JPH11335313A - Production of glyceryl ether and cleanser composition containing the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To profitably obtain the subject ether having singular aliphatic groups and useful as a nonionic surfactant by reacting a hydroxy compound with a glyceryl carbonate compound. SOLUTION: This method for producing a glyceryl ether of formula III [(m) is 1-20] comprises reacting (A) a hydroxy compound of formula I [R is a 8-24C aliphatic group; (n) is a number smaller by at least one than (m)] with (B) a glyceryl carbonate of formula II. The reaction is preferably carried out, for example, by reacting 1 mole of the component A with 0.1-6.0 moles of the component B in the presence of a base catalyst (for example, sodium hydroxide), an acid catalyst (for example, sulfuric acid) or a salt catalyst (for example, a phosphate salt) at a reaction temperature of 50-250 deg.C for 0.1-20 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing glyceryl ether useful as a nonionic surfactant and a detergent composition containing glyceryl ether obtained by the method.

[0002]

2. Description of the Related Art Conventionally, as a method for producing (poly) glyceryl ether having an alkyl group, a method of reacting an alkylalkyl glycidyl ether with water or glycerin to open its epoxy ring and a Williamson etherification reaction are used. A general method is to introduce an alkyl group by reacting an alkyl halide or the like with a hydroxyl group of glycerin. However, these methods have several problems and are not yet satisfactory as industrial methods. For example, the above method has the following essential problems. (I) When the alkyl glycidyl ether is reacted with water to open the epoxy ring, polymerization of the alkyl glycidyl ether itself occurs and a large amount of high molecular weight products are produced as by-products. In this case, in order to suppress the by-product of the high-molecular-weight product, the epoxy ring is opened in the presence of a protective group-introducing agent in the reaction system to form a glyceryl ether having a protective group bonded to a terminal hydroxyl group, and then A method of removing this protective group by hydrolysis or hydrogenolysis is known (Japanese Patent Publication No. 6-21087). However, this method
The reaction operation is complicated, and it is not yet a satisfactory industrial method. (Ii) When an alkyl glycidyl ether is reacted with glycerin to open its epoxy ring, a large amount of a product obtained by reacting a plurality of alkyl glycidyl ethers with one glycerin molecule is produced. Such a polyalkylated product having a plurality of alkyl groups has a poor balance between hydrophilicity and hydrophobicity, resulting in poor surface activity. In this case, in order to suppress the by-product of the polyalkylated product, glycerin in which one hydroxyl group is kept in a free hydroxyl group state and all other hydroxyl groups are kept in a protecting group-introduced state is used. A method is known in which an alkyl glycidyl ether is reacted to form a monoalkyl ether compound, and then a protecting group bonded to the monoalkyl ether compound is eliminated (Japanese Patent Application Laid-Open No. 57-197235).
However, such a method is also complicated in its operation, and is not yet satisfactory as an industrial method. On the other hand, the above method has a problem that a large amount of polyalkylated glycerin is produced as a by-product, and it is difficult to obtain an alkyl halide. Therefore, the method has not been satisfactory as an industrial method.

[0003]

SUMMARY OF THE INVENTION The present invention provides a method for industrially advantageously producing glyceryl ether having one aliphatic group, and contains the glyceryl ether obtained by the method as a detergent component. It is an object of the present invention to provide a cleaning composition that performs the following.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, the following general formula (1)

Embedded image RO— (C ₃ H ₆ O ₂ ) m—H (1) (wherein, R represents an aliphatic group having 8 to 24 carbon atoms, and m represents 1)
A glyceryl ether represented by the following general formula (2):

## STR00002 ## RO- (C ₃ H ₆ O ₂ ) n-H (2) (wherein, R has the same meaning as described above, and n represents a number at least one less than m). The following hydroxy compound has the following formula (3)

Embedded image Wherein the glyceryl carbonate represented by the formula is reacted. Further, according to the present invention, there is provided a cleaning composition comprising the glyceryl ether obtained by the above method.

