Cosmetic additive

Abstract

To provide a cosmetic additive that is derived from natural materials, provides a superior sensory feel upon application to skin, and reduces environmental burden.SOLUTION: A cosmetic additive comprising a crosslinked product of a water-soluble polymer in which acidic groups are introduced into a partial degradation product of starch.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cosmetic additive. [Background technology]

[0002] In recent years, there has been a growing demand for cosmetics that are made from natural ingredients and that use fewer synthetic chemicals, due to concerns about skin-friendliness and environmental friendliness. Against this backdrop, research and development into cosmetics that utilize natural ingredients such as starch is progressing.

[0003] Patent Document 1 discloses that legume starch or its chemically modified form has the effect of protecting the skin from particulate air pollutants. Patent Document 2 discloses that blending carboxyalkylated granular starch into a cosmetic emulsion improves the cushioning effect and softness of the emulsion. Patent Document 3 discloses that an oil-in-water emulsion containing a starch-based thickener can be used as a cosmetic composition. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special table number 2022-526791 [Patent Document 2] Special table number 2022-526782 [Patent Document 2] Special table number 2019-526575 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a cosmetic additive that is derived from natural materials, has an excellent feel when applied to the skin, and has a low environmental impact. [Means for solving the problem]

[0006] The present inventors have discovered that a cosmetic additive that provides an excellent feel when applied to the skin can be obtained from a material derived from starch, and have thus completed the present invention.

[0007] That is, the present invention includes the following aspects. <1> A cosmetic additive comprising a crosslinked product of a water-soluble polymer in which an acidic group has been introduced into a partially hydrolyzed product of starch. <2> Item 2. The cosmetic additive according to Item 1, wherein the crosslinked water-soluble polymer has an average particle size of 5 to 850 μm. <3> Item 3. The cosmetic additive according to Item 1 or 2, wherein the weight-average molecular weight of the partially hydrolyzed starch is 50,000 to 7,500,000. <4> Item 3. The cosmetic additive according to Item 1 or 2, wherein the water-soluble polymer has a total acid value of 50 to 350 mgKOH / g. <5> Item 3. The cosmetic additive according to Item 1 or 2, wherein the water-soluble polymer has a free acid value of 0 to 100 mgKOH / g. <6> Item 3. The cosmetic additive according to Item 1 or 2, which is a thickener, a texture improver, a dispersant, an emulsifier, an emulsion stabilizer, a water-retaining agent, or a stabilizer. <7> Item 3. A cosmetic composition comprising the cosmetic additive according to Item 1 or 2. <8> Item 8. The cosmetic composition according to item 7, which is a water-based or oil-in-water emulsion system. <9> Item 8. The cosmetic composition according to Item 7, which is a skin care cosmetic, a hair care cosmetic, a body care cosmetic, or a makeup cosmetic. <10> a step of introducing an acidic group into a partially hydrolyzed product of starch to obtain a water-soluble polymer; cross-linking the water-soluble polymer; and The crosslinked water-soluble polymer is pulverized to have an average particle size of 5 to 850 μm. A method for producing cosmetic additives. [Effects of the Invention]

[0008] The cosmetic additive of the present invention is derived from natural materials and has an excellent feel when applied to the skin. Furthermore, since the cosmetic additive of the present invention is derived from starch, it is highly biodegradable, has a small environmental impact, and is sustainable. [Brief explanation of the drawings]

[0009] [Figure 1] 1 shows the appearance of the gels of Examples 1 and 2 and Comparative Examples 1 to 3. [Figure 2] 1 shows the appearance of the lotions of Example 10 and Comparative Examples 5 to 7. [Figure 3] 1 shows the appearance of the lotions of Example 11 and Comparative Examples 8 to 10. DETAILED DESCRIPTION OF THE INVENTION

[0010] <<Cosmetic additives>> The cosmetic additive of the present invention is characterized by comprising a crosslinked product of a water-soluble polymer in which an acidic group has been introduced into a partial hydrolyzate of starch. In the present invention, the term "water-soluble polymer" refers to a partial hydrolyzate of starch in which an acidic group has been introduced.

[0011] <Partially hydrolyzed starch> The use of starch as a raw material for the water-soluble polymer makes it possible to provide a cosmetic additive that is highly safe for the human body and has a small environmental impact. The plant from which the starch is derived is not particularly limited, and examples thereof include tapioca starch, potato starch, corn starch such as waxy corn starch and high-amylose starch, wheat starch, rice starch, and sweet potato starch.

[0012] The starch may be a derivative (also called processed starch or chemically modified starch) in which the hydrogen atom of the hydroxyl group of the glucose unit constituting the starch has been substituted with a functional group, or bleached starch. The position of the hydroxyl group where the hydrogen atom is substituted may be any of the 1st, 2nd, 3rd, 4th, and 6th positions of the glucose unit, with the 2nd, 3rd, and 6th positions being preferred. Examples of functional groups include hydrocarbon groups such as methyl and ethyl groups; substituents having a hydroxyl group such as hydroxypropyl and hydroxyethyl groups; and substituents having a carboxyl group such as carboxymethyl groups. Examples of starch derivatives include acetylated adipate cross-linked starch, acetylated phosphate cross-linked starch, acetylated oxidized starch, sodium octenylsuccinate starch, acetate starch, oxidized starch, hydroxypropyl starch, hydroxypropylphosphate cross-linked starch, phosphate monoesterified phosphate cross-linked starch, phosphated starch, phosphate cross-linked starch, cationic starch, urea phosphate esterified starch, etc. Also usable are methylethylated starch and hydroxypropylmethylated starch, which are substituted with two or more functional groups.

[0013] Partial starch hydrolysates are produced by decomposing some of the glycosidic bonds in starch. The position and manner of decomposition are not limited. The weight-average molecular weight (Mw) of the partial starch hydrolysates is not particularly limited, but is preferably 7.5 million or less, more preferably 5 million or less, even more preferably 4.5 million or less, and even more preferably 4 million or less. The lower limit of the weight-average molecular weight of the partial starch hydrolysates is not particularly limited, but is preferably 50,000 or more, more preferably 200,000 or more, even more preferably 1 million or more, and even more preferably 2 million or more. If the weight-average molecular weight is less than 50,000, the thickening properties tend to decrease when used as a thickener. If the weight-average molecular weight exceeds 7.5 million, the reaction during introduction of acidic groups and the operability in the purification process tend to decrease, and the thickening properties tend to decrease when used as a thickener. If the viscosity of the partial starch hydrolysates affects the production process, it is possible to use two or more partial starch hydrolysates with different weight-average molecular weights or other additives in combination, depending on the application and cost. The weight-average molecular weight can be determined by aqueous size exclusion chromatography based on a calibration curve of molecular weight and elution time prepared using pullulan of known molecular weight.

[0014] The dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the starch partial hydrolysate is not particularly limited, but is generally 5 or more, preferably 7 or more. If the dispersity is less than 5, the thickening properties tend to decrease when used as a thickener. There are no particular upper limits to the dispersity. The number average molecular weight can be determined by aqueous size exclusion chromatography based on a calibration curve of molecular weight and elution time prepared using pullulan with a known molecular weight.

[0015] <Acidic group> Examples of acidic groups to be introduced into the partial hydrolyzates of starch include acidic groups having a carboxyl group, such as a carboxyalkyl group or a carboxyalkenyl group; acidic groups having a sulfo group, such as a sulfoalkyl group or a sulfoalkenyl group; and acidic groups having a phospho group, such as a phosphoalkyl group or a phosphoalkenyl group.

[0016] A carboxyalkyl group is an alkyl group substituted with a carboxyl group. The number of carbon atoms in the alkyl group substituted with a carboxyl group is preferably 1 to 8, more preferably 1 to 5. The alkyl group may be either linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, and a 1-ethyl-n-propyl group.

[0017] Specific examples of the carboxyalkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group, and a carboxypentyl group.

[0018] A carboxyalkenyl group is an alkenyl group substituted with a carboxyl group. The number of carbon atoms in the alkenyl group substituted with a carboxyl group is preferably 2 to 8, more preferably 2 to 4. The alkenyl group may be either linear or branched. Specific examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, and 1-methyl-2-propenyl.

[0019] Specific examples of the carboxyalkenyl group include a carboxyethenyl group, a carboxypropenyl group, and a carboxybutenyl group.

[0020] A sulfoalkyl group is an alkyl group substituted with a sulfo group. Examples of the alkyl group substituted with a sulfo group include the alkyl groups mentioned in relation to the carboxyalkyl group. Specific examples of sulfoalkyl groups include a sulfomethyl group, a sulfoethyl group, and a sulfopropyl group.

[0021] The sulfoalkenyl group is an alkenyl group substituted with a sulfo group. The alkenyl group substituted with a sulfo group can be any of the alkenyl groups described above for the carboxyalkenyl group. Specific examples of the sulfoalkenyl group include a sulfoethenyl group and a sulfopropenyl group.

[0022] A phosphoalkyl group is an alkyl group substituted with a phospho group. The alkyl groups substituted with a phospho group can be the same as those mentioned for the carboxyalkyl group. Specific examples of the phosphoalkyl group include a phosphomethyl group, a phosphoethyl group, and a phosphopropyl group.

[0023] A phosphoalkenyl group is an alkenyl group substituted with a phospho group. The alkenyl group substituted with a phospho group can be any of the alkenyl groups described above for the carboxyalkenyl group. Specific examples of phosphoalkenyl groups include phosphoethenyl and phosphopropenyl groups.

[0024] Among the acidic groups, from the viewpoint of ease of introduction into partial hydrolyzates of starch, acidic groups having a carboxyl group or a sulfo group are preferred, a carboxyalkyl group, a carboxyalkenyl group or a sulfoalkyl group is more preferred, a carboxyalkyl group having 1 to 5 carbon atoms is even more preferred, and a carboxymethyl group is particularly preferred.

[0025] In the water-soluble polymer, the acidic group may bond with a metal ion to form a salt. Examples of the metal that constitutes the salt of the acidic group include alkali metals such as sodium, lithium, and potassium, and alkaline earth metals such as calcium, magnesium, and barium. Sodium salts, potassium salts, and calcium salts are preferred, and sodium salts and potassium salts are more preferred.

[0026] The molecular weight of the water-soluble polymer is not particularly limited, but the weight-average molecular weight, calculated as pullulan by aqueous size exclusion chromatography, is preferably 500,000 to 40,000,000, and more preferably 800,000 to 35,000,000. If the weight-average molecular weight is less than 500,000, the thickening effect when used as a thickener tends to decrease, while if it exceeds 40,000,000, the viscosity tends to be high, resulting in poor handling during production. The weight-average molecular weight, calculated as pullulan by aqueous size exclusion chromatography, can be determined based on a calibration curve of molecular weight and elution time prepared using pullulan of known molecular weight in aqueous size exclusion chromatography.

