JPS5941674B2 - liquid cleaning composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel liquid cleaning composition, more specifically, a liquid cleaning composition containing an anionic surfactant having a sulfonic acid group or a sulfate group that prevents rough hands or skin irritation. The present invention relates to a liquid cleaning composition.

Anionic surfactants with sulfonic acid groups and sulfate groups have excellent cleaning power, so they can be used in tableware, food, clothing,
It is widely used as a liquid cleaner for skin and furniture.

However, while cleaning agents must of course have high cleaning ability, they must also be safe, especially not causing rough hands (dry epidermal flaking changes) or skin irritation (erythema, edema, varicella changes, etc.). is important, and in recent years, its safety has become a particular concern. Anionic surfactants with sulfonic acid groups or sulfate groups have excellent cleaning power as mentioned above, but if liquid detergents containing them are used for a long time at a concentration higher than the concentration used, they may cause rough hands or skin. There was a problem that caused irritation.

In order to prevent this roughness, conventional methods have been used to add amine surfactants such as alkylamine oxide and polyoxyethylene alkylamine, but even with this method, the effect of light is limited. In addition, there was a drawback that an amine odor was produced during use, which caused discomfort to the user. [Under such circumstances, the present inventor conducted intensive research to solve the above-mentioned drawbacks, and as a result, the present inventors added hydroxypropyl etherified glycolipids represented by the following general formula (I) to the cleaning agent having the anionic surfactant. It has been found that the addition of Tsudoester (hereinafter abbreviated as POSL) can prevent rough hands and the like.

(In the formula, R1 represents CH3 or H; when R1 is CH3, R2 represents a saturated or unsaturated hydrocarbon group of C,, ~C,,; when R1 is H, R2 represents a saturated or unsaturated hydrocarbon group of Cl2 ~ Cl6; represents an unsaturated hydrocarbon group, A represents, and R3 represents C, ~C
2O saturated or unsaturated hydrocarbon group or (A) HH
(A, b, c, d, e, f, g, h are integers whose sum is 1 to 60) That is, the present invention was completed based on this new knowledge, and the sulfonic acid The present invention provides a liquid detergent composition containing an anionic surfactant having a group or a sulfate group and a hydroxypropyl etherified glycolipid ester (I).

The POSL used in the present invention is
It is produced as follows according to the method described in Publication No. 9 (Japanese Patent Application No. 53-24306). That is, first, sophorolipid obtained by culturing Torulopsis bombicola is reacted with methanol in the presence of an acid to perform methanolysis and methylation to obtain glycolipid methyl ester, or by further reacting this with other alcohols. Glycolipid ester is produced by a method in which transesterification is carried out, and glycolipid methyl ester is hydrolyzed to produce glycolipid. Next, the glycolipid or glycolipid ester thus obtained is reacted with propylene oxide in the presence of an alkali catalyst to produce POSL. As shown below, POSL is an extremely safe substance that has low toxicity and is less irritating to the skin and mucous membranes.

(1) Acute toxicity 1 oral rat: LD5Ol6.4O9/Kg (male), 15.5
0g/Kg (female).

Mouse: LD5Ol2. OO9/Kg (male), 10.5
09/Kg (female).

2 Subcutaneous rat: LD5O6.589/K9 Mouse: LD5O5.8O9/K9 (2) Subacute toxicity Using male and female Sprague-Dawley rats,
A POSL (7) month oral subacute toxicity study was conducted.

Administration was done by mixing feed with 4.0% and 1.0%.
, 0.25%, 0.0625%, and 0% (control group) were mixed into feed and administered to 12 rats per group by ingestion through the eyes. General condition: 4.0 for both sexes (
No particular abnormalities were observed except for soft stools in the Ft) group, and no cases of death were observed. Weight change; 4.0% male group, 1
．． Suppression of weight gain was observed in the 0% group.

Satiation intake: No particular abnormality was observed.

Water intake: An increase was observed in both sexes in the 4.0% group, but histopathologically there were no significant changes in the kidneys, etc.

Urinalysis: No particular abnormality was observed.