[0005]

According to the present invention, the following general formula (4) (in the above general formula (1), n = 1)

The glyceryl ether represented by RO- (C ₃ H ₆ O ₂ ) —H (4) (wherein R has the same meaning as described above) is obtained by converting glyceryl carbonate to an aliphatic alcohol (ROH). (Hereinafter simply referred to as GC)). The reaction in this case is represented by the following formula.

Embedded image Further, according to the present invention, the following general formula (7) (in the general formula (1), n = 2)

Embedded image The glyceryl ether represented by RO— (C ₃ H ₆ O ₂ ) ₂ —H (7) (wherein R has the same meaning as described above) is the glyceryl ether produced as described above. It is produced by reacting GC with the glyceryl ether of the general formula (4). According to the present invention, as described above,
By performing successively repeating the step of reacting a GC to glyceryl ether, glycerol residue _{- (C 3 H 6 O 2} ) - condensation number are n glyceryl ether of [RO- (C ₃ H
₆ O ₂ ) n-H].

In the aliphatic alcohol (ROH), the aliphatic group includes an alkyl group and an alkenyl group, and has 8 to 24, preferably 8 to 20 carbon atoms.
It is. The glycerin carbonate (GC) can be easily produced by a conventionally known method. For example, it can be obtained by a reaction between glycerin and phosgene or a reaction between epichlorohydrin and a carbonate, and can be produced from glycerin and ethylene carbonate more advantageously than the above-mentioned method (Japanese Patent Application Laid-Open No. 6-329661).

The above reaction proceeds in the presence of a base catalyst, an acid catalyst or a salt catalyst. As the base catalyst, hydroxides, oxides, carbonates, bicarbonates, and the like of alkali metals and alkaline earth metals are used, and a basic ion exchange resin can also be used. Of these, particularly preferred are hydroxides, carbonates and bicarbonates of sodium and potassium. The base catalyst may be used alone or in combination of two or more. Acid catalysts include sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid,
Inorganic acids such as phosphoric acid; organic acids such as p-toluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid, oxalic acid, and acetic acid; solid acids such as silica, alumina, zeolite, kaolin, and heteropolyacid / silica complex; A solid acid in which the above-mentioned inorganic acid is supported on a substance; As the acid-type ion exchange resin, it is preferable to use a sulfonic acid-type resin such as Nafion (DuPont) or Diaion (Mitsubishi Chemical). Salt catalysts include metal salts such as alkali metal salts and alkaline earth metal salts.
In these metal salts, the metal includes Na,
K, Li, Ca, Mg, Ba, and the like. The metal salt may be an inorganic acid salt or an organic acid salt, but is preferably an inorganic acid salt. Salts in this case include halides, phosphates (primary phosphates, secondary phosphates, pyrophosphates), sulfates, borates, carbonates, bicarbonates, and various carboxylate salts And the like. Examples of the salt preferably used in the present invention include LiF, NaF, K
F, CaF ₂ , MgF ₂ , LiCl, NaCl, KCl,
CaCl ₂ , BaCl ₂ , MgCl ₂ , NaBr, KB
r, KI, NaI, Li ₂ SO ₄ , Na ₂ SO ₄ , MgSO
₄ , CaSO ₄ , NaH ₂ PO ₄ , KH ₂ PO ₄ , Na ₂ HP
O ₄ , K ₂ HPO ₄ , Na ₂ B ₄ O ₇ , K ₂ B ₄ O _{7 and the} like.