[0027] The water-soluble polymer preferably has a total acid value of 50 to 350 mgKOH / g, more preferably 50 to 300 mgKOH / g. Furthermore, when improving the biodegradability of a crosslinked product of the water-soluble polymer, the total acid value is preferably 50 to 100 mgKOH / g, more preferably 50 to 80 mgKOH / g. When improving the crosslink density and physical strength of the crosslinked product, the total acid value is preferably 100 to 300 mgKOH / g, more preferably 130 to 300 mgKOH / g. When some or all of the acid groups introduced into the partially hydrolyzed starch product are neutralized by forming a salt, the total acid value refers to the acid value measured after returning the neutralized acid groups to their unneutralized state, and indicates the amount of all acid groups possessed by the water-soluble polymer. When the total acid value is less than 50 mgKOH / g or more than 350 mgKOH / g, the thickening effect tends to decrease when used as a thickener. The total acid number and the free acid number described below can be measured by neutralization titration using KOH.

[0028] The free acid value of the water-soluble polymer is preferably 0 to 100 mgKOH / g. The free acid value refers to the amount of acidic groups present in the water-soluble polymer that do not form salts. If the free acid value exceeds 100 mgKOH / g, the thickening properties when used as a thickener tend to decrease. Furthermore, to improve the thickening properties when used as a thickener, the free acid value of the water-soluble polymer is preferably 0 to 70 mgKOH / g, more preferably 0 to 50 mgKOH / g.

[0029] When acidic groups are introduced by reacting a haloalkyl compound having an acidic group with hydroxyl groups of starch to obtain a water-soluble polymer, the total acid value can also be expressed in terms of the degree of etherification. The degree of etherification is preferably 0.1 to 2.0, more preferably 0.1 to 1.6. Furthermore, to improve the biodegradability of the crosslinked water-soluble polymer, the degree of etherification is preferably 0.1 to 0.3, more preferably 0.16 to 0.26. To improve the crosslink density and the physical strength of the crosslinked product, the degree of etherification is preferably 0.3 to 1.6, more preferably 0.46 to 1.51. If the degree of etherification is less than 0.1 or more than 2.0, the thickening properties when used as a thickener tend to decrease. The degree of etherification can be determined by ashing titration or the like. Furthermore, the total acid value is detected by the introduction of acidic groups, and if the raw starch or partial hydrolyzate of starch does not contain acidic groups, the acidic groups detected by measuring the total acid value are considered to be equivalent to those introduced by the etherification reaction. Therefore, if the raw starch partial hydrolyzate does not contain acidic groups, the degree of etherification can be simply calculated from the above-mentioned total acid value. For example, if the acidic groups are carboxymethyl groups and all of them are neutralized as sodium salts, the degree of etherification can be calculated as follows: (162 × total acid value) ÷ (56100 - 80 × total acid value). The unit of the total acid value in this case is mgKOH / g.

[0030] The dispersity (weight average molecular weight / number average molecular weight) of the water-soluble polymer is not particularly limited, but is preferably 5 to 110, and more preferably 7 to 70. If it is less than 5 or exceeds 110, the thickening properties tend to decrease when used as a thickener. The number average molecular weight of the water-soluble polymer can be determined by aqueous size exclusion chromatography based on a calibration curve of molecular weight and elution time prepared using pullulan of known molecular weight.

[0031] The crosslinking of the water-soluble polymer is preferably formed via the acidic groups introduced into the water-soluble polymer. Examples of the crosslinked structure include ionic bonds between the acidic groups and coordinate bonds via metal ions, and when the acidic groups have carboxyl groups, hydrogen bonds such as dimerization of the carboxyl groups.

[0032] The crosslinked water-soluble polymer preferably has an average particle size of 5 to 850 μm, more preferably 7 to 800 μm. If the average particle size is less than 5 μm, the thickening effect when used as a thickener tends to decrease. Furthermore, when imparting crushability (easily disintegratable) to the crosslinked water-soluble polymer, the average particle size is preferably 100 to 800 μm, more preferably 300 to 800 μm. Furthermore, when imparting non-disintegratability or a smooth feel to the crosslinked water-soluble polymer, the average particle size is preferably 7 to 50 μm, more preferably 10 to 30 μm. Note that the average particle size in the present invention is the particle size at 50% cumulative volume (D50).

[0033] The cosmetic additives can be used as thickeners, texture improvers, dispersants, emulsifiers, emulsion stabilizers, water retention agents, stabilizers, and the like for cosmetics.

[0034] <<Manufacturing Method for Cosmetic Additives>> The method for producing the cosmetic additive of the present invention includes the steps of introducing acidic groups into a partially hydrolyzed product of starch to obtain a water-soluble polymer, crosslinking the water-soluble polymer, and pulverizing the crosslinked water-soluble polymer to an average particle size of 5 to 850 μm.

[0035] <Step of obtaining water-soluble polymer> The process for obtaining a water-soluble polymer includes, as its internal steps, step (1) of partially decomposing starch and step (2) of introducing acidic groups into the starch or the partially decomposed starch. The order of steps (1) and (2) is not limited.

[0036] In the step (1) of partially decomposing starch, the method of partial decomposition is not particularly limited, and examples thereof include methods of subjecting starch to enzyme treatment, acid treatment, physical crushing, etc. These methods may also be combined. The enzyme treatment may be carried out after gelatinization of starch, or may be carried out simultaneously with gelatinization. A method of carrying out the enzyme treatment after starch gelatinization includes a method in which the starch is first suspended in water and heated to gelatinize it, and then an enzyme is added to carry out the enzymatic reaction. A method of carrying out the enzyme treatment simultaneously with starch gelatinization includes a method in which the starch is suspended in water, and then the enzyme is added, and the resulting mixture is heated within a temperature range in which the enzyme is not completely inactivated. Among these methods, it is preferable to carry out the enzyme treatment while gelatinizing the starch by heating and kneading it at 70 to 110°C.

[0037] When partial degradation of starch is carried out by enzymatic treatment, the enzyme used may be either an exo-enzyme or an endo-enzyme. Specific examples of the enzyme include α-amylase, amylomaltase, cyclomaltodextrin glucanotransferase, 4-α-glucanotransferase, 4,6-α-glucanotransferase, neopullulanase, and amylopullulanase. These enzymes may also be used in combination. The pH during the enzymatic treatment is not particularly limited, but a pH of 5.0 to 7.0 is preferred. The pH can be adjusted by adding hydrochloric acid, acetic acid, sodium hydroxide, potassium hydroxide, or the like.

[0038] When partial decomposition of starch is carried out by acid treatment, the acid to be used is not particularly limited as long as it can decompose starch, and specific examples include hydrochloric acid, sulfuric acid, oxalic acid, acetic acid, formic acid, trifluoroacetic acid, etc. The temperature during the acid treatment is preferably 150 to 160°C. When partial decomposition of starch is carried out by physical disruption, specific means include irradiation, shearing, grinding, high-pressure treatment, ultrasound, thermal decomposition, photolysis, and combinations thereof.

[0039] In step (2) of introducing acidic groups into starch or a partial starch hydrolysate, if this step is carried out before step (1), acidic groups are introduced into starch, whereas if this step is carried out after step (1), acidic groups are introduced into the partial starch hydrolysate. The introduction of acidic groups is carried out by reacting starch or a partial starch hydrolysate with an acidic group-containing compound or its precursor. This reaction introduces acidic groups into hydroxyl groups of the starch or partial starch hydrolysate. The acidic group-containing compound is not particularly limited as long as it can introduce acidic groups, and examples thereof include haloalkyl compounds having acidic groups, haloalkenyl compounds having acidic groups, acid anhydrides, and salts thereof. Halogens constituting haloalkyl compounds and haloalkenyl compounds include chlorine and bromine.

[0040] Specific examples of the acidic group-containing compound include monochloroacetic acid, monobromoacetic acid, 3-bromopropionic acid, 6-bromohexanoic acid, succinic anhydride, maleic anhydride, vinylsulfonic acid, phosphorus oxychloride, ethyl monochloroacetate, and sodium and potassium salts thereof. Specific examples of the salts include sodium monochloroacetate, potassium monochloroacetate, and sodium vinylsulfonate.

[0041] Examples of the precursor of the acidic group-containing compound include acrylonitrile, etc. Examples of the method using acrylonitrile include a method in which acrylonitrile is first reacted with starch or a partial hydrolysis product thereof under basic conditions to introduce a cyanoethyl group, which is then converted into an amide group (Synthesis; 1989(12):949-950), and the resulting amide is then subjected to alkaline hydrolysis.

[0042] The reaction scheme for producing a water-soluble polymer by reacting starch or a partial starch hydrolysate with monochloroacetic acid is shown in formula (I). [ka]

[0043] The reaction scheme for producing a water-soluble polymer by reacting starch or a partial starch hydrolysate with 3-bromopropionic acid is shown in formula (II). [ka]

[0044] The reaction scheme for producing a water-soluble polymer by reacting starch or a partial starch hydrolysate with 6-bromohexanoic acid is shown in formula (III). [ka]

[0045] The reaction scheme for producing a water-soluble polymer by reacting starch or a partially hydrolyzed starch product with succinic anhydride is shown in formula (IV). [ka]

[0046] The reaction scheme for producing a water-soluble polymer by reacting starch or a partially hydrolyzed starch product with maleic anhydride is shown in formula (V). [ka]

[0047] The reaction scheme for producing a water-soluble polymer by reacting starch or a partially hydrolyzed starch product with sodium vinyl sulfonate is shown in formula (VI). [ka]

[0048] Although formulas (I) to (VI) show water-soluble polymers in which sodium salts of acidic groups have been introduced into all hydroxyl groups at the 6-position of glucose units, hydroxyl groups to which no acidic group has been introduced may remain. Furthermore, acidic groups that have not been neutralized by salts may also exist. The position at which the acidic group is introduced is not limited as long as it is a hydroxyl group present in starch or its partial hydrolyzate, and may be any of the 1-, 2-, 3-, 4-, and 6-positions.

[0049] When a haloalkyl compound or haloalkenyl compound is used as the acidic group-containing compound, it is preferable to use 1 to 1.5 equivalents of an alkaline agent relative to the haloalkyl compound or haloalkenyl compound. Examples of alkaline agents include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, sodium carbonate, and potassium carbonate. The acidic groups introduced into the starch or partial starch hydrolysate preferably form salts with the sodium, potassium, lithium, ammonia, or the like derived from the alkaline agent. For this reason, it is preferable to use an amount of alkaline agent necessary for both the reaction of the haloalkyl compound or haloalkenyl compound with the starch or partial starch hydrolysate and the neutralization of the acidic groups of the haloalkyl compound or haloalkenyl compound. For example, when chloroacetic acid is used as the acidic group-containing compound, it is theoretically preferable to use at least 2 equivalents of the alkaline agent relative to the chloroacetic acid. When sodium chloroacetate is used, it is preferable to use at least 1 equivalent of the alkaline agent relative to the sodium chloroacetate because the acidic groups are neutralized in advance.

[0050] The amount of the acidic group-containing compound used can be set arbitrarily depending on the total acid value (degree of etherification) to be achieved in the water-soluble polymer. Typically, 0.5 to 5.0 equivalents per mole of hydroxyl groups in starch or a partial starch hydrolysate are preferred, with 0.5 to 2 equivalents being more preferred. When using a haloalkyl compound such as chloroacetic acid and carrying out the reaction in an aqueous solution, the acidic group introduction reaction and the hydrolysis reaction of the haloalkyl compound compete with each other, so the haloalkyl compound is required in excess of the theoretical amount. The amount of haloalkyl compound used in the aqueous solution reaction is preferably set to 5 equivalents or less relative to the theoretical value.

