JP3447879B2 - Foam cleaning agent - Google Patents

Description

Description: BACKGROUND OF THE INVENTION Since the present invention is foamy, it can be effectively applied to a portion to be washed and has high safety.
The present invention relates to a novel wiping-removable foam cleaning agent that can remove dirt simply by wiping with a towel without rinsing with water, and has an excellent refreshing feel during and after use. 2. Description of the Related Art Generally, a shampoo needs to be rinsed with water or hot water after washing its hair, so that it cannot be used for bathing due to illness or injury, or where water cannot be easily used. Then, it is difficult to wash the hair. For this reason, a cleaning type rewiring which does not require rinsing has been devised. [0003] For example, an aerosol-type aqueous detergent composition (Japanese Patent Publication No. 57-47960), a foamed hair wash (Japanese Patent Application Laid-Open No. 61-28902).
3), Woven shampoo composition foamy hair wash (Japanese Unexamined Patent Publication No.
2-205011), dry hair washing method and chemicals therefor
63-14711), an aerosol shampoo composition (JP-A-63-1)
90813). [0004] However, in the prior art, in the case of using an electrolyte-based surfactant, it is not sufficient to stimulate the scalp and scalp hair by simply wiping. In addition, for those using a non-electrolyte type surfactant, in the case of a dosage form such as a spray, the detergent is scattered to unnecessary parts. It has not been satisfactory yet because the amount of alcohol to be formulated is limited to a low level and the cleaning effect and the refreshing feeling are insufficient. On the other hand, Japanese Patent Application Laid-Open No. Hei 6-100435 discloses that a foamed detergent having a high alcohol content can be obtained by using a specific amount of a combination of a non-electrolyte surfactant and a higher alcohol. On the other hand, when polyglycerin fatty acid ester was used as the non-electrolyte surfactant, the cleaning effect and refreshing feeling were still unsatisfactory. [0006] As a conventional method for producing polyglycerin fatty acid ester, it is produced by an esterification reaction between polyglycerin and a fatty acid. However, in this method, the desired polyglycerin fatty acid ester is generally contained in a desired form. It has been pointed out that not only monoesters, but also unreacted polyglycerin, diesters, triesters, and polysubstituted esterified products such as tetraesters remain. Due to the influence of the residue, there is a problem in stability over time, a cleaning effect, and a refreshing feeling, and further stability over time has been required. In view of such circumstances, as a result of diligent research, polyglycerin fatty acids having a monoester content of 70% or more synthesized as a non-electrolyte surfactant by an addition polymerization reaction of a fatty acid and glycidol. Ester blend
It has been found that the above-mentioned drawbacks of the prior art can be improved by obtaining a foamed detergent containing one or more reaction products containing a compound as a main component, thereby completing the present invention. Was. [0008] Therefore, an object of the present invention is to provide a highly safe, foamy, effective application to a portion to be washed, and to remove dirt by wiping with a towel without rinsing with water. Another object of the present invention is to provide a new wiping-type cleaning agent immediately with a refreshing feel. [0009] That is, the present invention provides:
“Monoester content 70% or more (high-performance liquid chromatography) synthesized by the addition polymerization reaction of fatty acid and glycidol.
(Based on the ratio of peak areas based on the method of chromatography) based on polyglycerol fatty acid ester mixture
0.5 to 10% by weight of one or more of the products ;
30 to 60% by weight of one or more lower monohydric alcohols having 1 to 3 carbon atoms and 30 to 60% by weight of water
And one of the higher alcohols having 12 to 22 carbon atoms.
And a propellant and a stock solution containing 0.1 to 5% by weight of a seed or two or more kinds thereof. Hereinafter, the configuration of the present invention will be described in detail. [0011] That is, the reaction product containing a polyglycerol fatty acid ester mixture as a main component and having a monoester content of 70% or more used in the present invention is the addition polymerization of glycidol and a fatty acid. It is obtained by the reaction, specifically, using methanol as an eluent,
Separation with a DS column, using an ultraviolet absorption rate measuring device, based on a high performance liquid chromatographic analysis method, wherein the monoester content is 70% or more in peak area ratio.