The amount of the catalyst used is as follows. In the case of a basic catalyst, the amount per 100 g of the starting material (2) of the general formula (2) is
It is 0.01 to 40 g equivalent, preferably 0.1 to 15 g equivalent. In the case of an acid catalyst, it is 0.01 to 40 g equivalent, preferably 0.1 to 15 g per 100 g of the reaction raw material (2).
In the case of a salt catalyst, the reaction material (2) 100 g
0.01 to 30 g equivalent, preferably 0.1 to 15
It is the ratio of g equivalent. The acid catalyst, the base catalyst, or the salt catalyst may be used in a state of being uniformly dissolved in the reaction solution or in a state of being insoluble in the reaction solution. . On the other hand, when used in a state insoluble in the reaction solution, the catalyst can be easily separated and recovered from the product solution after the reaction. When an insoluble catalyst is used in a reaction solution such as an ion exchange resin or a solid acid, the catalyst can be processed into pellets or sheets depending on the reaction method. These solid catalysts can be reused.

The GC is used in an amount of 0.1 to 6.0 mol, preferably 0.5 to 3.0 mol, per mol of the reaction raw material (2).
It is a mole ratio. The reaction between GC and reaction raw material (2)
Mixing and heating the reaction raw material (2) and GC; dropping GC into the heated reaction raw material (2); dropping the reaction raw material (2) into the heated GC;
Is preferred. In the method (1), since a large amount of the reaction raw material (2) and a small amount of GC are present in the reaction solution at the beginning of the reaction, the GC preferentially reacts with the reaction raw material (2) to suppress the reaction between the GCs. In addition, the newly dropped GC reacts with the reaction product of the GC and the reaction material (2), and the reaction proceeds sequentially, and as a result, a desired amount of the GC is reacted with the reaction material (2). Can be. G in this case
The temperature at which C is dropped varies depending on various reaction factors such as the type of the target substance, the reaction temperature, and the reaction amount, but is usually set to a rate at which the entire amount is dropped in 0.1 to 20 hours, preferably 1 to 10 hours. good. 1 to 15 hours after the completion of dropping, preferably 2 to
It is preferable to continue the reaction for 10 hours.
The entire amount of C can be reacted. Reaction temperature is 50 ~
The reaction temperature is 250 ° C, preferably 100 to 210 ° C, more preferably 110 to 180 ° C. When the reaction temperature is lower than 50 ° C, the reaction rate is extremely slow. There are problems such as coloring.

In the above reaction, a nucleophilic substitution reaction between GC and the reaction raw material (2) and a decarboxylation reaction of a carboxylate intermediate produced by the reaction occur, and a desired product is produced. The decarboxylation reaction of the reaction product of the reaction raw material (2) and GC occurs in parallel with the reaction of the reaction raw material (2) and GC, but after the reaction is completed, the reaction is carried out at 50 to 250 ° C., preferably 100 to 250 ° C. It can be completed by heating at 210 ° C. for 30 to 150 minutes, preferably 60 to 120 minutes. The reaction between the reaction raw material (2) and GC and the decarboxylation reaction of the reaction product are carried out under a normal pressure open system,
The method may be performed in any of a closed system under normal pressure, a pressurized system, and a depressurized system, but it is preferably performed in a depressurized system or a normal pressure open system in which generated carbon dioxide is easily removed. And in the case of a normal pressure release system, it is preferable to flow an inert gas such as nitrogen gas to facilitate removal of carbon dioxide. In carrying out the above reaction, no particular reaction solvent may be used, but various reaction solvents may be used as necessary. Examples of the reaction solvent in this case include hydrocarbons such as hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene; cyclic ethers such as dioxane and tetrahydrofuran; nitrogen-containing compounds such as dimethylformamide and acetonitrile; And sulfur-containing compounds such as sulfoxide.

According to the present invention, an aliphatic alcohol or a glyceryl etherified product thereof is used as a reaction raw material (2), and a predetermined amount of GC is reacted therewith sequentially,
A glyceryl ether having a glycerin residue having a desired degree of condensation can be obtained. In this method, the entire reaction can be completed in the same reactor, which is a very advantageous method in terms of equipment cost. In this case, a glyceryl ether having a glycerin residue having a degree of condensation at least two times higher than the degree of condensation of the glycerin residue contained in the reaction raw material (2) can be obtained by a one-step reaction operation. In this method, usually, a plurality of glyceryl ether mixtures having different degrees of condensation n of glycerin residues are obtained. Such a glyceryl ether mixture has a good surface-active activity, and has a nonionic surfactant as it is. It can be used advantageously as an agent. Further, according to the present invention, the condensation of glycerin residues is performed by using a high-purity reaction material (2) prepared in advance and reacting GC at a rate of about 1 mol per mol of the reaction material (2). Glyceryl ethers of one degree can be obtained. In this method, the target glyceryl ether can be obtained with high purity, and the reaction solution can be used as it is as a high-purity nonionic surfactant.