[0051] The reaction temperature between starch or a partial starch hydrolysate and an acidic group-containing compound is not particularly limited, but is preferably 0 to 120°C. The reaction time is not particularly limited, but is preferably 1 to 24 hours. The reaction may be carried out in water, or in a mixed solvent of water and an alcohol such as methanol, ethanol, isopropanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, or ethylene glycol monoethyl ether, or a glycol ether such as ethylene glycol dimethyl ether. Alternatively, the reaction may be carried out by dispersing dried starch or a partial starch hydrolysate powder in a hydrophilic solvent such as an alcohol such as methanol, ethanol, isopropanol, or butanol, or a glycol ether such as ethylene glycol dimethyl ether. When a mixed solvent is used, the proportion of solvents other than water in the mixed solvent is preferably 50% by volume or less. A reaction vessel or an extruder may be used as the reaction apparatus.

[0052] When a haloalkyl compound such as chloroacetic acid or a salt thereof is used as the acidic group-containing compound, the reaction temperature with starch or a partial decomposition product of starch is not particularly limited, but is preferably 0 to 100°C.

[0053] In particular, when chloroacetic acid or its salt is used as the haloalkyl compound, the reaction is preferably carried out at 25 to 90°C to prevent hydrolysis by water in the reaction solution. The reaction time is preferably the time until the raw material haloalkyl compound is consumed, and more preferably 1 to 12 hours to ensure the stability of the haloalkyl compound and the efficiency of the process. The reaction may be carried out in water, or in a mixed solvent of water with alcohols such as methanol, ethanol, isopropanol, and butanol, or glycol ethers such as ethylene glycol dimethyl ether. Alternatively, the reaction may be carried out by dispersing powder of dried starch or a partial starch hydrolyzate in a hydrophilic solvent such as alcohols such as methanol, ethanol, isopropanol, and butanol, or glycol ethers such as ethylene glycol dimethyl ether. When a mixed solvent is used, the proportion of solvents other than water in the mixed solvent is preferably 50% by volume or less. A reaction vessel or extruder may be used as the reaction apparatus.

[0054] When an acid anhydride is used as the acidic group-containing compound, the reaction proceeds simply by mixing starch or a partial starch hydrolyzate with the acid anhydride and heating. However, to promote the reaction, a catalyst such as sodium carbonate, sodium hydroxide, or a tertiary amine such as triethylamine, an imidazole such as 2-methylimidazole, a quaternary ammonium salt such as tetrabutylammonium bromide, or a phosphonium salt such as tetrabutylphosphonium bromide may be used. The amount of catalyst added is preferably 0.1 equivalents or less relative to the acidic group-containing compound. These catalysts may be used alone or in combination of two or more.

[0055] The reaction time is preferably the time until the acid anhydride, which is the raw material, is consumed, more preferably 1 to 12 hours. The end point of the reaction can be determined by acid value measurement or IR measurement. The reaction may be carried out in water, but to prevent hydrolysis or alcoholysis of the acid anhydride, the reaction solvent is preferably an aprotic solvent such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone. When a mixed solvent is used, the proportion of solvents other than water in the mixed solvent is preferably 50% by volume or more. When the reaction is carried out without a solvent, the acid anhydride can function as a solvent, so the reaction temperature is preferably above the melting point of the acid anhydride. When a solvent is used in the reaction, the reaction temperature is preferably 50 to 100°C, more preferably 70 to 90°C. A reaction kettle, extruder, or the like can be used as the reaction apparatus.

[0056] After step (2) of introducing acidic groups into starch or a partial hydrolyzate of starch, if salts of the acidic groups have been formed, it is preferable to neutralize some of them. Neutralization converts some of the acidic groups that formed salts into free acidic groups. For example, when monochloroacetic acid is used as the acidic group-containing compound and sodium hydroxide is used as the alkaline agent, sodium salts of carboxyl groups are added to the starch or partial hydrolyzate thereof. Adding an acid to this converts some of the carboxyl groups into free carboxylic acids.

[0057] The acid used for neutralization is not particularly limited. When the acidic group is a carboxyl group, an acid with a pKa equal to or lower than that of the carboxyl group is preferred. Examples include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, formic acid, trichloroacetic acid, fumaric acid, maleic acid, oxalic acid, malonic acid, succinic acid, malic acid, citric acid, and tartaric acid. A strong acid is preferably used to neutralize a sulfo or phospho group, and mineral acids such as hydrochloric acid and sulfuric acid, or strong acidic ion exchange resins are used. Neutralization can be carried out using known devices such as a reaction vessel or extruder. After the addition of the acid, the mixture is preferably stirred at 0 to 50°C for 0.2 to 4 hours to allow the neutralization reaction to proceed. The neutralization reaction is preferably carried out under conditions of pH 6.8 to 7.2.

[0058] In step (2) or the subsequent neutralization reaction, salts may be formed between the halogen derived from the acidic group-containing compound and the metal or ammonia derived from the alkaline agent, so desalting is preferred. Examples of desalting methods include a method in which a water-soluble polymer is dissolved in water to form an aqueous solution, which is then dropped into a dispersion solvent to reprecipitate the water-soluble polymer and recover it by filtration. The water-soluble polymer recovered by filtration is then dispersed in a cleaning solvent, stirred, and the water-soluble polymer particles are recovered by filtration. Examples of the dispersion solvent and cleaning solution include water, a hydrophilic organic solvent, and a mixture of water and a hydrophilic organic solvent. Examples of hydrophilic organic solvents include methanol, ethanol, n-propanol, isopropanol, propylene glycol, acetone, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide. Two or more hydrophilic organic solvents may be used in combination. When a mixture of water and a hydrophilic organic solvent is used, the proportion of water in the mixture is preferably 5 to 30% by volume, more preferably 15 to 25% by volume. The dispersion solvent and cleaning solution may be the same or different. Another example of a desalination method is to treat an aqueous solution of the water-soluble polymer with a filter having an ultrafiltration membrane. Desalination is preferably carried out until the salt concentration in the water-soluble polymer becomes 1% or less.

[0059] <Step of cross-linking the water-soluble polymer> In this step, water-soluble polymers are crosslinked. Crosslinking of water-soluble polymers is preferably performed without using a crosslinking agent. For example, a method of heating and drying the water-soluble polymer under hydrous conditions can be used. At the start of the heating and drying process, the water-soluble polymer may be in the form of an aqueous solution or a wet powder containing a hydrous solvent with a water content of 1% by weight or more. When drying a wet powder containing a hydrous solvent, the wet ratio of the wet powder at the start of drying is preferably 1 to 85% by weight, more preferably 20 to 80% by weight. The wet ratio refers to the ratio of the total amount of water and hydrophilic solvent to the wet powder. The heating temperature is preferably 50 to 200°C, more preferably 60 to 150°C. The pressure during heating and drying is not particularly limited, and can be normal pressure, preferably 0.9 to 1.1 atm. The drying method is not particularly limited, and examples include methods using a drum dryer, spray dryer, Nauta mixer, etc.

[0060] When crosslinking water-soluble polymers, a solvent other than water may be used in addition to water. Examples of the solvent other than water include lower aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, and propylene glycol; ketones such as acetone; ethers such as dioxane, tetrahydrofuran, and methoxy(poly)ethylene glycol; and amides such as ε-caprolactam and N,N-dimethylformamide. The proportion of the solvent other than water in the total solvent is preferably adjusted based on the boiling point of the solvent. When the boiling point of the solvent is 100°C or less, it is preferably 70% by volume or more, and when the boiling point is higher than 100°C, it is preferably 30% by volume or less.

[0061] The crosslinked structure between water-soluble polymers can be formed without using a crosslinking agent as described above, but a crosslinking agent may also be used. Examples of the crosslinking agent include epoxy compounds, polyhydric alcohol compounds, polyvalent amine compounds, polyisocyanate compounds, polycarboxylic acid compounds, polyhydric aldehyde compounds, alkylene carbonate compounds, haloepoxy compounds, halohydrin compounds, polyvalent oxazoline compounds, carbodiimide compounds, silane coupling agents, and polyvalent metal compounds.

[0062] Examples of the epoxy compound include succinic acid glycidyl ester, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and glycidol.

[0063] Examples of the polyhydric alcohol compound include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,3-propanediol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, polypropylene glycol, glycerin, polyglycerin, 2-butene-1,4-diol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,2-cyclohexanediol, trimethylolpropane, diethanolamine, triethanolamine, polyoxypropylene, oxyethylene-oxypropylene block copolymer, pentaerythritol, and sorbitol.

[0064] Examples of the polyvalent amine compounds include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, inorganic salts or organic salts (such as azithinium salts) of these polyvalent amine compounds, and polysaccharides having amino groups such as chitin.

[0065] Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate and hexamethylene diisocyanate, and examples of the polyoxazoline compound include 1,2-ethylenebisoxazoline.

[0066] Examples of the polycarboxylic acid compound include tartaric acid, adipic acid, citric acid, malic acid, glutaric acid, phthalic acid, maleic acid, and itaconic acid.

[0067] Examples of the polyhydric aldehyde compound include glutaraldehyde and glyoxal.

[0068] Examples of the alkylene carbonate compound include 1,3-dioxolan-2-one, 4-methyl-1,3-dioxolan-2-one, 4,5-dimethyl-1,3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2-one, 1,3-dioxan-2-one, 4-methyl-1,3-dioxan-2-one, and 4,6-dimethyl-1,3-dioxan-2-one.

[0069] Examples of the haloepoxy compound include epichlorohydrin, epibromohydrin, α-methylepichlorohydrin, and polyamine adducts thereof (eg, Kaimen (registered trademark) manufactured by Hercules).

[0070] Other known crosslinking agents that can be used include aqueous carbodiimide compounds (e.g., Carbodilite manufactured by Nisshinbo Chemical Inc.), silane coupling agents such as γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, and polyvalent metal compounds such as hydroxides and chlorides of zinc, calcium, magnesium, aluminum, iron, zirconium, etc.

[0071] The crosslinked structure between water-soluble polymers obtained in this step may be formed by a chemical bond, a physical bond, or both. Specific examples of the crosslinked structure include an ionic bond between an acidic group on the water-soluble polymer and a neutralized acidic group, a hydrogen bond between an acidic group or a salt thereof on the water-soluble polymer and a hydroxyl group on the water-soluble polymer, an ionic bond with a compound having an opposite charge to the water-soluble polymer (a compound containing a basic group such as a cationic group or an amino group when the acidic group of the water-soluble polymer is a carboxylic acid), an ionic bond by a divalent alkali metal ion, a coordinate bond via a metal ion, and a hydrogen bond such as dimerization of carboxylic acid when the acidic group is a carboxylic acid group.

[0072] The content of water and / or hydrophilic solvent in the crosslinked water-soluble polymer can be adjusted by treatment such as heating or drying. The content of water and / or hydrophilic solvent in the crosslinked water-soluble polymer is preferably 0.1 to 20%, more preferably 1 to 19%. Examples of hydrophilic solvents include methanol, ethanol, n-propanol, isopropanol, propylene glycol, acetone, ethylene glycol, dipropylene glycol, diethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, N,N-dimethylformamide, and dimethyl sulfoxide.