Autopsy and organ weights: No abnormalities were observed.

(3) Eye mucosal irritation test Using Japanese white rabbits (group 1, 5 rabbits), the test was conducted without eyewash treatment, and as a result, P
With a 50% aqueous solution of OSL, no reaction was observed in the cornea, iris, or conjunctiva.

(4) Skin irritation test The skin irritation of POSL was examined using female Hartley white guinea pigs using three methods: application, 5-hour closed patch, and 24-hour closed patch.

For coating, the average number of added moles n of propylene oxide was 4,
Six types of samples were used: 6, 8, 10, 12, and 15 (n-12 for POSL).

The solvent was ethanol, and the concentrations were 50, 25, and 1.
It was tested with 3 animals per group as 3 stages of 0%. As a result, the 05-hour closure patch, in which no irritation reaction was observed, was prepared using the above six samples and 50% ethanol was used as a solvent.
and 10% were tested in groups of 3 animals.

As a result, no irritant reaction was observed in any of the cases.

The 24-hour occlusive patch used 50% POSL white petrolatum and was tested on healthy and injured skin in groups of 10 animals.

As a result, no irritant reaction was observed in any of the cases.

(5) Allergy test The contact sensitization of POSL was investigated using female Hartley white guinea pigs.

In a preliminary study, groups of 5 animals were used, and propylene, .
The influence of the average number of moles added n (n=12 for POSL) was investigated.

Sensitization was carried out in two stages: intradermal (concentration 1%) and contact (concentration 50%) according to Maximlza-TiOnTest, and six types of samples, n24, 6, 8, 10, 12, and 15, were used. The challenge was carried out by painting (concentration 50%). As a result, no allergic reactions were observed with any of the six samples, regardless of n. In this study, there were 15 animals per group, and MaximizatiOnTes was used using POSL.
Sensitization was carried out in two steps: intradermal (concentration 1%) and contact (undiluted solution) according to the method described in t.

As a result of applying the drug and using a closed patch for 24 hours, no allergic reaction was observed. 6) Phototoxicity test POSL phototoxicity of female Hartley white guinea pigs 15
The study was conducted on animals.

A POSL 50% ethanol solution and a 10% ethanol solution were applied to the shaved back of a 002577Z11 guinea pig in two symmetrical locations, and one side was immediately covered with aluminum foil to serve as a non-irradiated control.

30 minutes later 3 Toshiba fluorescent lamps FL2OSE and FL2O
Irradiate three BLBs for 10 minutes from a distance of 20 cm,
Then, six FL2OBLBs were irradiated for 1 hour from a distance of 10 CrrL in height.

As a result, POSL5O% regardless of the presence or absence of light irradiation.
No skin reaction was observed due to the ethanol solution and the 10% ethanol solution.

1) Cumulative irritation test The cumulative irritation and sensitization properties of POSL were investigated using female Hartley white guinea pigs (15 animals in group I).

POSL was diluted with ethanol at 50(:f/) and 10(:
f) A solution of 0.0177 Z1 of each test solution was applied to the left flank of a shaved animal once a day, every day for 4 weeks, excluding Saturdays and Sundays, 20 times in total.

As a result, no skin reaction was observed.

11 days after the final application, animals thus treated (group l 15
50 on the left flank of untreated animals (15 animals in group I) and untreated animals (15 animals in group I).
% POSL ethanol solution, POSL-containing emulsion, and ethanol were applied to attempt induction. As a result, no reaction was observed.

After a further 13 days, 50% POSL was applied to the right flank of the animal.
Re-induction was attempted by applying white petrolatum, ethanol solution, and emulsion containing POSL for 24 hours.

As a result, no reaction suspected to be allergic was detected.

(8) Patch Test POSL skin primary irritation test was conducted on 60 healthy people (3 male).
(0 participants, 30 women).

The test samples were 50% POSL ion exchange aqueous solution, ion exchange water, 50% and 10% POSL vaseline solutions, and vaseline. 0.05 ml of this test sample was applied to the crooked side of the subject's forearm for 24 hours using a bandage for the Torii patch test. As a result, no skin reactions were observed in girls.