Polyglycerol fatty acid ester mixture
It is a reaction product . Conventionally, methods for producing polyglycerin fatty acid esters include (1) an esterification reaction of polyglycerin with fatty acids [JAOCS (Journal of American Oil Chloride).
emists' Society) Volume 58, Page 878 (1981),
No. 6-41007], (2) transesterification of polyglycerin with fatty acid esters, (3) transesterification of polyglycerin with oils and fats, (4) addition of glycidol with fatty acid monoglycerides Polymerization reaction [US Paten
t 5,515,775], and (5) an addition polymerization reaction of glycidol with a fatty acid (see JP-A-51-65705 ) . In the present invention, "the reaction between fatty acid and glycidol"
Monoester content, synthesized by addition polymerization
Mainly 70% or more of polyglycerin fatty acid ester mixture
The " reaction product as a component " is one produced by the method (5). As the fatty acid used in the addition polymerization reaction of glycidol and a fatty acid, a fatty acid having 6 to 22 carbon atoms is used, which may be a saturated fatty acid or an unsaturated fatty acid.
Further, it may be a straight-chain fatty acid, a fatty acid having a side chain, or a hydroxyl-substituted fatty acid. These fatty acids include, for example, caproic acid, caprylic acid, monoethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, linoleic acid Acids, behenic acid, erucic acid, ricinoleic acid, hydroxystearic acid and the like. The reaction between the fatty acid and glycidol is preferably performed in the presence of an acidic catalyst. Examples of the acidic catalyst include phosphoric acids and esters of phosphoric acid. Specific examples thereof include phosphoric acid, phosphoric anhydride, polyphosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid. Or acid phosphates such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, and 2-ethylhexyl acid phosphate. These acidic phosphates may be used in the form of a monoester, a diester, or a mixture thereof. These may be used alone or as a mixture of two or more. The amount of the catalyst is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the fatty acid. If it is less than 0.01% by weight, the reaction rate is low, and if it exceeds 10% by weight,
The effect cannot be expected to be improved, and depending on the catalyst used, a large amount of a glycidol addition polymer in which the catalyst serves as an initiator is generated, which is not preferable. The reaction method is to take fatty acids in a reaction vessel,
The above-mentioned soot is added thereto, and the reaction is carried out while adding glycidol little by little. The reaction temperature is 50-180 ° C, preferably 70-160 ° C, more preferably 120-180 ° C.
~ 140 ° C. If the temperature is lower than 50 ° C., the reaction rate is low.
If the temperature exceeds 80 ° C., coloring becomes intense, and if the temperature exceeds 230 ° C., glycidol is decomposed to cause a side reaction, which is not preferable. In this case, a low-boiling compound which does not react with glycidol may be added to prevent the reaction temperature from rising. The reaction is desirably performed in a nitrogen gas atmosphere, and may be pressurized if necessary. By the above reaction, glycidol is addition-polymerized to the fatty acid to produce a polyglycerol monofatty acid ester having a higher polymerization degree. The product has a monoester content of 70% or less.
Based on the above polyglycerin fatty acid ester mixture
Including . The reaction product containing the polyglycerol fatty acid ester mixture as a main component produced by the above method may contain 500 to 2000 ppm of oxirane oxygen considered to be derived from glycidol, depending on the production conditions. Therefore, water is added to the product obtained by the above-mentioned method, followed by heating and then dehydration, to obtain a high-purity reaction product containing a polyglycerin fatty acid ester mixture as a main component, which has a low detection amount of oxirane oxygen concentration. Purification is preferred. The amount of water to be added is determined based on the amount of the polyglycerol fatty acid ester mixture obtained in the first step as a main component.