[0073] The crosslinked water-soluble polymer may be subjected to treatments such as desalting and washing to remove impurities and by-products. Desalting can be performed using a filter having a reverse osmosis membrane. The washing liquid may be water, a hydrophilic organic solvent, or a mixture of water and a hydrophilic organic solvent. Examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, isopropanol, propylene glycol, acetone, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide. When a mixture of water and a hydrophilic organic solvent is used, the proportion of water in the mixture is preferably 5 to 30% by volume, more preferably 15 to 25% by volume.

[0074] <Step of pulverizing the crosslinked water-soluble polymer> In this step, the crosslinked water-soluble polymer is pulverized to an average particle size of 5 to 850 μm. The average particle size after pulverization is 5 to 850 μm, preferably 7 to 800 μm. If the average particle size is less than 5 μm, the thickening effect when used as a thickener tends to decrease. Furthermore, when imparting crushability (easily disintegratable) to the crosslinked water-soluble polymer, the average particle size is preferably 100 to 800 μm, more preferably 300 to 800 μm. Furthermore, when imparting non-disintegratability or a smooth feel to the crosslinked water-soluble polymer, the average particle size is preferably 7 to 50 μm, more preferably 10 to 30 μm. Note that the average particle size in the present invention is the particle size at 50% cumulative volume (D50).

[0075] The pulverization method is not particularly limited, and may be a method using a conventionally known pulverization device such as a jet mill, ball mill, sand mill, crusher, hammer mill, feather mill, disk mill, chopper, or a combination thereof. After pulverization, the powder may be classified using a sieve, if necessary.

[0076] The crosslinked water-soluble polymer may be pulverized in a dry state, or may be pulverized in a swollen state after being mixed with an aqueous medium such as water, alcohols, or polyols. When swollen, the polymer may become a gel-like crushed particle. When this gel is subjected to shearing (e.g., ultrasonication or high-speed shearing), the crushed particles are broken down, yielding a viscous liquid sol. This sol can be used to produce a cosmetic composition.

[0077] Alternatively, the crushing may be carried out under conditions that allow the crushed particles to remain in a gel state. In this case, the cosmetic additive is added to the cosmetic in the form of a crushed particle gel. Then, immediately before use, the user gently presses the mixture with their fingers to shear, thereby crushing the crushed particles in the cosmetic, thereby obtaining a viscous liquid sol.

[0078] <<Cosmetic Composition>> The cosmetic composition of the present invention contains the cosmetic additive. The amount of the cosmetic additive in the cosmetic composition is preferably 0.1 to 20 wt %, more preferably 0.2 to 10 wt %.

[0079] In the cosmetic composition, the cosmetic additive is preferably present in the aqueous phase in a state dissolved in an aqueous solvent. Examples of aqueous solvents include water, alcohols such as ethanol and isopropanol, and polyols such as polyethylene glycol, polybutylene glycol, propylene glycol, and glycerin. A mixed solvent of water and an aqueous medium other than water may be used. In this case, the amount of water in the mixed solvent is preferably 20 to 100 wt%, more preferably 40 to 100 wt%. The amount of aqueous solvent in the cosmetic composition is preferably 20 to 95 wt%, more preferably 25 to 90 wt%.

[0080] In addition to cosmetic additives, the cosmetic composition may contain other additives commonly used in cosmetics, such as thickeners, moisturizers, astringents, keratin softeners, emollients, surfactants, fragrances, colorants, preservatives, bactericides, antioxidants, pigments, ultraviolet absorbers, sequestering agents, and buffers. The amounts of these substances in the cosmetic composition can be adjusted as desired within the range that can solve the problems of the present invention.

[0081] (thickener) Examples of thickeners include guar gum, locust bean gum, queen seed, carrageenan, galactan, gum arabic, tara gum, tamarind, furcellaran, karaya gum, aoi, caragam, tragacanth gum, pectin, salts such as pectic acid and sodium salts, salts such as alginic acid and sodium salts, mannan, starch such as rice, corn, potato, and wheat, dextrin, xanthan gum, dextran, succinoglucan, curdlan, hyaluronic acid and salts thereof, xanthan gum, pullulan, and gellan gum. cellulose, chitin, chitosan, agar, cassou extract, chondroitin sulfate, casein, collagen, gelatin, albumin, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and its sodium salts, methylhydroxypropyl cellulose, sodium cellulose sulfate, dialkyldimethylammonium cellulose sulfate, crystalline cellulose, cellulose powder and other cellulose and derivatives thereof, soluble starch other than that of the present invention, carboxymethyl starch, Starch-based polymers such as methylhydroxypropyl starch and methyl starch, starch derivatives such as hydroxypropyltrimonium starch chloride and corn starch aluminum octenylsuccinate, alginic acid derivatives such as propylene glycol alginate, polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), vinylpyrrolidone-vinyl alcohol copolymer, vinyl alcohol-vinyl acetate copolymer, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyoxyethylene-polyoxypropylene copolymer, amphoteric methacrylate ester copolymers such as (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer, (acrylates / stearyl acrylate / ethylamine oxide methacrylate) copolymer, (dimethicone / vinyl dimethicone) crosspolymer, (alkyl acrylate / diacetone acrylamide) copolymer, (alkyl acrylate / diacetone acrylamide) copolymer AMP, partially saponified polyvinyl acetate, maleic acid copolymer, polyvinylpyrrolidone,Vinylpyrrolidone-dialkylaminoalkyl methacrylate copolymer; acrylic resin alkanolamine, polyester, water-dispersible polyester, polyacrylamide, polyacrylic acid ester copolymers such as ethyl acrylate, carboxyvinyl polymer, polyacrylic acid and its salts such as sodium salt, acrylic acid-methacrylic acid ester copolymer, acrylic acid-alkyl methacrylate copolymer, cationized cellulose such as Polyquaternium-10, diallyldimethylammonium chloride-acrylamide copolymer such as Polyquaternium-7, acrylic acid-diallyldimethylammonium chloride copolymer such as Polyquaternium-22, acrylic acid-diallyldimethylammonium chloride-acrylamide copolymer such as Polyquaternium-39, acrylic acid-cationized methacrylic acid ester copolymer, acrylic acid-cationized methacrylic acid amide copolymer, acrylic acid-methyl acrylate-methacrylamidopropyltrimethylammonium chloride copolymer such as Polyquaternium-47, methacrylic acid choline ester chloride polymer, cationized oligosaccharide, cationized dextran, guar gum Cationic polysaccharides such as hydroxypropyltrimonium chloride, polyethyleneimine, cationic polymers, 2-methacryloyloxyethyl phosphorylcholine polymers such as polyquaternium-51 and copolymers with butyl methacrylate copolymers, acrylic resin emulsions, polyethyl acrylate emulsions, polyacrylic alkyl ester emulsions, polyvinyl acetate resin emulsions, polymer emulsions such as natural rubber latex and synthetic latex, nitrocellulose, polyurethanes and various copolymers, various silicones, various silicone copolymers such as acrylic-silicone graft copolymers, various fluorine-based polymers, 12-hydroxystearic acid and its salts, dextrin fatty acid esters such as dextrin palmitate and dextrin myristate, cholesteryl hydroxystearate, silicic anhydride, fumed silica (ultrafine silicic anhydride particles), aluminum magnesium silicate, sodium magnesium silicate, metal soaps, dialkyl phosphate metal salts, bentonite, hectorite, organically modified clay minerals, sucrose fatty acid esters, fructooligosaccharide fatty acid esters, quince seed extract,Examples of the thickener include natural polymers, semi-synthetic polymers, and synthetic polymers such as hydroxyethyl guar gum, carboxymethyl guar gum, starch, carboxymethyl chitin, and carboxymethyl starch. One type of thickener may be used alone, or two or more types may be used in combination.

