JPS63161081A - Liquid detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a detergent composition, and more particularly to a detergent composition containing an amidoamine type amphoteric surfactant and a 5-oxo-3-pyrrolidine carboxylic acid derivative. , excellent cleaning power, etc.
Moreover, it relates to a detergent composition that is mild to the skin, hair, and eye mucous membranes.

[Conventional technology]

Conventionally, alkyl sulfate salts, polyoxyethylene alkyl sulfate salts,
Anionic surfactants such as alkylbenzene sulfonates and α-olefin sulfonates have been widely used. However, all of these surfactants have skin irritation properties, although there are differences in degree, and when used repeatedly, they irritate the skin. On the other hand, amidoamine type amphoteric surfactants are known to be extremely mild surfactants with low irritation to the skin and eye mucous membranes, and are used as a component of detergent compositions.

[Problem that the invention seeks to solve]

However, this amidoamine-type amphoteric surfactant has several drawbacks, including poor foaming properties, which is an essential performance required for detergent compositions, and it cannot be used as the main surfactant for detergent compositions. It was difficult to use. Therefore, there has been a demand for improving the performance of cleaning compositions containing amidoamine type amphoteric surfactants while taking advantage of their properties.

The present inventors have conducted intensive research into detergent compositions using amidoamine type amphoteric surfactants in order to eliminate the above-mentioned drawbacks, and as a result, unexpectedly, they have found that they also contain 5-oxo-3-pyrrolidinecarboxylic acid derivatives. The present invention was completed based on the discovery that the inherent characteristics of amidoamine-type amphoteric surfactants, which are low irritation to the skin, would not change if incorporated into the detergent composition, such as the lack of foaming properties, which are the drawbacks of the detergent composition. did.

That is, the present invention comprises the following components (A) and (B)
35% by weight of the following general formula (I) or (If) [wherein R
1 and R3 each represent a saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms, R2 and R4 represent a group -CH2COOM or -C
H2CH2C00M (where M represents hydrogen, alkali metal or alkanolamine), R5 is hydrogen or the group -CH2COOM or -CHzCH2COOM
(M has the meaning described above)] One or more amidoamine type amphoteric surfactants represented by (B) 1 to 17.5 fold flD following general formula (Ill) (wherein R6 represents a saturated or unsaturated hydrocarbon group having 8 to 20 carbon atoms, and M has the meaning described above.
A liquid cleaning composition containing an oxo-3-pyrrolidinecarboxylic acid derivative is provided.

Among the amidoamine type amphoteric surfactants which are component (A) of the present invention, preferred specific examples of those represented by general formula (I) include N-lauroyl-N'-carboxymethyl-N'-(2-hydroxy ethyl) ethylenediamine, N-lauroyl-N'-lupoxyethyl-N'-
(2-hydroxyethyl)ethylenediamine, N-myristoyl-N'-carboxy)fk-N'-(2-hydroxyethyl)ethylenediamine, N-myristoyl-
N'-carboxymethyl-N'-(2-hydroxyethyl)ethylenediamine, N-valmitoyl-N'-carboxymethyl-N'-(2-hydroxyethyl)ethylenediamine, N-valmitoyl-N'-carboxyethyl-N '-(2-hydroxyethyl)ethylenediamine and salts thereof are included. Moreover, the general formula (II
), N-lauroyl-N-(2-hydroxyethyl)-N'-carboxymethylethylenediamine, N-7uroyl-N-
(2-hydroxyethyl)-N', N'-bis(carboxymethyl)ethylenediamine, N-2uroyl N-(2-hydroxyethyl)-N', N'-
His(carboxyethyl)ethylenediamine, N-myristoyl-N-(2-hydroxyethyl)-N'-carboxymethylethylenediamine, N-myristoyl-
N-(2-hydroxyethyl)-N', N'-bis(carboxymethyl)ethylenediamine, N-myristoyl-N-(2-hydroxyethyl)-N',
N'-bis(carboxyethyl)ethylenediamine, N
-Valmitoyl-N-(2-hydroxyethyl)-N'
-carboxymethylethylenediamine, N-valmitoyl-N-(2-hydroxyethyl)-N', N'-bis(carboxymethyl)ethylenediamine, N-valmitoyl-N-(2-hydroxyethyl)-N', N'
-Bis(carboxyethyl)ethylenediamine and salts thereof.