It is preferred to select from 0.1 to 20% by weight based on the reaction product . If the amount of water is less than 0.1% by weight, the amount of unreacted glycidol cannot be sufficiently reduced, and if it exceeds 20% by weight, the post-treatment operation becomes complicated, and neither is preferable. A particularly preferred range of the amount of water to be added is
1 to 10% by weight. In this purification step, unreacted glycidol can be converted to glycerin by adding water to a reaction product containing a polyglycerin fatty acid ester mixture as a main component and then heating. The heating temperature at this time is preferably selected in the range of 60 to 200 ° C. If the heating temperature is lower than 60 ° C, the concentration of residual oxirane groups derived from unreacted glycidol or an oxirane group-containing compound which is expected to be a by-product cannot be sufficiently reduced. Any of these is not preferable because the reaction product containing the polyglycerol fatty acid ester mixture as a main component is colored. In the above temperature range, it is particularly preferable that the temperature is 80 to 1
It is in the range of 60 ° C. The heating time depends on the temperature,
The range is 0.5 to 15 hours, particularly preferably 1 to 7 hours. Dehydration can be performed by distillation, azeotropic distillation, vacuum distillation, or the like. The heating temperature at the time of distillation is 100 to 200.
It is preferable to select in the range of ° C. If the heating temperature is less than 100 ° C, the product polyglycerin fatty acid ester mixture
Is not sufficient to remove water contained in the reaction product mainly composed of polyglycerol fatty acid ester mixture as the main component.
None of them is preferable because the reaction product is colored. Particularly preferred in the above temperature range is a range of 110 to 160 ° C. The dehydration time depends on the temperature and the degree of decompression.
It is chosen in the range of 0 hours. Among them, 1 to 6 are preferable.
Time range. The reaction product containing the polyglycerin fatty acid ester mixture thus purified as a main component is described in A.
It is a high-purity reaction product containing , as a main component, a polyglycerin fatty acid ester mixture having an oxirane oxygen concentration of less than 100 ppm as determined by the titration method specified in OCS Test Method Cd. 9-57. The addition weight of the above fatty acid and glycidol
Monoester content 70% synthesized by combined reaction
The above polyglycerin fatty acid ester mixture as the main component
The reaction products can be used alone or in combination of two or more. The amount of the reaction products is 0.1% in the stock solution of the foamed detergent.
5 to 10% by weight. When the amount is less than 0.5% by weight, the foaming property (foaming) is insufficient, and when the amount is more than 10% by weight, the foam hardly breaks down and the feeling in use is deteriorated, which is not preferable. The non-electrolyte surfactant used in the present invention is, in addition to the above components, a sorbitan fatty acid ester, polyoxyethylene (hereinafter referred to as PO).
E) sorbitan fatty acid ester, POE alkyl ester, POE alkyl aryl ester, glycerin fatty acid ester, POE glycerin fatty acid ester, polyglycerin fatty acid ester, alkyl glyceryl ester,
POE alkyl glyceryl ester, alkyl glucoside, POE alkyl glucoside and the like. The carbon atom used in the present invention has 1 to 3 carbon atoms.
Examples of the lower monohydric alcohol include methanol, ethanol, n-propanol, and i-propanol. From the viewpoint of toxicity and the like, ethanol modified with brucine, vitorex, etc. is preferable. The amount of the lower l-valent alcohol used in the present invention is 30 to 60% by weight in the stock solution of the foamed detergent. If it is less than 30% by weight, a refreshing feeling after use (cool feeling) is insufficient during use, and the cleaning effect of sebum stains and the like is insufficient. Poor (foam is easily broken), and the feeling of use becomes poor, which is not preferable. The number of carbon atoms used in the present invention is l2
Examples of the higher alcohols which are 2222 include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol and the like. The blending amount of the higher alcohol having 12 to 22 carbon atoms used in the present invention is 0.5 to 5% by weight in the stock solution of the foamed detergent. If the amount is less than 0.5% by weight, foaming occurs, and the stability of the foam is inadequate. The propellants used in the present invention include propane, n-butane, i-butane, n-pentane and i-butane.
