JPS6375096A - Detergent composition - Google Patents

Abstract

(57) [Abstract] 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 cleaning composition, and more particularly to a cleaning composition containing a specific N-
This invention relates to superior detergent compositions based on acyl-N-hydroxyalkyl chrysins.

[Conventional technology and problems]

Naturally, cleaning products must have excellent cleaning properties such as detergency and foaming power, as well as detergents for cleaning the human body (shampoo, body shampoo, etc.), and detergents for tableware and cooking utensils. Cleaning agents, woolen detergents, and other cleaning agents that come into direct contact with the skin are additionally required to have low irritation to the skin and to the eyes.

The surfactants that are the main components of these cleaning agents are mainly soaps (fatty acid salts), linear alkylbenzene sulfonates (LAS), alkyl sulfate salts (As), and polyoxyethylene alkyl X--f A/ sulfuric acid-r-
Anionic surfactants such as ster [(AES), α-olefin sulfone rR salt (AO8), etc. are used. However, although anionic surfactants have good detergency, they are irritating to the skin and eye mucous membranes, and cannot be said to be the best main component surfactants for such detergents. Ten thousand,
Monoalkyl phosphates, N-acyl glutamic acids, and N-acyl phosphates have been proposed as hypoallergenic surfactants.
N-acylamino acid salts such as N-alkyl-β-alanine 4% N-acyl-N-alkylglycine salts are less irritating, but have the inherent performance of detergents such as hard water resistance, foaming properties, and detergency, and are economical. However, there were problems in formulation.

In addition, soap (fatty acid salt) produces lime soap (scum) which is insoluble in water when divalent or higher metal ions, such as calcium ions, are present. The same applies to N-acyl amino acid salts. This scum adheres to the items being washed and the washing tub when washing, and to the bathtub, washing tub, tiles, skin, hair, etc. when taking a bath, causing dirt to re-adhere to the items being washed and making the bathing environment unclean. This causes problems such as

Therefore, there has been a strong need for a cleaning agent that is hypoallergenic, has high cleaning power, and is resistant to hard water.

[Means for solving problems]

Under such circumstances, the present inventors have conducted intensive research to solve the above problems, and have found that by using specific N-acyl-N-hydroxyalkylglycines as a base, they have low irritation, high cleaning power, and The inventors completed the present invention by discovering that a detergent composition with excellent foaming properties and hard water resistance could be obtained.

That is, the present invention is based on the general formula (1) (wherein RCO represents a saturated or unsaturated aliphatic i1!2 residue having a prime number of 8 to 18, and X represents a hydroxyalkyl group having 1 to 4 carbon atoms). The present invention provides a cleaning composition containing one or more of the following N-acyl-N-hydroxyalkylglycines or salts thereof.

Among the N-acyl-N-hydroxyalkylglycine represented by the general formula (1) or its salt, which is the base of the cleaning composition of the present invention, preferred specific examples of the group represented by RCO include lauroyl, myristoyl, Valmitoil,
Examples include stearoyl, oleoyl, instearoyl, and coconut oil fatty acid residues. Examples of the group represented by X include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, and the like. In addition, as the salt of N-acyl-N-hydroxyalkylglycine (1), sodium,
Alkali metals such as potassium; alkaline earth metals such as calcium and magnesium; ammonium: If element a
Examples include alkanolamines having 1 to 3 hydroxyalkyl groups; alkyl-substituted ammoniums having 1 to 3 carbon atoms; and salts with basic amino acids such as lysine and arginine. Among these, N-lauroyl-N-(3-hydroxypropyl)glycine, its sodium salt, and its triethanolamine salt are particularly preferred.

N-acyl-N-hydroxyalkylglycine (1) or a salt thereof is produced, for example, according to the following reaction formula.

CH) (1) (wherein R and X have the same meanings as above) That is, the compound (+ ) is produced, the reaction is carried out, for example, by adding fatty acid chloride (1) dropwise at room temperature while adjusting the aqueous solution of N-hydroxyalkylglycine (p) to 110-12 with an aqueous potassium hydroxide solution. .

Fatty acid chloride (1) can be obtained by reacting the corresponding fatty acid with, for example, phosphorus trichloride. Further, N-hydroxyalkylglycine (1) can be obtained, for example, by dropping an appropriate amount of an aqueous monochloroacetate aqueous solution into an aqueous alkanolamine solution and heating under reflux for several hours after the addition (J, Amer.

Ch@m, See, 78*172+ (1956)).