[0082] (moisturizer) Examples of moisturizing agents include the following: Namely, glycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, trimethylolpropane, pentaerythritol, diglycerin, polyglycerin, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, isoprene glycol, isopentyldiol, hexylene glycol, triglycerin, 2-methacryloyloxyethyl phosphorylcholine, tetrahydrofurfuryl alcohol, polyoxyethylene (POE) tetrahydrofurfuryl alcohol, polyoxypropylene (POP) butyl ether, POP·POE butyl ether, tripolyoxypropylene glycerin ether, POP glycerin ether, POP glycerin ether phosphate, POP·POE pentaerythritol ether, ethylene glycol·propylene glycol copolymer polyhydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, monooleyl glycerol ether, diethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dibutyl ether, and other glycol alkyl ethers; sugar alcohols such as sorbitol, xylitol, erythritol, mannitol, maltitol, maltotriitol, maltotetriitol, and hydrogenated starch hydrolysates; sucrose, rhamnose, glucose, fructose, galactose, mannose, threose, xylose, arabinose, fucose, ribose, deoxyribose, maltose, maltotriose, maltotetraose, trehalose, lactose, raffinose, gluconic acid, glucuronic acid, sulfated trehalose, dextrin, cyclodextrin,Cyclonigerosilnigerose (cyclonigerosylnigelose) having the structure cyclo{→6)-α-D-glucopyranosyl-(1→3)-α-D-glucopyranosyl-(1→6)-α-D-glucopyranosyl-(1→3)-α-D-glucopyranosyl-(1→}, as disclosed in International Publication WO02 / 10361; cyclo{→6)-α-D-glucopyranosyl-(1→4)-α-D-glucopyranosyl-(1→6)-α-D-glucopyranosyl-(1→4)- Cyclic tetrasaccharide (cyclomaltosylmaltose) having the structure α-D-glucopyranosyl-(1→}, pullulan, isomerized sugar, sugars such as xylitylglucoside, valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, glycine, alanine, asparagine, glutamine, serine, cysteine, cystine, tyrosine, proline, hydroxyproline, aspartic acid, glutamic acid, sodium glutamate, hydroxylysine, arginine, ornithine, histidine Amino acids such as guar gum, pyrrolidone carboxylic acid, NMF components (natural moisturizing ingredients) such as sodium lactate, uric acid, sodium pyrrolidone carboxylate, glycogen, dextran, locust bean gum, xyloglucan, quince seed, carrageenan, pectin, mannan, curdlan, succinoglucan, galactan, arabinogalactan, dermatan sulfate, keratan sulfate, chondroitin, chondroitin sulfate, mucoitin sulfate, keratosulfate, chitin, chitosan, heparin, heparan sulfate, mucopolysaccharides such as hyaluronic acid, and hydrolysates of these mucopolysaccharides, soybeans Proteolytic peptides, wheat proteolytic peptides, hydrolyzed wheat protein, casein hydrolyzed peptides, acylated peptides such as palmitoyl oligopeptides, silylated peptides, conchiolin hydrolyzed peptides, hydrolyzed conchiolin, proteins and peptides such as silk and collagen and their hydrolysates, water-soluble polymeric substances such as hydrolyzed hyaluronic acid and hydrolyzed eggshell membrane, salts of these, lecithin derived from soybeans, egg yolks, etc., phosphatidylglycerol, phosphatidylinositol, phosphatidylserine, phosphatidylethanolamine, phosphatidic acid,Phospholipids such as sphingomyelin, sphingolipids, oils and fats such as olive oil, jojoba oil, squalane, silicones such as dimethylpolysiloxane and methylphenylsiloxane, culture supernatant of lactic acid bacteria and bifidobacteria, royal jelly extract, yeast extract, eggshell membrane protein, bovine submandibular gland mucin, hypotaurine, galactoarabinan, sesame lignan glycoside, albumin, whey, choline chloride, phosphorylcholine, placenta extract, coix seed extract, peony extract, seaweed extract, gentian extract, saxifrage extract, perilla extract, hydrolyzed rice bran extract, prune enzymes Hydrolyzate, trimethylglycine, N-methyl-L-serine, nicotinamide, Scutellaria root extract, tea extract, Centella asiatica extract, mulberry extract, hydrolyzed ginger extract, sodium acetyl hyaluronate, Althaea extract, Angelica acutiloba extract, aloe extract, sodium deoxyribonucleic acid, melothria extract, carrot extract, Houttuynia cordata extract, oolong tea extract, wheat germ extract, xylobiose mixture, Mokuzu extract, Phellodendron bark extract, Hypericum perforatum extract, Pueraria root extract, whey, cherry blossom leaf extract, peony extract, Sanguisorba officinalis extract, acerola Kiss, Belamcanda chinensis extract, Edelweiss extract, Almond extract, Glucosyl hesperidin, Yellow Himalayan raspberry root extract, Peppermint extract, Rehmannia root extract, Mevalonolactone, Angelica keiskei extract, Ginkgo extract, Horsetail extract, Hydrolyzed black bean extract, Thyme extract, Coptis japonica extract, Adenosine monophosphate, Adenosine triphosphate disodium, dl-α-tocopherol, DL-sodium malate, γ-amino-β-hydroxybutyric acid, Thujopsis dolabrata extract, Asparagus extract, Aspalathus linearis extract, Avocado extract, Apricot fruit Juice, Mussel glycogen, Inositol, Ibuki toranou extract, Nettle extract, Turmeric extract, Uva-ursi extract, Ageratum extract, Echinacea leaf extract, Ethyl glucoside, Crape myrtle extract, Panax ginseng extract, Ononis extract, Olive leaf extract, Oyster extract, Cattail extract, Camu camu extract, Camu camu seed extract, Carrot extract, Raspberry extract, Kiwi extract, Guava extract, Gardenia extract, Sasa kuma extract, Sophora flavescens extract, Glycolic acid, Grapefruit extract, Clematis extract, Chlorella extract, Cape aloe extract,Geranium Herb Extract, Coffee Extract, 2-(2-Hydroxyethoxy)ethylguanidine Succinate, Rice Bran Extract Hydrolyzate, Collagen Tripeptide, Chinese Cabbage Extract, Succinyl Atelocollagen, Hawthorn Extract, Sunflower Extract, Cyanocobalamin, Seagrass Extract, Tilia Extract, Dimethylsilanol-Hyaluronic Acid Condensate, Meadowsweet Extract, Calamus Root Extract, Birch Extract, Silk Extract, Silk Powder, Honeysuckle Extract, Starfruit Leaf Extract, Strawberry Juice, Ivy Extract, Hawthorn Extract, Swertia Extract, Morus Alba Extract, Sorbitol Fermented Polysaccharide Solution, Soybean Extract, Soybean Extract, Camellia Extract, Daisy Extract, Terminalia Extract, Angelica Extract, Peach Blossom Extract, Spruce Extract, Corn Extract, Tomato Juice, Wild Rose Extract, Hibiscus Extract, Houchi Sea Bean Extract, Bakuga Root Extract, Mugwort Extract, Lotus Seed Lactic Acid Bacteria Fermentation Liquid, Parsley Extract, Rugosa Extract, Witch Hazel Extract, Rose Extract, Parietaria Extract, Pancratium Maritimum Extract, Belamcanda Chrysanthemum Extract, Loquat Leaf Extract, Phytoglycogen, Butcher's Broom Extract, Impatiens Balsam Extract, Sodium Polyaspartate Liquid, Marjoram Extract, Lily Extract, Indigo Water Extract, Horse Chestnut Extract, Elastin, Natural Cera Examples of such surfactants include ceramides such as ceramides (types 1, 2, 3, 4, 5, 6, 9), caprooylphytosphingosine, caprooylsphingosine, hydroxyceramide, pseudoceramide, glycosphingolipids, ceramide and glycoceramide-containing extracts, deep sea water, alkaline simple hot spring water, polyoxyethylene methyl glucoside, sodium dl-pyrrolidone carboxylate, L-oxyproline, acetylglucosamine, taurine, etc. That is, glycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol, 3-methyl-1,3-butanediol, pentaerythritol, diglycerin, polyglycerin, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, trehalose, glycosyl trehalose, hydrolyzed hydrogenated starch, lysophosphatidic acid, lysolecithin, lecithin, ectoine, etidronic acid, squalane, ceramides,It is desirable to use at least one moisturizer selected from the group consisting of 2-methacryloyloxyethyl phosphorylcholine, hyaluronic acid, chondroitin sulfate, hydrolyzed hyaluronic acid, yeast extract, coix seed extract, peony extract, seaweed extract, gentian extract, trimethylglycine, N-methyl-L-serine, nicotinamide, and royal jelly extract. The moisturizer may be used alone or in combination of two or more.

[0083] (astringent) Astringents include citric acid, tannic acid, acetoxypropionic acid, isovaleric acid, aminovaleric acid, ethoxyacetic acid, ethoxypropionic acid, isoaminovaleric acid, epoxyoleic acid, elaidic acid, aminobutyric acid, erucic acid, oxaloacetic acid, formic acid, icosanoic acid, glucuronic acid, iduronic acid, crotonic acid, chloroisocrotonic acid, isocrotonic acid, acetic acid, dihydrolipoic acid, tartaric acid, ethylcrotonic acid, diphenylacetic acid, dimethoxyphthalic acid, ethylhydroxybutyric acid, succinamic acid, stearic acid, stearic acid, sorbic acid, tiglic acid, thyroxine, and decaacetic acid. Acid, Tropic Acid, Lactic Acid, Hydroxyisobutyric Acid, Hydroxyvaleric Acid, Pyruvate, Butylacetic Acid, Butyl Hydroperoxide, Brassidic Acid, Propiolic Acid, Propionic Acid, Bromoisovaleric Acid, Bromoisobutyric Acid, Bromopropionic Acid, Hexanoic Acid, Hexenoic Acid, Petroselinic Acid, Heptadecanoic Acid, Heptanoic Acid, Areanilic Acid, Maleamic Acid, Myristic Acid, Methacrylic Acid, Methylvaleric Acid, Methylthioacetic Acid, Methylbutyric Acid, Mevalonic Acid, Melissic Acid, Mercaptoacetic Acid, Iodoacetic Acid, Lauric Acid, Ricineladic Acid, Ricinoleic Acid, Linoleic Acid, Linolenic Acid Acid, Aconitic Acid, Oxalosuccinic Acid, Oxoglutaric Acid, Adipic Acid, Calcein, Carboxyphenylacetic Acid, Acetoxysuccinic Acid, Carboxycomellonic Acid, Camphoronic Acid, Isocamphoronic Acid, Glutaconic Acid, Glutaric Acid, Isocitric Acid, Crocetin, Succinic Acid, Phthalic Acid, Fumaric Acid, Isocinchomeronic Acid, Diethylenetriaminepentaacetic Acid, Isophthalic Acid, Citramalic Acid, Dinioctinic Acid, Itaconic Acid, Dibromosuccinic Acid, Dichlorosuccinic Acid, Ethylmalonic Acid, Dimethylsuccinic Acid, Oxalic Acid, Cinchomeronic Acid, Hemimellitic Acid, Pelargonic Acid, Berberonic Acid, Berberonic Acid Benzenehexacarboxylic acid, benzenepentacarboxylic acid, maleic acid, malonic acid, mesaconic acid, mesotartaric acid, mesoxalic acid, methylisophthalic acid, methylsuccinic acid, methylmalonic acid, mercaptosuccinic acid, mellophanic acid, peroxyphthalic acid, malic acid, lutidic acid, leukotriene bromoanthranilic acid, aminocinnamic acid, isopropylcinnamic acid, oxanilic acid, arecaidine, carboxycinnamic acid, cinnamic acid, galloyl gallic acid, tranexamic acid, nitrocinnamic acid, hydroxycinnamic acid, methoxycinnamic acid, hydroxyhydrocinnamic acid, phenylcinnamic acid,Ellagic acid, orotic acid, camphanic acid, quinic acid, hydroxyproline, etiocholanic acid, caulmoglic acid, carnosine, carbazole acetic acid, quinoline carboxylic acid, quinolinic acid, quinoline dicarboxylic acid, coumaric acid, chlorophenoxyacetic acid, chenodeoxycholic acid, cholanic acid, cholic acid, santonic acid, dihydroorthoic acid, succinic acid, thiophene carboxylic acid, tetrahydrofolic acid, dehydrocholic acid, terpenic acid, hydroxypyrone carboxylic acid, hydroxypyrone dicarboxylic acid, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, bicarbonate Phenyldicarboxylic acid, homogentisic acid, mandelic acid, muricholic acid, methyldopa, methylphenylacetic acid, methylfurancarboxylic acid, methyl red, mefenamic acid, lysergic acid, lithocholic acid, lipoic acid, reserpic acid, retinoic acid, levopimaric acid, glycolic acid, salicylic acid, zinc paraphenolsulfonate, Althaea officinalis, Arnica officinalis, Iris, Fennel, Crape myrtle, Orange, Rubus idaeus, Guava, Black currant, Geranium herb, Hawthorn, Meadowsweet, Peony, Birch, Honeysuckle, Horsetail, and European jasmine Ivy, thyme, tea, parsley, hamamelis, grapes, cornflower, lemon, astragalus, burnet, cinchona, salvia, linden tree, ginseng, juniper, rosemary, St. John's wort, ginkgo, melissa, ononis, horse chestnut, Swertia japonica, garlic, chamomile, thyme, peppermint, nettle, chili pepper, ginger, hops, horse chestnut, lavender, carrot, mustard, zelkova, pine, cnidium, elderberry, mountain watercress, water hyacinth, peony, Japanese bayberry, Houttuynia cordata, water hyacinth, water chestnut, calendula, lily of the valley, gentian , extracts of plants such as sea laurel, bitter orange, yuzu, calamus, summer mandarin, mary locust, Japanese pepper, eucalyptus, mugwort, emmeisou, rice, sophora flavescens, ginger, clove, walnut leaves, Scutellaria root, sage, rosemary, Polygonum multiflorum, Coptis Rhizome, Phellodendron bark, Scutellaria lobata, heavy medicine, dried orange peel, ginseng, Angelica sinensis, tassium sieboldii, tannins, birch tar, propolis, royal jelly, yeast extract, tuberose polysaccharide solution, oolong tea, alum, zinc chloride, zinc sulfate, aluminum sulfate, aluminum chloride, allantoin chlorohydroxyaluminum,Examples of the astringent include allantoin dihydroxyaluminum, chlorohydroxyaluminum, zinc oxide, zinc sulfide, zinc sulfophenone, sodium sulfophenone, and organic composite salts of aluminum and zirconium. One type of astringent may be used alone, or two or more types may be used in combination.