Liquefied petroleum gas such as pentane, and a mixture such as dimethyl ether are exemplified. The compounding amount of the propellant used in the present invention is 2 to 15% by weight in the foamed detergent. 2% by weight
If it is less than 15%, the foaming properties (foaming) are insufficient, and if it exceeds 15% by weight, the foam quality and foam stability deteriorate, and the feel upon use is also unpreferable. In the present invention, it is preferable that the mixing ratio between the stock solution and the propellant is stock solution / propellant = 85 / l5 to 98/2. The dosage form of the present invention is an aerosol, and may be a gas / liquid two-phase system or a gas / liquid / liquid three-phase system. In addition to the above-mentioned components, the foam-like detergent of the present invention may be a polyhydric alcohol, a high molecular weight substance, a polysaccharide, or a protein shoe in a quantitative and qualitative range according to the purpose, without impairing the effects of the present invention. , A plant extract, an ultraviolet absorber, a drug, a chelating thorn, an antioxidant, a fragrance, and the like. Examples of the polyhydric alcohol include propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerin, diglycerin, sorbitan, sorbitol, maltitol, glucose, sucrose and the like. Examples of the polymer substance include poly (dimethyldiallylammonium halide) and Merquat 100>, a copolymer of dimethyldiallylammonium halide and an acrylic monomer such as Merquat 550>, polyethylene glycol / epichlorohydrin / propyleneamine, and taroylamine or cocoyl. Condensation products of amines such as PolyquatH> or quaternary nitrogen-containing cellulose such as Polymer JR etc.> cationic polymers such as xanthan gum, carrageenan, sodium alginate, gum arabic, pectin, carboxypinyl polymer and other anionic polymers , Polypinylpyrrolidone and copolymers of vinylpyrrolidone and vinyl acetate, vinylpyrrolidone, pinyl acetate, copolymers of acrylaminoacrylate, hydroxyethyl cellulose, hydroxypropyl cellulose Scan, hydroxypropyl cellulose, methyl cellulose, dextrin, galactan, nonionic polymers, dialkylamino acrylate such as pullulan,
I want to copolymerize dialkylaminoethyl methacrylate, diacetone acrylamide, etc. with alkyl acrylate, alkyl methacrylate ester, methacrylic acid alkyl ester, etc., and amphoterate with halogenated acetic acid, etc. Amphoteric polymers such as Yukaformer AM-75> Is mentioned. Examples of the polysaccharide include hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate, heparan sulfate, and salts thereof. As an ultraviolet absorber,
As benzoic acid-based compounds, para-aminobenzoic acid, glyceryl para-aminobenzoic acid, ethyldihydroxypropyl para-aminobenzoic acid, cinnamic acid-based octyl methoxycinnamate, 2-ethoxyethyl-P-methoxy cinnamate, and benzophenone-based , 4-dihydroxy-benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methylbenzophenone, other ethyl urocanates, 2-phenyl-5-methylbenzoxazole, 4-methoxy-4-t-butyldibenzoylmethane And the like. As other drugs, drugs commonly used in cosmetics such as vitamin Cs, vitamin Es, various amino acids, crude drugs, anti-inflammatory agents, bactericides and the like can be blended. [Examples] The present invention will be described in more detail with reference to the following examples. The invention is not limited to the embodiments shown. All amounts are by weight. Prior to this, test methods and evaluation methods employed in the examples will be described. Stability (denaturation rate of protein): Good correlation with the eye irritation intensity of the Draize method. Protein denaturation rate using hemoglobin (HDR
%) And evaluated as follows. [0036] ◎: HDR is less than 5% ○: HDR is 5% or more and less than 15% △: HDR is 15% or more and less than 50% ×: HDR is 50% or more Detergency: A certain amount of artificial sebum dirt containing an ultraviolet absorber The washing operation was performed by reciprocating the sample-moistened paper towel three times with a constant load on the rubber coated with the amount in three times. Dirt before and after washing was collected with a solvent, the amount of the ultraviolet absorber was quantified, and the washing rate was determined. The evaluation was performed as follows. ○ = 60% or more cleaning rate Δ = 40% to less than 60% cleaning rate × = 40% or less cleaning rate Foamability: Prepare and fill aerosol with constant stock solution / propellant ratio,- It was taken out by hand at each temperature of 5, 25 and 30 ° C., and the foaming property was evaluated by sensory evaluation. Foam persistence (foam stability): The ratio of the foam volume immediately after the aerosol was sprayed and the foam volume after 30 minutes (Fr%) was measured and evaluated as follows. [0039] ＝= 80% or more of Fr △ = 50% or more and less than 80% Fr: Fr of less than 50% Feeling after use: 5 g of the prepared sample was picked up by 8 panelists, hair was washed, and towel And wiped it off. Thirty minutes later, the smoothness of the headwear was sensory evaluated. The evaluation was performed on a scale of 1 to 5, with 5 being “good” and 1 being “poor”, and the average value of 8 persons was obtained. The evaluation was shown as follows. ：: Rating 3.5 or more (good) ×: Less than 3.5 (poor) Stability: The prepared sample was stored at -5, 0, 25, and 35 ° C. for one month. After that, observe the state of the system and the state of the sprayed foam at the same temperature and returned to 25 ° C. did. REFERENCE EXAMPLE 1 0.5 mol (100.1 mol) of lauric acid was placed in a 1-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder.