In three boys, faint erythema was observed in POSL 50% Vaseline solution. The skin irritation reaction in these three patients disappeared 24 hours after removal, and in the remaining one, the reaction remained until 48 hours, but the intensity of the reaction did not increase and only faint erythema was observed. . The subject also showed a strong reaction to ion-exchanged water. Taking these into consideration, we have determined that this product is a hypoallergenic substance. As the anionic surfactant in the composition of the present invention, one having a sulfonic acid group or a sulfate group is used, and examples of those having a sulfonic acid group include alkylbenzenesulfonic acid whose alkyl group has 8 to 18 carbon atoms; Alkali metal salts, ammonium salts, amine salts, etc. of α-olefin sulfonic acid or alkanesulfonic acid, and those having a sulfate group include alkyl sulfates or polyoxyethylene alkyl ether sulfates in which the alkyl group has 8 to 18 carbon atoms. Alkali metal salts, ammonium salts or amine salts of ates are used. In the composition of the present invention, other surfactants such as soaps, carboxylic acid type surfactants such as alkyl ether carboxylates; phosphate ester type surfactants such as alkyl phosphate esters; polyoxy Nonionic surfactants such as ethylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid mono- or diethanolamide, etc. can also be used in combination. The liquid detergent composition of the present invention is produced by forming the above-mentioned anionic surfactant and POSL into a liquid detergent by a conventional method.

The amount of anionic surfactant varies depending on its intended use and the amount of other active agents used, but is usually between 5 and 3 % of the total composition.
0% by weight (hereinafter simply referred to as %) is preferable, and POS
L is 5 to 100%, especially 1 to the anionic surfactant.
It is preferable to mix it in an amount of 0 to 50%. The liquid cleaning composition of the present invention may be light or heavy. In the latter case, inorganic builders such as sodium orthophosphate, sodium pyrophosphate, sodium silicate, sodium carbonate, sodium metaborate, and borax can be contained to an extent that does not impair solution stability. In either case, alkali metals such as gluconic acid, tartaric acid, and malic acid, ammonium and amine salts, potassium pyrophosphate, and sodium nitrilotriacetate can be used in combination.

In order to further increase the solution stability, alkali metal salts, ammonium salts and amine salts of paratoluenesulfonic acid, xylene sulfonic acid, ethylbenzenesulfonic acid, cumenesulfonic acid, as well as methanol, ethanol, propyl alcohol, propylene glycol, glycerin,
It is also possible to add solubilizers or solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, ethyl carbitol urea. Next, the present invention will be described with reference to Examples and Reference Examples. Example 1 The hair on the backs of two male and female Omi mini pigs was shaved using a parigan and an electric razor, and the following sample diluted 20 times with water was applied to the skin using a cotton swab.
13cTi1 was applied.

Do this operation twice a day. I went there a total of 10 times over 5 days. After 6 days, epidermal desquamation changes were determined, the epidermis was sacrificed, and the skin was collected for histological examination.

1 Sample A Sample b 0i) Histological Findings The collected skin was fixed in formalin, sections were prepared at the light microscope level by a conventional method, stained with H-E, and examined under a microscope.

As a result, peeling of the upper layer of the stratum corneum and dissociation between the stratum corneum cells were observed in the regions treated without the addition of POSL and with the addition of 2% POSL. On the other hand, no exfoliation of the stratum corneum or dissociation of the stratum corneum cells was observed in the areas treated with 4% or more of POSL. As is clear from the above results, POSL is 5% for anionic surfactants.
If it is added in an amount of % or more, it is possible to prevent rough hands.

Example 2 The hair on the backs of two male and female vehicle dogs was shaved using a parigan and an electric razor, and the same sample a as in Example 1 was applied to their skin.
-c diluted 20 times with water, about 0.5ml 1/13
d was applied.

This operation was performed twice a day for 7 days, 14 times in total. 8
After determining primary irritant changes on day one, the skin was sacrificed and the skin was harvested for histological examination.

(1) Primary irritative changes: See Table 2.