[0084] (keratin softener) Examples of keratin softening agents include ethanol, isopropyl alcohol, propanol, butanol, polyethylene glycol, benzyl alcohol, phenylethyl alcohol, propylene carbonate, hexyldodecanol, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, triethanolamine, diisopropyl adipate, ethyl laurate, lanolin, fatty acid dialkylolamide, urea, sulfur, resorcinol, phytic acid, lactic acid, lactate salts, glycolic acid, sodium hydroxide, potassium hydroxide, etc. One type of keratin softening agent may be used alone, or two or more types may be used in combination.

[0085] (Emollient) As the emollient (softener), an oily component similar to sebum is desirable, and examples of the oily component include hemp seed oil, Astrocaryum murumuru oil, rapeseed oil, African mango kernel oil, Camellia sinensis seed oil, Argania spinosa kernel oil, apricot kernel oil, sea buckthorn oil, Ethium plantagineum seed oil, emu oil, orange roughy oil, canola oil, kaya seed oil, Garcinia indica seed oil, caraway seed oil, apricot kernel oil, kukui nut oil, crambe avianica seed oil, cranberry seed oil, walnut seed oil, black currant seed oil, Cowberry seed oil, rice germ oil, Japanese white pine seed oil, camellia oil, sal seed oil, oxidized corn oil, shea butter, Shorea sthenoptera oil, white lupin seed oil, hydrogenated avocado oil, hydrogenated olive oil, hydrogenated beef tallow, hydrogenated soybean oil, hydrogenated rapeseed seed oil, hydrogenated milk fat, hydrogenated palm kernel oil, hydrogenated palm oil, hydrogenated castor oil, hydrogenated jojoba oil, hydrogenated vegetable oil, hydrogenated coconut oil, Sclerocarya birrea oil, ostrich oil, passionflower seed oil, tea seed oil, camellia oil, cranberry seed oil, Theobroma grandiflorum seed fat, lard, milk fat, Job's tears oil, babassu oil, peanut oil, peanut oil Stasio seed oil, Hippophae rhamnoides oil, sunflower seed oil, bilberry seed oil, grape seed oil, partially hydrogenated perilla oil, partially hydrogenated horse oil, prune seed oil, broccoli seed oil, loofah seed oil, pepo pumpkin seed oil, tomato coccus pluvialis oil, rubus chamaemorus seed oil, pine seed oil, mango seed oil, mango seed oil, mink oil, Melia azadirachta seed oil, peach kernel oil, vegetable oil, camellia sinensis oil, European rubus seed oil, apple seed oil, borage seed oil, rosehip oil, moringa seed oil, macadamia nut oil, castor oil, olive oil, almond oil, Vegetable or animal fats and oils such as cacao oil, camellia oil, coconut oil, palm oil, wood wax, jojoba oil, grapeseed oil, avocado oil, safflower oil, sesame oil, tea oil, evening primrose oil, wheat germ oil, hazelnut oil, meadowfoam oil, persic oil, peppermint oil, tea tree oil, corn oil, rapeseed oil, sunflower oil, linseed oil, cottonseed oil, soybean oil, peanut oil, rice bran oil, cocoa butter, shea butter, fennel oil, perilla oil, chamomile oil, carrot oil, cucumber oil, egg yolk oil, beef tallow, horse fat, fish oil, turtle oil, orange roughy oil, urushi peel wax, Jasmine flower wax,Waxes such as orange peel wax, orange flower wax, hydrolyzed jojoba ester, carnauba wax, candelilla wax, daffodil flower wax, rice bran wax, white bayberry fruit wax, sweet acacia flower wax, tuberose flower wax, beeswax, spermaceti, orange roughy oil, lanolin, rice wax, montan wax, and ozokerite, isoeicosane, isododecane, isohexadecane, diethylhexylcyclohexane, pentahydrosqualene, mineral oil, liquid paraffin, polyisobutene, hydrogenated polyisobutene, polybutene, Squalane, squalene, microcrystalline wax, ceresin wax, paraffin wax, petrolatum, ozokerite, α-olefin oligomer, hydrocarbons such as tetradecene, isomerized linoleic acid, beef tallow fatty acid, fatty acids (C14-28), fatty acids (C20-40), hydrogenated coconut fatty acid, palm kernel fatty acid, 10-hydroxydecanoic acid, branched fatty acids (C14-28), branched fatty acids (C12-31), behenic acid, capric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lanolin fatty acid, linoleic acid, linolenic acid, lauric acid, oleic acid Natural and synthetic fatty acids such as stearic acid, isostearic acid, undecylenic acid, 1,2-hydroxystearic acid, palmitoleic acid, erucic acid, docosahexaenoic acid, eicosapentaenoic acid, isohexadecanoic acid, anteisohenicosanoic acid, isononanoic acid, 2-ethylhexanoic acid, and their salts, (C12-16) alcohol, (C14-22) alcohol, (C20-22) alcohol, (C20-40) alcohol, (C30-50) alcohol, rapeseed sterol, isocetyl alcohol, isopropanol, caprylyl glycol Cole, rice bran sterol, hydrogenated rapeseed oil alcohol, cetyl alcohol, stearyl alcohol, hexyldecanol, octyldodecanol, lauryl alcohol, caprylic alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, arachyl alcohol, behenyl alcohol, jojoba alcohol, chimyl alcohol, selachyl alcohol, batyl alcohol, isostearyl alcohol, cetyl alcohol, cholesterol, phytosterol, lanolin alcohol, hydrogenated lanolin alcohol, palmityl alcohol,Natural and synthetic higher alcohols such as 2-decyltetradecynol, (C12-15) Pareth-9 carboxylate isopropyl, octyldodecyl pyrrolidone carboxylate, menthyl pyrrolidone carboxylate, lauryl pyrrolidone carboxylate, PEG-2 isodeceth-7 carboxylate cetyl, diPPG-3 myristyl adipate, diPPG-2 myreth-10 adipate, diisopropyl adipate, diheptylundecyl adipate, avocado fatty acid ethyl, avocado oil fatty acid butyl, methyl gluceth-20 benzoate, ethyl isostearate, (isostearyl Castor Oil (Isostearate / Succinic Acid), Hydrogenated Castor Oil Isostearate, Batyl Isostearate, Hexyldecyl Isostearate, Castor Oil (Isostearate / Beeswax / Succinic Acid), Isodecyl Isononanoate, Isotridecyl Isononanoate, Isononyl Isononanoate, Octyl Isononanoate, Cetearyl Isononanoate, Sucrose Acetate Isobutyrate, Caprylyl Eicosenoate, Butyl Ethyl Propanediol Ethylhexanoate, Octyldodecyl Erucate, Oleyl Erucate, Alkyl Octanoate (C14, 16, 18), (Octanoate / Stearic Acid / Azido) Glyceryl pinate, cetyl octanoate, cetearyl octanoate, hexyldecyl octanoate, ethyl olivate, oleyl oleate, caprylic / capric glycerides, caprylic / capric / coconut acid glyceryl, caprylic / capric / succinic acid triglyceride, cetyl caprate, triisostearyl citrate, triisooctyldodecyl citrate, glyceryl citrate / lactic / linoleate / oleate, isostearyl diglyceryl succinate, diethoxyethyl succinate, dioctyl succinate, rice bran oil fatty acid fluoride Fritillyl acetate, cetyl acetate, farnesyl acetate, lanolin alcohol acetate, linalyl acetate, propylene glycol diisostearate, dimer dilinoleyl diisostearate, neopentyl glycol diisostearate, neopentyl glycol diethylhexanoate, PEG-18 castor oil dioleate, butylene glycol dicaprylate / caprate, isosorbide dicaprate, polyethylene glycol dicaprylate / caprate, dicocoyl pentaerythrityl distearyl citrate, polyethylene glycol distearate,PG-20 methyl glucose distearate, pentaerythrityl distearate, diethyl pentanediol dineopentanoate, methyl pentanediol dineopentanoate, polyethylene glycol dinonanoate, fatty acid (C10-30) (cholesteryl / lanosteryl), fatty acid (C12-18) cetyl, glycol dilaurate, diisopropyl dilinoleate, pentaerythrityl hydrogenated rosinate, hydrogenated methyl rosinate, glyceryl (hydrogenated rosin / diisostearate), ethylhexyl stearate, isocetyl stearoyloxystearate, Octyldodecyl Stearoyl Stearoyl Stearate, Dibutyloctyl Sebacate, Octyldodecyl Dimer Dilinoleate / PPG-3 Myristyl Ether, Di(isostearyl / phytophytosteryl) Dimer Dilinoleate, Dicetearyl Dimer Dilinoleate, Hydrogenated Castor Oil Dimer Dilinoleate, Stearyl / PPG-3 Myristyl Ether Dimer Dilinoleate, Dimer Dilinoleyl Dimer Dilinoleate, Bis(behenyl / isostearyl / phytophytosteryl) Dimer Dilinoleate, Dimer Dilinoleyl (F) Phytosteryl / Isostearyl / Cetyl / Stearyl / Behenyl), Dimer Dilinoleyl Hydrogenated Rosin Condensate, Dialkyl Carbonate (C14,15), Diethylhexyl Carbonate, Dicaprylyl Carbonate, Pentaerythrityl Tetraisostearate, Pentaerythrityl Tetraoctanoate, Dodeca (Caprylic / Capric) Polyglyceryl-10, Diisocetyl Dodecanedioate, Dioctyldodecyl Dodecanedioate, Triisostearin, Erythrityl Triethylhexanoate, Ditrimethylolpropane Triethylhexanoate, Trioctanoin, Trioctanoin Trimethylolpropane Phosphate, Tricaprylin, Caprylic / Capric Triglyceride, Caprylic / Capric / Stearic Triglyceride, Caprylic / Capric / Myristic / Stearic Triglyceride, C8-12 Triglycerides, Tristearin, Tripalmitin, Tripalmitoleic, Trihydroxystearin, Tribehenin, Dipentaerythrityl Tri-Polyhydroxystearate, Trimyristin, C12-15 Alkyl Lactate, Ethyl Lactate, Octyldodecyl Lactate, Butyl Lactate, Menthyl Lactate,Isodecyl neopentanoate, myristyl neopentanoate, octyl nonanoate, cholesteryl nonanoate, ethylhexyl palmitate, cetyl palmitate, bis-diglyceryl polyacyladipate-1, bis-diglyceryl polyacyladipate-2, dipentaerythrityl hydroxystearate / isostearate, ethylhexyl hydroxystearate, octyl hydroxystearate, hydrogenated castor oil hydroxystearate, dipentaerythrityl hydroxystearate / stearic acid / rosinate, hydroxystearic acid Phytosteryl, Castor Fatty Acid PPG-5.5, Castor Fatty Acid Methyl, Myristyl Propionate, C12-31 Branched Cholesteryl Fatty Acid, Dipentaerythrityl Hexahydroxystearate, Dipentaerythrityl Hexa(hydroxystearate / hexastearic acid / hexarosinate), Stearyl Heptanoate, Glyceryl Behenate / Eicosanedioate, Jojoba Esters, Jojoba Fatty Acid Isopropyl, Ethyl Macadamiate, Cholesteryl Macadamiate, Phytosteryl Macadamiate, Dioctyl Maleate, Malonic Acid Diethylhexyl syringylidene, hexyldecyl myristoyl methylaminopropionate, citronellyl methylcrotonate, meadowfoam estolide, octyldodecyl meadowfoam oil fatty acid, glyceryl cocoate / citric acid / lactic acid, decyl cocoate, cholesteryl butyrate, dihydrocholesteryl butyrate, octyldodecyl lanolinate, cholesteryl lanolinate, octyldodecyl ricinoleate, diethylhexyl malate, trioleyl phosphate, tricetyl phosphate, glyceryl tri-2-ethylhexanoate (triethylhexyl) Xanoin), cetyl 2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, isopropyl myristate, butyl myristate, isopropyl palmitate, ethyl stearate, octyl palmitate, isocetyl isostearate, butyl stearate, ethyl linoleate, isopropyl linoleate, ethyl oleate, isocetyl myristate, isostearyl myristate, isostearyl palmitate, octyldodecyl myristate, diethyl sebacate, diisopropyl dipicate, isoarachidyl neopentanoate,Caprylic / capric triglyceride, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, cetyl caprylate, decyl laurate, hexyl laurate, decyl myristate, myristyl myristate, cetyl myristate, glycerin trimyristate, stearic acid, Stearyl phosphate, decyl oleate, cetyl ricinoleate, isostearyl laurate, isotridecyl myristate, isocetyl palmitate, octyl stearate, isocetyl stearate, isodecyl oleate, octyldodecyl oleate, octyldodecyl linoleate, isopropyl isostearate, cetostearyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, hexyl isostearate, ethylene glycol dioctanoate, ethylene glycol dioleate, propylene glycol dioleate, proline dicaprate Pyrene glycol, propylene glycol dicaprylate, caprylic / capric triglyceride, propylene glycol dicaprylate, neopentyl glycol dicaprate, neopentyl glycol dioctanoate, glyceryl tricaprylate, glyceryl triundecylate, glyceryl triisopalmitate, glyceryl triisostearate, octyldodecyl neopentanoate, isostearyl octanoate, hexyldecyl neodecanoate, octyldodecyl neodecanoate, isostearyl isostearate, octyl isostearate Tyldecyl, Polyglycerin Oleate, Polyglycerin Isostearate, Dipropyl Carbonate, Dialkyl Carbonate (C12-18), Triisocetyl Citrate, Triisoarachyl Citrate, Triisooctyl Citrate, Lauryl Lactate, Myristyl Lactate, Cetyl Lactate, Octyldecyl Lactate, Lanolin Lactate, Triethyl Citrate, Acetyltriethyl Citrate, Acetyltributyl Citrate, Trioctyl Citrate, Diisostearyl Malate, 2-Ethylhexyl Hydroxystearate, Di-2-Ethylhexyl Succinate, Diisostearate, Diisostearate, esters such as butyl, diisopropyl sebacate, dioctyl sebacate, cholesteryl stearate, cholesteryl isostearate, cholesteryl hydroxystearate, cholesteryl oleate, dihydrocholesteryl oleate, phytosteryl isostearate, phytosteryl oleate, isocetyl 12-stearoylhydroxystearate, stearyl 12-stearoylhydroxystearate, isostearyl 12-stearoylhydroxystearate, hexyldecyl dimethyloctanoate, and isopropyl lanolinate;Examples of the oil-soluble surfactant include lanolins such as liquid lanolin, reduced lanolin, adsorption-purified lanolin, acetated lanolin, acetated liquid lanolin, hydroxylanolin, polyoxyethylene lanolin, hard lanolin fatty acid, and cetyl lanolyl acetate ester; sphingophospholipids such as sphingomyelin; phospholipid derivatives such as hydrogenated soybean phospholipid, partially hydrogenated soybean phospholipid, hydrogenated egg yolk phospholipid, and partially hydrogenated egg yolk phospholipid; sterols such as dihydrocholesterol, lanosterol, dihydrolanosterol, and cholic acid; silicone-based oils such as methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, stearoxysilicone, decamethylcyclopentasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, and dodecamethylcyclohexasiloxane; sapogenins; saponins; fluorine-based oils such as perfluoropolyether, perfluorodecalin, and perfluorooctane. The emollients may be used alone or in combination of two or more.