Examples of the salt include alkali metal salts such as sodium salts, alkaline earth metal salts such as magnesium salts, alkanolamine salts such as triethanolamine salts, and ammonium salts. In addition, when these salts are used, they tend to contain inorganic salts as contaminants, but if some or all of these inorganic salts are removed, the amount of contaminant inorganic salts in the final liquid cleaning composition is 1% by weight (hereinafter referred to as 1% by weight). It is preferable to use a desalted amidoamine type amphoteric surfactant having the following properties (simply indicated by H).

Desalted amidoamine-type amphoteric surfactants can be prepared by solvent extraction, electrodialysis, and other methods, but in particular,
The secondary amidoamino product represented by the following general formula (Ia) is made into a salt of ammonia or triethanolamine, and the amount of contaminant inorganic salts in the final liquid detergent composition is adjusted to 1%, which is water-soluble and concentrated inorganic. This is preferred because 0.05 to 10% of polymers insoluble in the solution can be easily blended.

The polymers that are water-soluble and insoluble in concentrated salt solutions include cationic cellulose, cationic starch, diallyl 4
Cationic polymers that show conditioning properties for the skin and hair fibers, such as class ammonium salt homopolymers; Anionic polymers that show viscosity-thickening properties, such as alginic acid, carboxymethylcellulose, and carboxyvinyl polymers; Furthermore, hydroxyethylcellulose, polyvinyl alcohol, A nonionic polymer such as polyethylene oxide that has thickening properties and improves the feel of the skin and hair.

Among the 5-oxo-3-pyrrolidinecarboxylic fermentation conductors as component (B), preferred are N-lauryl-5-oxo-3-pyrrolidinecarboxylic acid, N-
myristyl-5-okino-3-pyrrolidinecarboxylic acid,
Examples include N-palmityl-5-oxo-3-pyrrolidinecarboxylic acid and salts thereof. In the cleaning composition of the present invention, the amount of component (A) is 5 to 35%, preferably 10 to 30%, and the amount of component (B) is 1 to 17%.
．． 5%, preferably 1-15%.

The thus obtained liquid detergent composition of the present invention may further contain known optional ingredients, such as higher fatty acid salts, alkylamine oxides, fatty acid alkanolamides; feel improvers such as squalene and lanolin; inorganic and Organic salts, diluents, fragrances, pigments, bactericides, viscosity modifiers, solubilizers, preservatives, water-soluble polymer compounds, and the like can be blended.

〔Effect of the invention〕

The detergent composition of the present invention described above has improved foaming properties such as foaming properties, which were disadvantageous to amidoamine type amphoteric surfactants. Therefore, cleaning agents that are required to be less irritating to the skin, mucous membranes, etc., such as hair for infants,
It can be advantageously used as a skin cleanser, wool for housewives who tend to get rough hands, kitchen detergent, daily shampoo for people who wash their hair every day, etc.

〔Example〕

Next, the present invention will be further explained with reference to Examples and Synthesis Examples.

Synthesis Example 1 Into a four-bottle flask equipped with a stirrer, condenser, dropping funnel, and temperature gauge, put 268F (1 mol) of 1-hydroxyethyl-2-laurylimidacillin, 90% of water, and 22% of sodium hydroxide. The temperature was raised to 80° C. with stirring, and stirring was continued at that temperature for about 2 hours to open the ring of imidacillin. Next, separately prepared sodium monochloroacetate 233
A solution of r (2 mol) and 2347.2 t of water was dropped into this container over about 1 hour. The solution temperature during dropping is 70~
It was kept at 80°C. Following this, add another 200 ml of 40% sodium hydroxide aqueous solution. was added dropwise over 4 hours at the same temperature. After dropping, ripening is performed at a temperature of 75 to 80°C, and N-
An approximately 12% aqueous solution of lauroyl-N'-2-hydroxyethyl-N'-sodium carboxymethylethylenediamine was obtained. After cooling this solution, 35% salt r1!213
．． 8F was added dropwise over about 3 hours. In this way, a 12% aqueous solution 33549 of N-lauroyl-N'-2-hydroxylethyl-N'-sodium carboxymethylethylenediamine hydrochloride represented by the following formula was obtained. This solution is a light brown viscous liquid, and its 1% aqueous solution has a pH of 2.
．． It was 5.