The amount of N-acyl-N-hydroxyalkylglycine (1) or its salt added to the cleaning composition of the present invention varies depending on the form of the cleaning agent, the acyl group, and the type of salt; When using, 5 to 5 when using a liquid cleaning agent.
50% by weight (hereinafter simply referred to as %), preferably 15% to 80% in the case of a paste-like cleaning agent. In either case, it is substantially balanced with water and purified using an appropriate acid or alkali.
It is also possible to make solid or powdered products by using an excipient containing 4 H as necessary.

In addition, N-acyl-N-hydroxyalkylglycine (
1) or a salt thereof, compared to anionic or amphoteric surfactants that have traditionally been used as main cleaning active ingredients.
When used at a ratio of /20 to 1/1, it has the effect of enhancing foaming. As these anionic surfactants, alkyl sulfates, alkyl ether sulfates, alpha olefin sulfonates, alkyl phosphoric acids or alkyl ether phosphates, sulfosuccinate ester surfactants, etc. are used, and as amphoteric surfactants, , imidacillin-based amphoteric surfactants, etc. are used.

Particularly preferred are sodium alkyl ether sulfate and imidacillin type amphoteric surfactants. These anionic or amphoteric surfactants are present in liquid detergents at a concentration of 5-50%.
In the case of pasty cleaning agents, it is used in a proportion of 15 to 80%, and in the case of solid or powder, it is used in a proportion of 50 to 99%.

In addition to N-acyl-N-hydroxyalkylglycine (1) or its salt, the cleaning composition of the present invention includes alkanolamide of higher fatty acid, N-acyl amino acid salt, N-
Auxiliary cleaning active ingredients commonly used in cleaning agents, such as amphoteric surfactants such as alkyl amino acid salts, alkyl amine oxides, betaines, sulfobetaines, and hydroxysulfobetaines, are added to the range of 0 to 10% without impairing their performance. It can be blended within a range. Additionally, fragrance if necessary.
Medicinal agents such as pigments, humectants, preservatives, antioxidants, thickeners and anti-dandruff agents, bactericides, anti-inflammatory agents, vitamins, etc. can be added.

[Effect]

Hard water resistance of N-acyl-N-hydroxyalkylglycine l) or its salt, which is the base of the cleaning composition of the present invention,
The mechanism of the foaming detergency-improving effect is estimated as follows.

In general, surfactants fully demonstrate their surfactant ability when used at temperatures above the melting point of the surfactant water-use solid, that is, the Kraft temperature, and anionic surfactants also have a high Krafft point. Therefore, there are often restrictions on usage conditions.

In particular, the presence of divalent or higher metal ions, such as calcium ions, causes counterion exchange in the surfactant and significantly increases the Krafft point. It precipitates in water as a water-use solid such as, or adheres to the items to be washed, and loses its surfactant ability. Therefore, in order to improve hard water resistance, it is necessary to lower the kraft point of the surfactant calcium salt to below the operating temperature, thereby achieving good foaming properties and detergency even in hard water.

The point will be higher.

On the other hand, N-acyl-N-alkyl amino acid salts that have lost intermolecular hydrogen bonding properties by replacing the hydrogen atom in the peptide 1 bond with an alkyl group, for example, N-acylsarcosine 4. Although the Kraft point of N-acyl-N-methyl-p-alanine salts etc. decreases, in the presence of divalent gold and ions such as calcium ions, 2 moles of surfactant per 1 mole of calcium ions decreases. As a result of association, they appear to be diacyl-type, and their hydrophobicity becomes too strong, making it impossible for them to be dissolved in water in the form of micelles, and they aggregate with each other to form scum, making them ineffective as detergents.

The N-acyl-N-hydroxyalkylglycines of the present invention reduce the crystallinity of surfactant water solids by introducing a highly sterically hindered N-hydroxyalkyl substituent into the peptide bonding moiety. In addition to significantly lowering the Krafft point, even if divalent gold 11 is formed in the calcium-based ring, it dissolves in a micellar form due to the hydrophilicity provided by the hydroxyl group, so it exhibits sufficient surfactant ability even in hard water.
It is estimated that good foaming properties and detergency can be obtained.

〔Effect of the invention〕

According to the present invention, it is possible to obtain a detergent that is extremely hard water resistant, hypoallergenic, and has excellent detergency, so it can be used as a kitchen detergent for housewives who are prone to dry hair and skin. It is suitable for use as a daily shampoo for people who wash their hair every day.

Furthermore, it is suitable as a hypoallergenic beauty shampoo for people who have to come into contact with shampoo for a long time due to their occupation.

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〕

Next, the present invention will be explained with reference to reference examples and examples.