The glyceryl ether containing one aliphatic group R obtained by the method of the present invention is advantageously used as a nonionic surfactant as described above. In the method of the present invention, when a solid catalyst that is easily separated is used as the catalyst, the production of by-products is suppressed, and the purity of glyceryl ether in the obtained product is high. The solid catalyst contained therein can be used as it is as a surfactant by simply separating it by filtration or the like. Therefore, according to the present invention, a nonionic surfactant can be produced at low cost. Of course, when a higher purity glyceryl ether is required, a conventionally known purification treatment may be applied.

The glyceryl ether having an aliphatic group R produced according to the method of the present invention has excellent interfacial tension lowering ability, high detergency as a detergent, and excellent mildness. In order to have the effect of preventing protein denaturation caused by other surfactants, skin, hair cleaners, shampoos, body shampoos, soaps and the like, toothpastes, mouthwashes such as mouthwashes,
It is most suitable as a nonionic surfactant applicable to vegetables, fruits, dishwashing detergents, automatic washing detergents, solid, liquid, and paste detergents for clothing.

The glyceryl ether according to the invention is advantageously used as a detergent composition, if necessary, in admixture with other surfactants. Specific examples of the surfactant used in this case are as follows.

(Anionic surfactant) Alkyl sulfate, polyoxyethylene alkyl sulfate, α-
Sulfo fatty acid ester salt, α-olefin sulfonate, alkyl or hydroxyalkyl ether carboxylate, N-acylated taurine, N-acylated methyl taurine, N-acylated glycine, N-acylated aspartic acid, N-acyl Sarcosine, N-acylated glutamic acid, monoalkyl phosphate, alkyl amide ether sulfate, fatty acid monoglyceride sulfate, alkyl glyceryl ether sulfate, alkyl iminodicarboxylate, secondary amide type N-
Acyl amino acid salts, alkyltartaric acid alkylamides, malic acid alkylamides, citric acid alkylamides and the like can be mentioned.

(Nonionic surfactant) alkyl polyhydric alcohol ether, hydroxyalkyl polyhydric alcohol ether, 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, acyl glucamide and the like.

(Amphoteric surfactant) Amido-amino acid type amphoteric surfactant, long-chain alkyldimethylcarboxymethylbetaine, sulfobetaine, amidopropylbetaine, imidazolium betaine, glycine type, alanine type amidic acid type amphoteric surfactant, Carboxybetaine, sulfobetaine, phosphobetaine, amide amino acid, imidazolinium betaine surfactant and the like.

(Cationic surfactant) Mono- or di-alkyl quaternary ammonium salts, mono- or di-alkyl quaternary ammonium salts having an ether group or ester group, or their hydrochlorides, sulfates, organic acid salts and the like.

A nonionic surfactant (A) comprising the glyceryl ether according to the present invention and another surfactant (B)
When used as a mixture, the mixing ratio (A) /
(B) has a weight ratio of 98/2 to 10/90, preferably 80/20 to 30/70. At a lower mixing ratio, the characteristics of the nonionic surfactant (A) cannot be sufficiently exhibited. The amount of the nonionic surfactant (A) incorporated in the detergent composition varies depending on the dosage form of the detergent, but when it is liquid, it is 0.5 to 50% by weight of the composition, when it is in a paste form, 1 to 70% 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 varies depending on the type and use of the active agent to be blended.
PH 5 for shampoo, body shampoo and kitchen detergent
-8, 7-11 are preferable in the detergent for clothes. The p
Outside the H range, it is not preferred in terms of irritation to the skin and damage to the object to be washed. Further, when used as a commercial or industrial hard surface cleaner, use under alkaline conditions containing an alkaline agent is preferred.