The aqueous solution 33549 thus obtained was subjected to electrodialysis.

In the electrodialysis method, an anion exchange membrane (C) is used in Figure 1.
and N-lauroyl-N'-2-hydroxyethyl-N' in a compartment (organic substance) sandwiched between cation exchange membranes (A).
-2-Hydroxyethyl-N'-sodium carboxymethylethylenediamine hydrochloride solution, 1% saline solution in the adjacent compartment (electrolyte compartment), and 3% sodium sulfate solution as polar solution were circulated. This was done by pouring a liquid and applying a direct current. The electrodialysis apparatus used in this synthesis example was equipped with 10 negative and positive ion exchange membranes of 0.02 rl each. Also, the applied current has an initial current density of 1.5 amperes/dn? The current was applied for 15 hours. The final current density after 15 hours is 0.1 ampere/dn? Met.

After performing electrodialysis in this manner, water was completely removed by drying under reduced pressure to obtain white powder crystals. Analysis of the amine value, AV, and IRX NMR of this product confirmed that N-yuroyl-N'-2-hydroxyethyl-N'-carboxymethylethylenediamine was produced. The purity of the acid form is 97% according to NaXCL analysis,
The amount of salt is N-lauroyl-N'-2-hydroxyethyl-N'-carboxymethylethylenediamine 100
It was 1.4 t (0,024 mol) with respect to F. Furthermore, as a result of recrystallizing this crystal with ethanol-acetone and conducting elemental analysis, it was determined that it was the desired acid represented by the following formula.

The elemental analysis results are shown below.

The salt content of the obtained product was 0.125' or less per 100 t of the target acid.

Dissolve this acid in water to the highest concentration possible, and add triethanolamine or concentrated ammonia water to a pH of 7.0.
It was added dropwise to obtain an aqueous solution of the neutralized product, which was used in the following examples.

Synthesis Example 2 2689 (I mol) of 1-hydroxyethyl-2-laurylimidacillin, 902 of water, and 22 of sodium hydroxide were placed in a four-bottle flask equipped with a stirrer, a condenser, and a dropping funnel thermometer, and the mixture was stirred while stirring. The temperature was raised to 80° C., and stirring was continued at that temperature for about 2 hours to open the ring of imidacillin. Next, separately prepared sodium monochloroacetate 233
5' (2 moles) and water 427. A solution of Of was charged into this container. Next, 40% NaOH aqueous sodium hydroxide solution 2002 was added dropwise over 4 hours while maintaining the temperature of the solution at 70 to 80°C. After finishing dropping, further heat to 75-80℃
A about 30% aqueous solution of N-lauroyl-N'-2-hydroxyethyl-N'-sodium carboxymethylethylenediamine was obtained. Triethanolamine 149,29 (1 mole) was added to this solution and the solution was cooled. The solution was a light brown liquid with a pa of about 9.

The solution thus obtained was subjected to electrodialysis.

In the electrodialysis method, in Fig. 1, anion exchange membrane (A)
and a compartment sandwiched between cation exchange membranes (C) (organic substances)
N-lauroyl-N'-2-hydroxyethyl-N'
- A mixed solution of sodium carboxymethyl ethylene diamine and triethanolamine was circulated through the adjacent compartment (electrolyte chamber), 1 t NaCl water was passed through the adjacent compartment (electrolyte chamber), and 3 ts NaCl water was circulated as the polar liquid, and a DC current was applied. This was done by applying . At this time, 35% HCj21 was added to this mixed solution.
Electrodialysis was performed while adding 3.8r (2.05 mol) evenly over about 4 hours.