6g) and 0.0622g of phosphoric acid (85% product)
Heated to 40 ° C. Then, while maintaining the reaction temperature at 140 ° C., 3.0 mol (222.24 g) of glycidol was added dropwise over 5 hours. The temperature was further maintained, and the reaction was continued for 26 hours. After cooling, the reaction product was taken out to obtain about 300 g of a reaction product mainly composed of a mixture of hexaglycerin laurate. When the reaction product containing the obtained mixture of hexaglycerin laurate as the main component was evaluated under the following high-performance liquid chromatography (hereinafter abbreviated as HPLC) analysis conditions, the monoester content was 87.
7%. (HPLC analysis conditions) Column: Wakosil 5C18 * 2 Developing solvent: MeOH Flow rate: 0.75 ml / min. Column oven temperature: 40 ° C. Detection method: UV absorption method (λ = 210 nm) Sample concentration: 10% Injection amount Reference Example 2 4.0 mol of glycidol (296.3)
2g) The same operation as in Reference Example 1 was carried out except that the mixture was used. After cooling, the reaction product was taken out to obtain about 400 g of a reaction product mainly composed of an octaglycerin laurate ester mixture . Polyglycerin laurate mixture obtained
When the reaction product containing as a main component was analyzed by HPLC, the monoester content was 84.5%. Reference Example 3 Glycidol 5.0 mol
(370.40 g) The same operation as in Reference Example 1 was performed except that the mixture was used. After cooling, the reaction product was taken out to obtain about 470 g of a reaction product mainly composed of a mixture of decaglycerin laurate. The reaction product mainly comprising resulting decaglycerol lauric acid ester mixture was analyzed by HPLC, the monoester content was 77.2%. COMPARATIVE REFERENCE EXAMPLE 1 / Case of Reaction of Fatty Acid with Polyglycerin Polyglycerin [Daicel] was placed in a 1-liter four-necked flask equipped with a nitrogen inlet tube, stirrer, cooling tube, temperature controller, and dropping cylinder. PG manufactured by Chemical Industry Co., Ltd.
L06; hexaglycerin, hydroxyl value 960] 175.
3 g (0.5 mol) was taken, heated to 80 ° C., and while maintaining the reaction temperature at 80 ° C., 0.5 mol (10 mol) of lauric acid.
0.16 g) was added and dissolved. Next, 0.75 g of sodium carbonate and 0.25 g of sodium bisulfite were added, and an esterification reaction was performed at 210 ° C. After 2 hours of reaction, the acid value became 0.89. After cooling to 100 ° C., the reaction product was taken out. When the obtained polyglycerol monolaurate was analyzed by HPLC, the mono substitution rate was 5%.