[0086] (surfactant) Examples of surfactants include sorbitan monolaurate, sorbitan coconut oil fatty acid, sorbitan distearate, sorbitan monostearate, sorbitan tristearate, sorbitan monoisostearate, sorbitan monooleate, sorbitan trioleate, sorbitan fatty acid esters, sorbitan monopalmitate, sorbitan sesquioleate, sorbitan sesquistearate, polyoxyethylene sorbitan monolaurate, polyoxetylene sorbitan monostearate, ethylene glycol monostearate, ethylene glycol distearate, diethylene glycol distearate, ethylene glycol fatty acid esters, glyceride monostearate, glyceryl distearate, glyceryl isostearate, polyoxyethylene glyceryl isostearate, polyoxyethylene glyceryl triisostearate, diglyceryl isostearate, glyceryl diisostearate, glyceryl triisostearate, diglyceryl triisostearate, Propylene glycol monostearate, self-emulsifying propylene glycol stearate, glyceryl ricinoleate, propylene glycol ricinoleate, propylene glycol fatty acid esters, propylene glycol dioleate, propylene glycol laurate, glyceryl linoleate, glyceryl diisopalmitate, glyceryl sesquioleate, glyceryl monooleate, glycerin trimyristate, isopropyl lanolinate, hexyldecyl dimethyloctanoate , Acetoglyceryl, Glyceryl Triisooctanoate, Glyceryl Di-2-heptylundecanoate, Glyceryl Oleate Pyroglutamate, Decaglyceryl Decaoleate, Dipentaerythrityl Fatty Acid Ester, Glyceryl Stearate Malate, Polyoxyethylene Hydrogenated Castor Oil Laurate, Polyoxyethylene Alkyl (12-14) Ether (7E.O.), Polyoxyethylene Alkyl (12-14) Ether (12E.O.), Polyoxyethylene Alkyl Ether (20E.O.)), Polyoxyethylene lauryl ether, Polyoxyethylene myristyl ether, Polyoxyethylene cetyl ether, Polyoxyethylene cetostearyl ether (ceteareth-25), Polyoxyethyl stearyl ether, Polyoxyethylene oleyl ether, Polyoxyethylene oleyl cetyl ether, Polyoxyethylene behenyl ether, Polyoxyethylene octylphenyl ether, Polyoxyethylene nonylphenyl ether, Polyoxyethylene alkyl (12,13) ​​ether (10E.O.), Polyoxyethylene octyldodecyl ether, Polyoxyethylene cetylstearyl diether, Polyoxyethylene methyl glucoside sesquistearate, Carboxylated polyoxyethylene trehalose ether, polyethylene glycol (4) octanoate, polyoxyethylene nonylphenyl ether (14E.O.) mixture, polyoxyethylene lanolin alcohol, polyoxyethylene (5) lanolin alcohol, polyoxyethylene (10) lanolin alcohol, polyoxyethylene (15) lanolin alcohol, polyoxyethylene (20) lanolin alcohol, polyoxyethylene (25) lanolin alcohol, polyoxyethylene (40) lanolin alcohol, polyoxyethylene (alkylol lanolin alcohol) ether (16E.O.), polyoxyethylene lanolin alcohol acetate, polyoxyethylene lanolin, polyoxyethylene reduced lanolin, polyoxyethylene sorbitol lanolin (40E.O.).), Polyoxyethylene polyoxypropylene reduced lanolin, Polyoxyethylene polyoxypropylene lanolin, Polyoxyethylene polyoxypropylene liquid lanolin, Polyoxyethylene stearic acid amide, Polyoxyethylene phytosterol, Polyoxyethylene dinonylphenyl ether, Polyethylene glycol monolaurate, Polyethylene glycol dilaurate, Polyethylene glycol palmate, Polyethylene glycol dipalmitate, Polyethylene glycol dipalmitate, Polyethylene glycol monooleate, Polyethylene glycol 150 dioleate, Polyethylene glycol monostearate, Polyethylene glycol distearate, Polyoxyethylene glyceryl tristearate, Polyethylene glycol 300 lanolinate, Polyethylene glycol 600 lanolinate, Polyethylene glycol 1000 lanolinate, Polyethylene monooleate Propylene glycol (36), polyoxyethylene sorbitan monolaurate (20 E.O.), polyoxyethylene sorbitan cocoate (20 E.O.), polyoxyethylene sorbitan monopalmitate (20 O.E.), polyoxyethylene sorbitan oleate (40 E.O.), polyoxyethylene sorbitan monooleate (6 E.O.), polyoxyethylene sorbitan monooleate (20 E.O.), polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan tetraoleate, polyoxyethylene sorbitan trioleate (20 E.O.), polyoxyethylene sorbitan monostearate (6 E.O.), polyoxyethylene sorbitan monostearate (20 E.O.), polyoxyethylene sorbitan tristearate (6 E.O.), polyoxyethylene sorbitan hexastearate, polyoxyethylene sorbitan isostearate (3 E.O.)), Polyoxyethylene glyceryl monostearate, Polyoxyethylene sorbitan beeswax, Polyoxyethylene polyoxypropylene butyl ether, Polyoxyethylene (20) polyoxypropylene (15) butyl ether, Polyoxyethylene (35) polyoxypropylene (28) butyl ether, Polyoxyethylene (36) polyoxypropylene (36) butyl ether, Polyoxyethylene (37) polyoxypropylene (38) butyl ether, Polyoxyethylene polyoxypropylene cetyl ether, Poly Polyoxyethylene polyoxypropylene decyl tetradecyl ether, polyoxyethylene polyoxypropylene oligosuccinate (3E.O.) (20P.O.), polyoxyethylene polyoxypropylene hexylene glycol ether (300E.O.) (75P.O.), trimethylolpropane tri(polyoxyethylene isostearate) (3E.O.), polyoxyethylene glyceryl oleate, polyoxyethylene (10), polyoxypropylene glycol (30), polyoxyethylene (16), polyoxypropylene Propylene glycol (30), polyoxyethylene (25), polyoxypropylene glycol (30), polyoxyethylene (160), polyoxypropylene glycol (30), polyoxyethylene (30), polyoxypropylene glycol (35), polyoxyethylene (200), polyoxypropylene glycol (40), polyoxyethylene (200), polyoxypropylene glycol (70), polyoxyethylene (20), polyoxypropylene glycol (15), butyl ether, polyoxyethylene (6), polyoxy Propylene glycol (30), polyoxyethylene (1), polyoxypropylene (4), cetyl ether, polyoxyethylene (1), polyoxypropylene (8), cetyl ether, polyoxyethylene (20), polyoxypropylene (4), cetyl ether, polyoxyethylene (20), polyoxypropylene (8), cetyl ether, polyoxypropylene (9) diglyceryl ether, polyoxypropylene stearyl ether, ethylenediaminetetraacetic acid, polyoxyethylene polyoxypropylene, polyoxyethylene (6E.O.) Caprylic / Capric Glycerin, Polyoxyethylene Glyceryl Laurate, Polyoxyethylene Glyceryl Cocoate, Polyoxyethylene Diethanolamine Laurate (4E.O.), Dioctyldodecyl Lauroyl Glutamate, Dipolyoxyethylene Stearyl Ether Diester of Lauroyl Glutamate, Polyoxyethylene Octyldodecyl Ether Diester of Lauroyl Glutamate, Polyoxyethylene Glyceryl Pyroglutamate Isostearate, Polyoxyethylene Hydrogenated Castor Oil Pyroglutamate Isostearate, Capric Diethanolamide, Undecylenic Acid Monoethanolamide, Coconut Oil Monoethanolamide, Coconut Oil Diethanolamide (1:2 Type), Coconut Oil Diethanolamide, Lauric Acid Ethanolamide, Lauric Acid Diethanolamide, Lauric Acid Isopropanolamide, Lauric Acid Dimyristate Ethanolamide, lauric myristic triethanolamine, myristic diethanolamide, palmitic ethanolamide, stearic monoethanolamide, stearic diethanolamide, stearic diethylaminoethylamide, isostearic diethanolamide, oleic diethanolamide, linoleic diethanolamide, beef tallow fatty acid monoethanolamide, beef tallow fatty acid diethanolamide, hardened beef tallow fatty acid diethanolamide, lanolin fatty acid diethanolamide, polyoxyethylene coconut oil fatty acid amide (5E.O.), polyoxyethylene (2) coconut oil fatty acid monoethanolamide, polyoxyethylene (5) coconut oil fatty acid monoethanolamide, polyoxyethylene (10) coconut oil fatty acid monoethanolamide, polyoxyethylene coconut oil fatty acid diethanolamide, polyoxyethylene beef tallow alkyldiethanolamine (2E.O.)), polyoxyethylene coconut oil alkyl dimethylamine oxide, coconut oil alkyl dimethylamine oxide liquid, stearyl dimethylamine oxide, oleyl dimethylamine oxide, dihydroxyethyl laurylamine oxide liquid, pentaerythritol rosinate, hexaglyceryl oleate, methyl glucoside sesquistearate, polyethylene glycol monooleate, polyethylene glycol alkylate, polyoxyethylene alkyl ether, polyglycol diether, lauroyl diethanolamide, fatty acid isopropanolamide, maltitol hydroxy fatty acid ether, alkylated polysaccharide, alkyl glucoside, trehalose monomyristate, trehalose