Reference example 1 3-amino-1-propatol 250? and 50,054 ml of water, and added 30 ml of sodium monochloroacetate from the dropping funnel while stirring at room temperature.
And water 100? The mixture was added dropwise over about 1 hour.

After the addition was completed, the reaction mixture was heated at 90-100°C for another 3 hours.
The reaction was completed by heating under reflux. Next, 30% of a 30% aqueous sodium hydroxide solution was added, and water and unreacted 3-amino-1-propatol were distilled off under heating and reduced pressure. 100% ethanol in the residue? Add 500ml of acetone, stir thoroughly and make sure it is dissolved, then add 500ml of acetone. added. After cooling, the reaction product precipitated in the reactor was collected door to door, the solvent was distilled off under reduced pressure, and N-(3-hydroxypropyl)glycine sodium salt 40? I got it.

IR(KBr)cWl-': 3100-3500(
WHH, l'□H), 2850-2950 (1'cH,
), 1600.1400(ν(0), 1060 +211A) N-( obtained in (1)
3-Hydroxypropyl) glycine sodium salt 35?
And water 100? and lauric acid chloride 52? from the dropping funnel while stirring at room temperature. was added dropwise over about 1 hour. During this time, a 25% aqueous sodium hydroxide solution was added dropwise from another dropping funnel to adjust the pH of the reaction solution to maintain it at 10 to 11. After the addition is complete, continue stirring until the pH of the reaction mixture does not change to complete the reaction.9.

Hydrochloric acid was added to the reaction mixture to adjust the pH to about 3, ether was added, and the mixture was thoroughly stirred to extract the reaction product. The ether layer was thoroughly washed with water, then dehydrated with anhydrous sodium sulfate, and the solvent was distilled off. The residue was dried under reduced pressure to give N-lauroyl-N.
-(3-hydroxypropyl)glycine white solid 5
5? I got it.

m, p,: 55°C IR (KBr) crn-': 3200-3400
(νOH), 2850-2950(!'CH4),
1735 (1'co).

1625 (VCO) 'C-NMR (DMSO-d, LH complete decoupling conditions, approximately 3oC, rMs standard) COOH (δ: 172.3, 172.6) CON (
δ:171.4,170.9)Ci(,0)l(δ:
57.7.58.4') N-C mountain-CO (δ: 47
．． 3.49.5 )-CH, (δ: 13.9) Reference Example 2 N-Lauroyl-N-(3-hydroxypropyl) obtained in Reference Example 1 was placed in a reaction vessel in vessel 1 equipped with a stirrer. Glycine 20P (0,0634 mol) and ethanol 20WL't were charged and stirred at room temperature to uniformly dissolve.

Then sodium hydroxide 2.5365' (0,06
A solution prepared by dissolving 34 mol) of ethanol in 50 IIItK was added dropwise and thoroughly stirred to neutralize N-lauroyl-N-(3-hydroxypropyl)glycine. Add 700 ml of acetone to this neutralized product, cool it to 0°C, and leave it to stand for N-
Lauroyl-N-(3-hydroxypropyl)glycine sodium salt was precipitated.

The precipitate was filtered and the solvent was distilled off under reduced pressure to obtain N-lauroyl-N-(3-hydroxypropyl)glycine sodium salt 15? I got it.

IR(KBr)>-': 3100-3400(ν
oH), 2850-2950 (νC□,), 1625
(νco).

1600.1400 (VCO) Example 1 Liquid cleaning agent with the composition shown in Table 1 (pH
(adjusted to 7) was prepared and evaluated for hard water resistance, foaming power, and detergency.

Evaluation method〉 fil foaming power test method ■ 0.2 inch of artificial dirt was added to a 1% aqueous detergent solution in which a detergent composition was dissolved in hard water with a German hardness of 10 Di, and the mixture was heated to 40°C with a flat propeller. The mixture was stirred in a cylinder for 5 minutes at a rotation speed of 1000 rpm and inverted every 10 seconds.
Evaluation was made based on the amount of foam 30 seconds after the stirring was completed.

@ Sensory evaluation 25 according to the report? After soaking the foam in warm water (40° C.), a cleaning composition of 0.59°C was applied and rubbed for about 2 minutes, and the amount of foam was sensory evaluated.

Evaluation criteria ◎ Foams well ○ Average Δ Slightly foams poorly Rinse and dry to apply the artificial oil stain evenly. This cloth was used as a test piece of 10cy×10c1n for an experiment.

(B) Cleaning conditions and cleaning method A cleaning composition was dissolved in hard water with a German hardness of 15'D)i, and a 3% detergent aqueous solution 1! Prepare.