The cleaning composition of the present invention may further contain, if necessary, known auxiliary components to be added to the cleaning composition. 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.

[0021]

Next, the present invention will be described in more detail with reference to examples.

Example 1 Synthesis of dodecyl monoglyceryl ether (C12AGE) 9.4 g (50 m) of dodecyl alcohol was placed in a four-necked flask.
mol) and 2.0 g (10 mmol) of sodium methoxide (28 wt% methanol solution) and heated to 40 ° C. in an oil bath. Subsequently, the pressure is reduced to about 30 mmHg with an aspirator, and methanol is discharged out of the system.
A dropping funnel and a reflux tube were attached to the reaction vessel, 30 mL of dimethylformamide (a dehydrating reagent) was added, and the mixture was heated to 120 ° C. 1.2 g of glycerin carbonate (10 mm
ol) in dimethylformamide (dehydrated solvent) 20 mL
Was added dropwise over 1 hour using a dropping funnel. After completion of the dropwise addition, heating and stirring were continued at 120 ° C. for 3 hours. After the reaction mixture was washed and extracted, it was isolated and purified by silica gel chromatography. As a result, 1.7 g (yield: 65%) of dodecyl monoglyceryl ether (C12AGE) as a target substance was obtained.

Example 2 Synthesis of dodecyl diglyceryl ether (C12AG2E) Dodecyl monoglyceryl ether 1 was placed in a four-necked flask.
3.0 g (50 mmol) and 0.2 g of metallic sodium
(10 mmol) and heated to 40 ° C. in an oil bath. Stirring was continued until hydrogen evolution ceased (about 0.5 hour). A dropping funnel and a reflux tube were attached to the reaction vessel and heated to 120 ° C. Glycerin carbonate 1.2g
(10 mmol) was added using a syringe over 0.5 hours. After the completion of the dropwise addition, stirring was continued at 120 ° C. for 3 hours. The reaction mixture was washed and extracted, and then isolated and purified by silica gel chromatography. As a result, 2.1 g (yield: 61%) of dodecyl diglyceryl ether (C12AG2E) as a target substance was obtained.

Example 3 Oleyl triglyceryl ether (C18F1AG3
Synthesis of E) Oleyl diglyceryl ether (C1
8F1AG2E) and 2 g (50 mmol) of sodium hydroxide and 0.4 g (10 mmol) of sodium hydroxide were charged and heated to 80 ° C. in an oil bath. Subsequently, the pressure is reduced to about 30 mmHg with an aspirator, and water is discharged out of the system. A dropping funnel and a reflux tube were attached to the reaction vessel, 50 mL of dimethylformamide was added, and the mixture was heated to 120 ° C. A solution obtained by diluting 1.2 g (10 mmol) of glycerin carbonate with 20 mL of dimethylformamide was added dropwise over 1 hour using a dropping funnel. After the completion of the dropwise addition, stirring was continued at 120 ° C. for 3 hours. After washing and extracting the reaction mixture,
As a result of isolation and purification by silica gel chromatography, 3.1 g (yield: 63%) of the target substance, oleyl triglyceryl ether (C18F1AG3E), was obtained.

COMPARATIVE EXAMPLE 1 After adding sodium metal (1 g, 0.043 mol) to anhydrous glycerin (380 g, 4.13 mol) under a nitrogen atmosphere, the mixture was stirred at 130 ° C. for 1 hour to dissolve the metal sodium. . Then glycidyl decyl ether (200
g, 0.826 mol) was added dropwise at 180 ° C. for 1 hour, and the reaction was further stirred for 8 hours. After cooling the reaction solution to room temperature, the reaction mixture was dissolved in ethanol and neutralized by treatment with carbon dioxide pellets. After ethanol was distilled off from the reaction mixture, the reaction mixture was subjected to column chromatography on silica gel (1 kg) to give chloroform / methanol (98/98).
Fractionation was carried out using 2) as a solvent, and the obtained fraction was recrystallized from petroleum ether to obtain 95.2 g of dodecyl diglyceryl ether, but the yield was low (35%).