(:1) Capillary dilation and small round cell infiltration were observed in the areas treated with samples without POSL and with 2% POSL added, but no abnormalities were observed in areas treated with samples added with POSL4 (Ft) or higher. Nakatsuta. Example
3 Using the same liquid detergent samples A, b, and c as in Example 1, the detergency and foaming power were measured.

(b) Detergent power Beef tallow: Add 0.1% of a red pigment (Stan) as an indicator to a mixture of fats and oils at a ratio of 9:l, apply this 59 on a magnetic plate (diameter 25CTfL), and Cleaning agent 3
The dishes were scrubbed with a sponge soaked in 0% aqueous solution until no oil or fat was removed from the dishes.

The cleaning power was expressed by the number of plates. The results are shown in Table 3. (b) Foaming power 0.1 with 0.1% of commercially available butter added as a staining ingredient
The foaming power of detergent solutions of 5% and 0.25% concentration was measured.

The measurement method was as follows: 40 ml of the above detergent solution to which butter had been added was placed in a glass cylinder with a diameter of 5 CTrL, rotated and stirred for 10 minutes, and foaming was measured after stopping.

The results are shown in Table 4. Example (liquid dishwashing detergent) The above ingredients are mixed in a conventional manner to form a product.

Example 5 (Household detergent) Alkyl ether sulfate toner A product is prepared by mixing 2% or more of the ingredients using a conventional method.

Example 6 (Bathroom detergent) The above ingredients are mixed in a conventional manner to form a product.

Example 7 (Toilet detergent) The above ingredients are mixed in a conventional manner to form a product.

Example 8 (Liquid laundry detergent) The above ingredients are mixed in a conventional manner to form a product.

Example 9 (Liquid dishwashing detergent) 1? ? ? \t? J The above ingredients are mixed in a conventional manner to form a product.

Reference example 1 (1) Glucose 15009, yeast extract 7
59. Add water to urea 159 so that the total amount is 151,
Sterilize and make fermentation liquid.

This fermentation liquid was inoculated with Torulopsis pombicola that had been cultured at 30°C for 48 hours in a medium with the same composition, and the temperature was increased to 20°C.
, stirring number 300 rP! 11 Start fermentation at an aeration rate of 0.33 VM. After culturing for 24 hours after inoculating the bacteria, beef tallow 1509
After that, the same amount of beef tallow was added at 24-hour intervals for a total of 9,009 ounces, and fermentation was continued for another 24 hours after the last addition, making a total of 1
Fermentation was carried out for 68 hours. After the fermentation is completed, the sophorolipid phase that has settled at the bottom of the fermenter is filtered through a slant, and the sophorolipid 1
300g was obtained. This product contains about 50% water and is paste-like at room temperature. (4) This Sophorolipid 1009 was placed in a 200ml round bottom flask with a stirrer together with polypropylene glycol 2.59 having an average molecular weight of 200, a Liebig condenser was attached, and water was distilled off under a reduced pressure of 250HI1Hg while stirring in an 80°C oil bath. I left.

After about 2 hours of water distillation, the water content was 10/
) below. (J[I) Polypropylene solution of sophorolipid prepared in this way (methanol 150%
After adding 9 and 2,59 sulfuric acid, heat at 40℃±2.
The reaction was carried out for 90 minutes at a temperature of .degree.

The reaction was investigated using silica gel thin layer chromatography [developing solution: chloroform-methanol monoacetic acid (75:20:5)] and was completed when many spots of the raw material sophorolipid converged on one spot of glycolipid methyl ester. .
After the reaction is complete, neutralize with a predetermined amount of potassium hydroxide, filter, put the reactor liquid into a round bottom flask with a Liebig condenser, and distill off methanol and methyl acetate to form a brown paste [(2!-0- [(2! -0-β
-D-glucopyranosyl-β-D-glucopyranosyl)
Oxy]alkanoic acids and alkenoic acid methyl esters are obtained.

IR (Cm-1): 1740 ('-C=0 ester) 1
380-3200 (-0H sugar) 900-750 (glucopyranose ring) NMR [δ (pyridine)]: 1.