Five pieces of artificially contaminated cloth and this aqueous solution were placed in a turbotome.
The mixture was transferred to a stainless steel beaker and stirred in a turbotometer at 75 rpm for 13 minutes at 40'C. After rinsing under running water, it was iron pressed and subjected to reflectance measurement.

(C) Calculation of cleaning rate The cleaning rate was calculated according to the formula below.

The reflectance at 460 mμ of the original fabric before washing and the contaminated fabric before and after washing was measured using a self-recording colorimeter (manufactured by Takaguruma Seisakusho), and the cleaning rate (chi) was calculated using the following formula.

The average value of the five sheets is shown below. Note that the pH of the detergent aqueous solution before washing was 7.0.

(3) Hard water resistance test The effective content of the cleaning composition was adjusted to Q, 5 wt%, and the hardness was 10.20, 40 on the German hardness scale using calcium chloride.
, 100'DH. The appearance of each aqueous solution placed in a 100 mJ transparent glass container was visually judged at room temperature.

Evaluation was performed based on the following criteria.

○: The whole was uniform, and no abnormality such as separation, precipitation, or aggregation was observed, and the solution was transparent.

Δ: Uniform throughout, but translucent and turbid.

×; Non-uniformity with separation, precipitation, aggregation, etc. observed.

Results〉 The results are shown in Table 1.

Example 2 Liquid cleaning compositions shown in Table 2 were prepared, and their performance was evaluated by the evaluation method shown in Example 1. Second result
Shown in the table.

The product of the present invention has excellent hard water resistance and exhibits good foaming and cleaning properties.

]・Margin Example 3 (bath agent for infants) A bath agent for infants having the following composition was obtained.

Composition> Imidacillin type amphoteric surfactant*) 5.
0 Polyethylene Glycol 6000 Diste ZO Alate Irgasan DP-3000,1 Fragrance, pigment Trace amount of water Balance total 100 (In the formula, M means a mixture of Na and hydrogen atoms) Example 4 Shampoo with the following composition I got it.

Lauric acid jetanolamide 2.0 Cationized cellulose 0.3 Fragrance 0.3
Preservative 0.1 dye
Appropriate amount of citric acid
Total appropriate amount: 100 Example 5 A liquid cleaning composition having the following composition was obtained.

Ethanol 2. ．．
0 propylene glycol 3.
0 fragrance
0.1 water
Balance total: 100 Each of the cleaning compositions of Examples 3 to 5 had good detergency and foaming properties, was less irritating to the skin, and showed no scum formation even when used in hard water, demonstrating excellent performance. It was recognized that the performance could be achieved.

Example 6 (Solid detergent) Composition> il) N-7,Oyl-N-(3-H)"O#shi50.0 (%) Prohyrcoglycine sodium (3) Coconut fatty acid jetanol Amide 5
．． 0(4) Cetyl alcohol
10.0(5) Glycerin
5.0(6) Flavorings, preservatives
Appropriate amount (force water)
Balance components (3) to (7) are mixed, heated and emulsified, then added to (1) and (2) and sufficiently kneaded using a small roll. This was extruded using a small soap prototype device with a nozzle maintained at 40-50°C, and the obtained bar-shaped detergent was molded with a foot-type hammer to obtain a solid detergent.

Quartz has a mild and rich lather on the skin, and even when used in hard water, no scum formation was observed, demonstrating excellent performance.

Example 7 A shampoo having the following composition was obtained. (f) Polyoxyethylene (2,5) sodium lauryl ether sulfate 12,0 lauric acid zoethanolamide 3. ON-lauroyl-N-(2-hydroxyethyl)glycine sodium 5.0% alkyl ether 0.8%
120) Hydrogenated castor oil 0.8
ethanol
2.0 Fragrance 0.3 Preservative
0.1 dye
Appropriate amount of citric acid
appropriate amount of water
Balance total: 100 Example 8 A shampoo having the following composition was obtained. (f) Imiline-type amphoteric surfactant” 1
0.0? Lioxyethylene (2,5) lauryl ether sulfur m sodium 5.0 Fragrance 0.3 Preservative 0.1
Pigment Appropriate amount of citric acid (amount to make pH=7) Appropriate amount of water
Rose 73 *) Same as those used in Example 3, total 100 or more

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, RCO represents a saturated or unsaturated fatty acid residue having 8 to 18 carbon atoms, and X is A cleaning composition comprising one or more N-acyl-N-hydroxyalkylglycines or salts thereof represented by the formula (representing a hydroxyalkyl group having 1 to 4 carbon atoms).