In addition, the electrodialyzer used in this synthesis example was one sheet of 0,02
It has 10 each of RL negative and positive ion exchange membranes. Also, the applied current has an initial current density of 2 amperes/d
d, and electricity was applied for 12 hours. Final current density after 12 hours is 0.1 ampere/drr! Met.

A 35% solution of N-lauroyl-N'-2-hydroxyethyl-N'-triethanolaminocarboxymethylethylenediamine was thus obtained. From the analysis of Na and triethanolamine in this product by liquid chromatography,
98 counterions have been exchanged 1? r, confirmed. Furthermore, from the Ct analysis, N-lauroyl-N'-2-hydroxyethyl-N'-totritanolaminocarpoxymethylethylenediamine 143P (100
5') 1.43%! 0.024 mol). A portion of the obtained product was dried under reduced pressure, and IR analysis confirmed that it was the above substance.

Synthesis Example 3 In a four-bottle flask equipped with a stirrer, condenser, dropping funnel and thermometer, 268 P (I mol) of 1-hydroxyethyl-2-laurylimidacillin and 90 mol of water were added. and 2F of sodium hydroxide, the temperature was raised to 80° C. with stirring, and stirring was continued at that temperature for about 2 hours to open the ring of imidacillin. Next, separately prepared sodium monochloroacetate 233F
(2 mol) and water 4272 was charged into this container. Next, while keeping the temperature of the solution at 70-80°C,
1 NaOH sodium hydroxide aqueous solution 200? was added dropwise over 4 hours. After completion of the dropwise addition, ripening was further carried out at a temperature of 75 to 80°C to obtain a water bath solution of about 3096 N-lauroyl-N'-2-hydroxyethyl-N'-sodium carboxymethylethylenediami/.

The solution thus obtained was subjected to electrodialysis.

In Figure 1, the electrodialysis method is performed using anion or dialysis (A).
and in a compartment sandwiched between cation exchange membranes (C) (organic storeroom)
N-lauroyl-N'-2-hydroxyethyl-N'
- A solution of sodium carboxymethylethylenediamine was circulated through the adjacent compartment (electrolyte chamber), 1% NaCl water was passed through the adjacent compartment (electrolyte chamber), and 3% sodium sulfate solution was circulated as the polar solution, and a DC current was applied. Ta. At this time, electrodialysis was performed while adding 20% NHaCt535f (2,0 morph) evenly over a period of about 4 hours to this mixed solution.

In addition, the electrodialyzer used in this synthesis example was one sheet of 0,02
10 negative and positive ion exchange membranes each are arranged.The applied current has an initial current density of 2 amperes/
dttl', the current was turned on for 12 hours. The final current density after 12 hours was 0.1 Amps/d/.

An approximately 20% solution of N-lauroyl-N'-2-hydroxyethyl-N'-ammoniocarboxymethylethylenediamine was thus obtained. Analysis of Na and N% of this product indicates that 95% of counterions have been exchanged, and C
From the analysis of t, N-lauroyl-N'-2-hydroxyethyl-N'-7moniocarboxymethylethylenediamine 1052 (1002 as acid form, Na
It was confirmed that C1 was 2.1% (0,036 mol).

In addition, a part of the obtained product was dried under reduced pressure and confirmed to be the above substance by IR analysis.

Example 1 A cleaning composition having the composition shown in Table 1 was prepared, and its foaming power was measured. Also, the appearance of the obtained foam was
In addition to the creaminess, skin irritation was also evaluated. The results are also shown in the same table.

(Measurement method) Measuring conditions and method for foaming power: Add 0 lanolin as an artificial stain to a 1% aqueous solution of sample detergent.
．． 5%, and 10 rotations at 40℃ with a flat propeller.
The mixture was stirred in a cylinder for 5 minutes at 0.00 rpm and reversed every 5 seconds, and the volume of foam was measured 30 seconds after the stirring was completed.