Example 4 The surfactants shown in Table 1 were evaluated for the ability to lower the interfacial tension (vs. soybean oil), the washing performance and the ability to prevent protein denaturation according to the following methods. Table 1 shows the results. <Interfacial tension lowering ability> The liquid-liquid interfacial tension with respect to soybean oil was measured using an automatic surface tension measuring device (K12 / MK4) manufactured by KRUSS. 1 ml of the surfactant aqueous solution was injected with a syringe into a cylindrical glass tube of the measuring device while removing bubbles. Next, 4 μL of soybean oil was injected and the cylindrical glass tube was rotated. The minor axis of the soybean oil droplets formed at this time was measured, and the interfacial tension value γ was determined from the following equation. γ (mN / m) = 3.427 × 10 ⁻⁷ × {0.32 (short diameter)} ³ × (rotation speed) ² × (difference between density of water and oil) ○: γ <0.5 mN / m Δ: 0.5 ≦ γ <0.5 mN / m ×: γ ≧ 1.5 mN / m

<Washing performance> 180 ml of a surfactant aqueous solution (active agent concentration: 0.026 wt%) was added to a polypropylene cup to which artificial fat and oil stain containing oil red was adhered.
, And washed with stirring using a rotating blade for 5 minutes. The solution was discarded, and the cup was air-dried. The cleaning performance was evaluated as follows: て い る, in which the dirt of the cup was uniformly removed: 、, partially removed, △, and not completely removed, ×.

<Protein denaturation preventing ability> Egg albumin aqueous solution (concentration 0.02 wt%, phosphate buffer [pH 7], 81
0 μl) and a surfactant aqueous solution (concentration: 0.1 wt%,
A phosphate buffer solution [pH 7], 90 μl) was placed in a vial, and left at 25 ° C. for 20 hours. Then, the mixture was filtered through a 0.5 μm filter and analyzed by liquid chromatography.
Only the ovalbumin aqueous solution was treated under the same conditions and analyzed by liquid chromatography. Using these results, the protein denaturation rate was determined by the following equation.

(Equation 1) The degree of protein denaturation was indicated by the following notation. ：: Protein denaturation rate 1% or less △: Protein denaturation rate 1 to 10% ×: Protein denaturation rate 10% or more

[0029]

[Table 1]

Next, the dodecyl diglyceryl ether (C12AG2E) of Example 2 or the oleyl triglyceryl ether (C18F1) of Example 3 obtained according to the present invention.
Formulation examples of the cleaning composition containing AG3E) are shown below.

Formulation Example 1 (Cleaning agent for kitchen) (Component) Surfactant (C12AG2E) 20.0% Diethanolamide laurate 3.0% n-Dodecyldimethylamine oxide 1.0% Ethanol 1.0% Yellow 203 No. Fine amount Perfume Fine amount Ion-exchange water balance A kitchen detergent (pH 7.0) having the above composition was produced. This kitchen cleaning agent was excellent in the ability to prevent re-contamination, and there was no stain left on the dishes, and a good cleaning effect was obtained. Further, this kitchen cleaner did not make the user feel rough after use.

Formulation Example 2 (Liquid soap) (Component) Surfactant (C12AG2E) 20.0 (% by weight) Lauryl sulfate sodium salt 10.0 Appropriate amount of perfume / emulsifier Water residue合計 Total 100.0 Liquid soap (pH 7.0) having the above composition was produced. This liquid soap had an excellent feeling in use and exhibited a good cleaning effect. Also, this liquid soap has no irritation to the skin,
It gave a good feeling to the skin after use.