1 to 1.6 (-CH2-CH2) 36 (-0-CH3) 35 to 5.0 (sugar) 5,5 (-CH-CH monounsaturated fatty acid) Todorohano'VIμs υ 1 This product is 5 When decomposed in a normal hydrochloric acid-methanol solution and analyzed by gas chromatography, 2 moles of methyl glycoxide and 1 mole of hydroxy fatty acid methyl ester are obtained.

Reference Example 2 [(2/-0-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy]alkanoic acid and coexistence product of alkenoic acid methyl ester and polypropylene glycol 1009 obtained in Reference Example 1 was mixed with potassium hydroxide 0 .25
9 was placed in an autoclave, and reacted for 6 hours at 100 to 12°C while blowing propylene oxide gas corresponding to the number of added moles shown in Table 3 below.

After the reaction, it is neutralized with phosphoric acid and separated under pressure to obtain a brown paste-like crude product, which is further purified by silica gel chromatography to obtain a pale yellow paste-like polyoxypropylene [
(2/-O-β-D-glucopyranosyl-βD-glucopyranosyl)oxy]alkanoic acid and alkenoic acid methyl ester were obtained. The results of oil and fat characteristic analysis confirmed that the specified amount of propylene oxide was added.

Reference Example 3 (:) Coexistence product of [(2'-0-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy]alkanoic acid and alkenoic acid methyl ester and polypropylene glycol 1009 obtained in Reference Example 1 and water 309 and ethanol 709 were placed in a 500 ml round bottom flask, mixed to form a homogeneous solution, potassium hydroxide 91 was added, and the mixture was refluxed for 2 hours.

After the reaction, the mixture was neutralized with sulfuric acid, the precipitated potassium sulfate was removed, and the aqueous solution was placed in a 500 ml three-neck flask equipped with a Liebig condenser, and methanol and ethanol were first distilled off under normal pressure, and then water was distilled off under reduced pressure. [(2 Ren 0-β-D-
Glucopyranosyl-β-D-glucopyranosino(ha)oxy]alkanoic acid and alkenoic acid were obtained. (4)(1)
The product obtained in step 1 was placed in an autoclave with 0.259 g of potassium hydroxide, and 100 g of propylene oxide corresponding to the number of added moles shown in Table 5 below was blown into the autoclave.
The reaction was carried out at ~120°C for 6 hours.

After the reaction, it is neutralized with phosphoric acid and separated under pressure to obtain a brown viscous product, which is further purified by silica gel column chromatography to obtain a light yellow paste of polyoxypropylene [
(21-O-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy]alkanoic acid and alkenoic acid ester were obtained. It was confirmed that the specified amount of propylene oxide was added by oil and fat characteristic analysis.

Reference Example 4 Addition of ethylene oxide to glycolipid octyl ester The glycolipid methyl ester-polypropylene glycol mixture 209 obtained in Reference Example 1 was placed in an autoclave, and then octyl alcohol 4.2
After adding 5 g of methanol to make a homogeneous solution, 0.19 g of sodium methylate was added.

After distilling off most of the methanol at a temperature of 70°C, the pressure was reduced to 250°C. The methanol produced was distilled off under H2O with stirring to allow the transesterification reaction to proceed, and the progress of the reaction was measured using a gas coulomatograph under the following conditions. Gas chromatography conditions are 3% as analytical column.
Silicon JXR-Chromosolve W6O~80mesh1
Inner diameter 3? , using a glass column with a length of 1 m, 25'C~
Column open temperature raised to 350°C, helium gas 0.
6k9/d pressure, hydrogen flame detector. The analysis method is to take a portion of the reaction solution, trimethylsilylate it with a trimethylsilylation reagent, and then measure it. The progress of the reaction is determined from the peak area ratio of glycolipid methyl ester and glycolipid octyl ester. The end point of the reaction was determined by the disappearance of the methyl ester peak. Then, while blowing in a predetermined amount of ethylene oxide gas shown in Table 7, a reaction was carried out at 100 to 120° C. for 6 hours to obtain an ethylene oxide adduct. The amount of ethylene oxide charged was adjusted according to the specified number of moles added according to Table 7. After neutralizing with phosphoric acid and separating the produced sodium phosphate under pressure, sample 59 was purified using a column chromatograph packed with 5009 silica gel (Cucaroform-methanol; gradient elution method), and purified with polyoxyethylene. [(2/-0-β-D
-Glucopyranosyl-β-D-glucopyranosyl)oxy]alkanoic acid and alkenoic acid octyl ester fractions were obtained.