It was 5.1%. [Comparative Reference Examples 2, 3 / Evaluation Results of Commercially Available Polyglycerol Fatty Acid Esters] As commercial polyglycerin fatty acid esters produced from the reaction of polyglycerin and fatty acids, two products of SY Glyster (manufactured by Sakamoto Yakuhin Kogyo) (ML-500, ML-750) were selected. When these polyglycerin monolaurates were analyzed by HPLC, the monosubstitution rates of ML-500 and ML-750 were 52.0% and 44.3%, respectively. Further, these are referred to as Comparative Reference Examples 2 and 3, respectively. Examples and comparative examples are shown below. A foam detergent having the composition shown in Table 1 was prepared, and its safety, foamability, foam sustainability, detergency, and stability were shown together with Comparative Examples. Table 1 Example Comparative Example 1 2 3 1 2 3 A1 1.0 A2 1.0 A3 1.0 A4 1.0 A5 1.0 A6 1.0 Characteristic stability ○ ○ ○ ○ 安全 Safety (protein denaturation rate) ◎ ◎ △ Foaming ○ ○ ○ △ △ △ Foam persistence ○ ○ ○ △ △ △ Usability (when used) ○ ○ ○ △ ○ ○ (after use) ○ ○ ○ △ ○ ○ Examples 1-3 and Comparative Examples 1 In Example 3, cetyl alcohol was 2.0% for all, ethyl alcohol was 50.0% for all, purified water was 42.0% for all, L.P. P. G was mixed in 5.0%. A1: Reaction product containing the polyglycerin fatty acid ester mixture obtained in Reference Example 1 as a main component A2: Polyglycerin fatty acid ester mixture obtained in Reference Example 2
Reaction product A3 containing compound as main component : Polyglycerin fatty acid ester mixture obtained in Reference Example 3
The reaction product is a compound mainly A4: Comparative Example 1 obtained in the polyglycerol fatty acid ester A5: Comparative Example 2 obtained polyglycerol fatty acid ester A6: polyglycerin fatty acid ester tables obtained in Comparative Reference Example 3 As shown in the result of No. 1, the foam detergent of the present invention was higher in safety, more excellent in foamability, foam sustainability, detergency, and better in stability than the comparative example. A mousse-like detergent having the following composition was prepared and evaluated for the same items as in Table 1. Example 4 (Component Name) (% by Weight) Reaction Product (A1) Mainly Containing Polyglycerol Fatty Acid Ester Mixture Obtained in Reference Example 1 2.5 Cetostearyl Alcohol 2.0 Fragrance 2 Purified water 53.5 Ethyl alcohol 35.0 L. P. G. FIG. 7.0 <Example 5> (Ingredient name) (% by weight) Reaction product (A1) mainly containing the polyglycerin fatty acid ester mixture obtained in Reference Example 1 1.5 Cetyl alcohol 3.0 Safflower oil 0 .1 Perfume 0.2 Purified water 36.2 Ethyl alcohol 55.0 L. P. G. FIG. 4.0 <Example 6> (Ingredient name) (% by weight) Reaction product (A1) mainly containing the polyglycerin fatty acid ester mixture obtained in Reference Example 1 1.2 Behenyl alcohol 0.5 POE (4) Stearyl Ether 1.0 Orange oil 0.1 Fragrance 0.1 Purified water 47.1 Ethyl alcohol 45.0 L. P. G. FIG. 5.0 The foam detergents of Examples 4 to 6 all have high safety,
The foaming properties, foam persistence, detergency were excellent, and the stability was also good. The foaming detergent of the present invention can be effectively applied to a portion to be washed, and has high safety. It is possible to remove dirt simply by wiping with a towel without rinsing with water. During use, the feel was excellent after use. (Below)

──────────────────────────────────────────────────の Continued on the front page (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1/00-17/08 A61K 7/00 A61K 7/075 A61K 7/50 C07C 67/26 C07C 69 / 30

Claims (1)

(57) [Claims] [Claim 1] For the addition polymerization reaction of fatty acid and glycidol
Was synthesized from, monoester content of 70% (high
To peak area ratio based on fast liquid chromatography
Based on polyglycerol fatty acid ester mixture
One or more of the reaction products
% Of one or more lower monohydric alcohols having 1 to 3 carbon atoms, 30 to 60% by weight, and 30 to 30% by weight of water.
A foam characterized by comprising a stock solution containing 60% by weight, 0.1 to 5% by weight of one or more of higher alcohols having 12 to 22 carbon atoms, and a propellant. Cleaning agent.