Formulation Example 3 (Shampoo) (Component) Surfactant (C12AG2E) 10.5 (% by weight) Lauryl ethoxy sulfate sodium salt 3.5 Cocoyl diethanolamide 2.0 Sodium sulfate 1.5 Fragrance / emulsion Appropriate amount Water remaining 合計 Total 100.0 Shampoo of the above composition (pH 6. 5) was produced. This shampoo was excellent in the ability to prevent re-contamination, had a high cleaning effect, had no squeaky feeling during use, and was well washed.

Formulation Example 4 (Toothpaste) (Components) Dicalcium phosphate dihydrate 45.5% Glycerin 5.0% Sorbitol 15.0% Sodium carboxymethylcellulose 1.0% Surfactant (C12AG2E) 0.5 % Sodium lauryl sulfate 1.0% Flavor / sweetener Appropriate amount Ion-exchanged water balance A dentifrice having the above composition was produced. This toothpaste had little irritation to the oral mucosa at the time of use, had a high cleaning effect, and had a good refreshing feeling after use.

Formulation Example 5 (Cleaning agent for hard surface) (Component) Surfactant (C18F1AG3E) 7.5% Higher alcohol polyoxyethylene (3) sulfate ester Na salt 3.5% Yellow No. 203 Fine amount Fragrance Fine amount Ion-exchanged water balance A hard surface cleaner (pH 7.0) having the above composition was produced.
When this hard surface cleaner is used to clean hard surfaces such as automobiles, it does not cause discomfort even when it adheres to the skin at the time of use and after use. It gave the sex.

Formulation Example 6 (Residential detergent) (Components) Surfactant (C18F1AG3E) 5.0% Polyoxyethylene (5) dodecyl ether 2.5% Yellow No. 203 Fine perfume Fine ion exchange water Balance Above A residential cleaner (pH 7.0) of the composition was produced. This cleaning agent for home use was excellent in the ability to prevent re-contamination, and a good cleaning effect was obtained. In addition, even when the cleaning agent for a house adheres to the hand, it does not make the user feel rough.

Formulation Example 7 (Cleaning agent for clothes (granular detergent)) (Component) Surfactant (C18F1AG3E) 22.5% Alkylbenzenesulfonic acid K salt 10.0% Alcohol ethoxylate 5.0% Zeolite 22.5% Potassium carbonate 5.0% Sodium silicate 10.0% Sodium carbonate 23.5% Oxygen 0.5% Moisture 6.0% A granular detergent for clothing having the above composition was produced. This granular detergent for clothes was excellent in the ability to prevent re-contamination, and a good cleaning effect was obtained.

Formulation Example 8 (Alkaline detergent for hard surface) (Component) Surfactant (C12AG2E) 5.0% NaOH 22.0% EDTA-4Na 3.0% Moisture 70.0% For hard surface having the above composition An alkaline detergent was produced. This alkaline cleaning agent for hard surfaces showed a good cleaning effect on oil stains.

[0039]

According to the method of the present invention, glyceryl ether can be produced with good yield while suppressing the generation of by-products. The aliphatic group-containing glyceryl ether obtained by the present invention has excellent nonionic surfactant activity.By using this as a detergent component, a detergent composition having excellent mildness and a large detergency can be obtained. Obtainable.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Haruhiko Toda 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation

Claims (2)

[Claims] 1. The following general formula (1): ## STR1 ## RO- (C ₃ H ₆ O ₂ ) m -H (1) (wherein, R represents an aliphatic group having 8 to 24 carbon atoms; Is 1
In the method for producing a glyceryl ether represented by the following formula (2), RO- (C ₃ H ₆ O ₂ ) n -H (2) Has the same meaning as described above, and n represents a number at least one less than m)), and a hydroxy compound represented by the following formula (3): Wherein the glyceryl carbonate represented by the formula is reacted. 2. A detergent composition comprising the glyceryl ether obtained by the method of claim 1.