The amount of this distillate corresponded to 91 to 94% by weight of the sample. Reference Example 5 Addition of ethylene oxide to glycolipid oleyl ester The 20:9 mixture of glycolipid methyl ester and polypropylene glycol obtained in Reference Example 1 was placed in an autoclave, and then 8.99% of oleyl alcohol was added to the mixture.
was added, 59% of methanol was added, and 0.19% of sodium methylate was added.

All transesterification reaction conditions and ethylene oxide addition reaction conditions were performed in the same manner as in Reference Example 4. Ethylene oxide gas was reacted with 21.09 moles of ethylene oxide so that the average number of moles of ethylene oxide added was 15 moles. The obtained ethylene oxide adduct was 2989. Then, after neutralizing with phosphoric acid and separating the produced sodium phosphate under pressure, sample 5f! was purified under the same silica gel column chromatography conditions as in Reference Example 4, and purified with polyoxyethylene [(27-0-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy]alkanoic acid and alkenoic acid oleyl ester distillate. Minute 4.59 was obtained. R(CTrL-1
):3380~3200(-0H)1740(]C=O
) 1100 (-0-riether group) 1050 (-0H) Reference Example 6 Addition of Glycolipid Lauryl Ester with Propylene Oxide The glycolipid methyl ester-polypropylene glycol mixture 209 obtained in Reference Example 1 was placed in an autoclave, After adding 6.19 grams of lauryl alcohol and further adding 59 grams of methanol, 0.19 grams of sodium methylate was added.

The method for preparing glycolipid lauryl ester is shown in Reference Example 4.
I did the same thing. After the transesterification reaction is completed,
1 while blowing in a predetermined amount of propylene oxide gas.
The mixture was reacted at 00-120°C for 6 hours to obtain a propylene oxide adduct. The amount of propylene oxide gas charged was adjusted according to Table 9 1 according to the specified number of moles added. After neutralizing the obtained propylene oxide adduct with phosphoric acid and pressurizing and separating the produced sodium phosphate, Sample 59 was purified by silica gel column chromatography in the same manner as in Reference Example 4 to obtain polyoxypropylene [( 2/-0
-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy]alkanoic acid and alkenoic acid lauryl ester fractions were obtained. This fraction corresponded to 90-93% by weight of the sample. IR (CTrL-1): 3380-3200 (
-0H)1740(]C=O)1100(-0-riether)

Claims (1)

[Claims] 1 Alkylbenzenesulfonic acids in which the alkyl group has 8 to 18 carbon atoms; α-olefin sulfonic acids; alkali metal salts, ammonium salts, or amine salts of alkanesulfonic acids; alkyl sulfates in which the alkyl group has 8 to 18 carbon atoms; 5 to 30 anionic surfactants selected from the group consisting of alkali metal salts, ammonium salts, or amine salts of oxyethylene alkyl ether sulfate.
Weight%, as well as the following general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R^1 represents CH_3 or H, and when R^1 is CH_3, R^2 is C_1_
1 to C_1_5 saturated or unsaturated hydrocarbon groups, R^
When 1 is H, R^2 represents a saturated or unsaturated hydrocarbon group from C_1_2 to C_1_6, A represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^3 represents a saturated or unsaturated hydrocarbon group from C_1 to C_2_0. Indicates a saturated hydrocarbon group or (A)_hH, and a, b, c, d, e, f, g, h have a total sum of 1 to
A liquid detergent composition comprising 5 to 100% by weight of an anionic surfactant of hydroxypropyl etherified glycolipid ester (representing an integer of 60).