Appearance of foam: Sample detergent 12 was applied to mold 202, and the appearance of the foam produced after lathering for 1 minute was evaluated based on the following criteria.

O: The appearance of the foam is creamy.

Δ... It's normal.

×... I Not good.

Irritation to the skin: Patch test adhesives impregnated with 0.1 ml of aqueous solution of sample cleaning agent were applied to 20 subjects for 24 hours, and irritation was determined 24 hours after removal of the adhesive. and evaluated based on the following criteria.

O: Out of 20 people, the number of people who showed erythema was 2 Å or less.

Δ: Out of 20 patients, the areas that showed erythema were 3 Å or more and 10 Å or less.

x: Out of 20 people, those who showed erythema were 11 Å or more.

(Results) As is clear from Table 1 below, the product of the present invention was found to have excellent foaming properties and less irritation to the skin.

Example 2 Shampoo Compositions: Shampoo compositions A, B, and C having the following compositions were produced, and a hair washing test was conducted on 20 long-haired women to compare and evaluate their sensory evaluations. The results are shown in Table 2.

Shampoo A (product of the present invention): Preservative 0.1% Fragrance 0.3% Pigment
trace amount of water
Balance (pH 6,5) Shampoo B (comparative product): Lauric acid jetanolamide 3 preservatives
0.1% fragrance
0.3% dye
trace amount of water
Balance (pH 6,5) Shampoo C (comparison product): Preservative 0.1 III
Fragrance, Group 0.3 Pigment, Trace amount of water, Rose (pH 6,5) Table 2 Examples 3 to 5 The following shampoos, detergents, and detergents for tableware and cooking utensils are all irritating to the skin. It was extremely weak and had good cleaning properties.

Example 3゜Shampoo: (Synthesis Example 2) 10% by weight Lauric acid jetanolamide 1 fragrance 9 pigments (appropriate t)
Water total 10
0 (pH 7,2) Example 4゜Wool/Light Detergent: (Synthesis Example 3) Lauryl dimethylamine oxide 5 Methylcellulose 0.5
Ethyl alcohol 8 fragrances (appropriate amount) Water 1 total
00 Example 5〜Cleaning agent for tableware cooking utensils: (Synthesis Example 2) 15% by weight N-myristyl-5-oxo-3-pyrrolidinecarboxylic acid sodium salt 5a-olefinsulfonic acid triethanolamine salt (average carbon number 1
2) 5-lauric acid diethanolamide 2-ethyl alcohol
8 Fragrance 9 Pigment 8 J Glimpse
(appropriate amount) water
Total 100 Example 6 The anti-dandruff shampoo composition shown below had extremely low irritation to the skin and also had good anti-dandruff effects.

(Synthesis Example 2) 10% by weight Lauric acid jetanolamide 1 Viractone auramine (Octovirox) 1 Ethyl alcohol 2 Fragrance 1
Pigment (appropriate water)
Total 100 Examples 7゜The following bathroom cleaning agent exhibits good cleaning properties and efficiently removes soap scum that has adhered to bathtubs and the like.

(Synthesis Example 1) Sodium chloride 0.15 Citric acid 0.7 Water
Total 100

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an example of an electrodialysis tank used in a synthesis example. that's all

Claims (1)

[Claims] 1. The following components (A) and (B) (A) 5 to 35% by weight of the following general formula (I) or (II)
▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R_1 and R_3 each represent a saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms, R_2 and R_4 are groups -CH
_2COOM or -CH_2CH_2COOM (where M represents hydrogen, an alkali metal or an alkanolamine), and R_5 represents hydrogen or a group -CH_2COOM or -CH_2CH_2COOM (M has the above meaning)] One or more surfactants, (B) 1 to 17.5% by weight of the following general formula (III) ▲ Numerical formula, chemical formula, table, etc. ▼ (III) (In the formula, R_6 is carbon number 8 A liquid cleaning composition containing a 5-oxo-3-pyrrolidinecarboxylic acid derivative represented by: