fine foaming, had less residual feeling on the skin during rinsing, and had a good feel upon use.

Claims (3)

[Claims] 1. A glyceryl etherified polyhydric alcohol ether carboxylic acid compound represented by the following general formula (1). Embedded image 2. An anionic surfactant comprising the glycerylated polyhydric alcohol ether carboxylic acid compound of claim 1. 3. A detergent composition comprising at least one anionic surfactant according to claim 2.