monoisostearate, trehalose monoundecylenate and other trehalose mono fatty acid esters, polyoxyethylene methyl glucoside dioleate (120E.O.), sugar esters such as sucrose fatty acid esters, coconut oil fatty acid glyceryl, lipophilic glycerin monostearate, self-emulsifying glycerin monostearate, polyglycerin monostearate, polyglycerin alkylate, sorbitan monooleate, polyethylene glycol monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylated sterol, polyoxyethylated lanolin, polyoxyethylated beeswax, polyoxyethylated hydrogenated castor oil, glycerin fatty acid esters, polyglycerin fatty acid esters (polyglyceryl-10 stearate, polyglyceryl-6 pentastearate), POE sorbitan fatty acid esters, POE sorbit fatty acid esters, P POE glycerin fatty acid ester, POE alkyl ether, POE fatty acid ester, POE hydrogenated castor oil, POE castor oil, POE-POP copolymer, POE-POP alkyl ether, polyether modified silicone lauric acid alkanolamide, alkylamine oxide, hydrogenated soybean phospholipid, caprylyl glucoside, glyceryl citrate, glyceryl stearate citrate, corn oil PEG-8 esters, cocamide DEA, cocamide MEA, cocamide MIPA, sucrose acetate stearate, hydrogenated palm kernel oil glycerides, hydrogenated palm oil PEG-200 glyceryl, hydrogenated palm oil glycerides, sorbitan sesquiisostearate, polyglyceryl sesquiisostearate. Nonionic surfactants such as lyceryl-2, polyglyceryl-2 sesquicaprylate, PEG-20 methyl glucose sesquistearate, sodium stearate, zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, aluminum isostearate, triethanolamine stearate, potassium palmitate, sodium cetyl sulfate, sodium lauryl phosphate, disodium lauryl phosphate, triethanolamine palmitate, polyoxyethylene sodium lauryl phosphate, sodium N-acyl glutamate, sodium palmitate, sodium laurate, potassium laurate, zinc laurate, triethanolamine laurate, sodium laurate, sodium lauryl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, monoethanolamine lauryl sulfate, diethanolamine lauryl sulfate, triethanolamine lauryl sulfate, sodium lauryl diaminoethylglycine, triethanolamine alkyl sulfate ether, turmeric oil, linear dodecyl benzene sulfate, polyoxyethylene hydrogenated castor oil, maleic anhydride Phosphate, acyl methyl taurine, fatty acid soap, α-acyl sulfonate, alkyl sulfonate, alkyl aryl sulfonate, alkyl naphthalene sulfonate, alkyl sulfate, POE alkyl ether sulfate, alkyl amide sulfate, alkyl phosphate, POE alkyl phosphate, alkyl amide phosphate, alkyloyl alkyl taurine salt, N-acyl amino acid salt, POE alkyl ether carboxylate, alkyl sulfosuccinate, sodium alkyl sulfoacetate, acyl isethionate, acylated hydrolyzed collagen peptide salt , perfluoroalkyl phosphate ester, soap base, potassium soap, zinc undecylenate, potassium-containing soap base, potassium coconut oil fatty acid, sulfated castor oil, sodium myristate, potassium myristate, zinc myristate, magnesium myristate, sodium oleate, potassium oleate, N-acyl-L-glutamic acid triethanolamine, N-acyl-L-glutamic acid sodium, N-coconut oil fatty acid acyl-L-glutamic acid sodium, N-coconut oil fatty acid / hydrogenated beef tallow fatty acid acyl-L-glutamic acid sodium,N-Coconut oil fatty acid acyl-L-glutamic acid triethanolamine, stearoyl-L-glutamic acid disodium, N-hydrogenated beef tallow fatty acid acyl-L-glutamic acid sodium, N-lauroyl-L-glutamic acid sodium, N-stearoyl-L-glutamic acid, N-lauroyl-L-lysine, lauroyl-L-glutamic acid triethanolamine, L-arginine ethyl DL-pyrrolidone carboxylate, N-coconut oil fatty acid acyl-L-arginine ethyl DL-pyrrolidone carboxylate, coconut oil fatty acid sarcosine, coconut oil fatty acid sarcosine Sodium, Cocoyl Sarcosine Triethanolamine, Lauroyl Sarcosine, Sodium Lauroyl Sarcosine, Triethanolamine Lauroyl Sarcosine, Carboxylated Polyoxyethylene Tridecyl Ether Sodium Salt (3E.O.), Sodium β-Laurylaminopropionate, Lauryl Aminopropionic Acid Solution, Potassium Cocoyl Methyl Taurate, Sodium Cocoyl Methyl Taurate, Sodium Lauroyl Methyl Taurate, Sodium Lauryl Sulfoacetate, Sodium Cocoyl Methyl Alanine Solution, Cocoyl Fatty Acids Triethanolamine solution, lauroylmethyl-β-alanine sodium solution, lauryl-N-carboxymethoxyethyl-N-carboxymethylimidazolinium disodium dodecanoyl sarcosine, coconut oil alkyl-N-carboxyethyl-N-hydroxyimidazolinium betaine sodium, coconut oil alkyl-N-carboxyethoxyethyl-N-carboxyethylimidazolinium disodium hydroxide, coconut oil alkyl-N-carboxymethoxyethyl-N-carboxymethylimidazolinium disodium hydroxide, coconut oil alkanol Kyl-N-carboxymethoxyethyl-N-carboxymethylimidazolinium disodium lauryl sulfate, myristoylmethyl-β-alanine sodium solution, stearoylmethyl taurine sodium, sodium tetradecene sulfonate, sodium dodecylbenzenesulfonate, dodecylbenzenesulfonic acid triethanolamine, sodium alkane sulfonate, ammonium alkyl sulfate, sodium octylphenoxydiethoxyethyl sulfonate, magnesium coconut oil alkyl sulfate, triethanolamine, sodium myristyl sulfate,Sodium Cetostearyl Sulfate, Sodium Oleyl Sulfate, Triethanolamine Oleyl Sulfate, Sodium Polyoxyethylene Lauryl Ether Sulfate, Ammonium Polyoxyethylene Lauryl Ether Sulfate (2E.O.), Triethanolamine Polyoxyethylene Lauryl Ether Sulfate, Ammonium Polyoxyethylene Alkyl Ether Sulfate (3E.O.), Diethanolamine Polyoxyethylene Alkyl Ether Sulfate (3E.O.), Triethanolamine Polyoxyethylene Alkyl Ether Sulfate (3E.O.), Sodium Polyoxyethylene Alkyl Ether Sulfate, Hydrogenated Sodium Cocoglyceryl Sulfate, Polyoxyethylene (5) Cocoglyceride Monoethanolamide Phosphate, Polyoxyethylene Alkyl (12-14) Ether Phosphate (2E.O.), (8E.O.), (10E.O.), Polyoxyethylene Lauryl Ether Phosphate, Sodium Polyoxyethylene Lauryl Ether Phosphate, Polyoxyethylene Cetyl Ether Phosphate, Sodium Polyoxyethylene Cetyl Ether Phosphate, Polyoxyethylene Stearyl Ether, Polyoxyethylene ethylene cholesteryl ether, polyoxyethylene stearyl ether phosphate, polyoxyethylene oleyl ether phosphate, sodium polyoxyethylene oleyl ether phosphate, diethanolamine polyoxyethylene oleyl ether phosphate, polyoxyethylene alkylphenyl ether phosphate, triethanolamine polyoxyethylene alkylphenyl ether phosphate, polyoxyethylene polyoxypropylene cetyl ether phosphate, polyoxypropylene glyceryl ether phosphate, polyoxypropylene butyl ether phosphate, disodium polyoxyethylene lauryl sulfosuccinate, sodium coconut oil fatty acid ethyl ester sulfonate, dioctyl sodium sulfosuccinate, sodium octylphenoxydiethoxyethyl sulfonate, disodium lauryl sulfosuccinate, disodium oleic acid amide sulfosuccinate, polyoxyethylene alkyl (C12-15) ether phosphate, disodium polyoxyethylene alkyl (C12-14) sulfosuccinate (7E.O.), disodium polyoxyethylene lauroylethanolamide sulfosuccinate (5E.O.),Sodium isostearoyl lactylate, sodium undecylenoyl hydrolyzed collagen, potassium undecylenoyl hydrolyzed collagen, sodium undecylhydroxyethylimidazolinium betaine, sodium laurate hydrolyzed collagen, sodium coconut oil fatty acid hydrolyzed collagen, potassium coconut oil fatty acid hydrolyzed collagen, potassium coconut oil fatty acid hydrolyzed collagen solution, triethanolamine coconut oil fatty acid hydrolyzed collagen, isostearoyl hydrolyzed collagen, isostearoyl hydrolyzed silk, isostearoyl hydrolyzed collagen Decomposing Collagen Aminomethylpropanediol Salt, Ethylenediamine-N,N,N',N'-Tetrakis(2-Hydroxypropyl) Dioleate, Dodecanoyl Sarcosine, Sodium Laurylaminodipropionate Solution (30%), Oleoyl Sarcosine, Sodium Myristoyl-β-Alanine Solution, Sodium Undecyl Hydroxyethylimidazolinium Betaine, Ammonium Alkyl (C12,13,16) Sulfate, Triethanolamine Alkyl (C11,13,15) Sulfate, Triethanolamine Alkyl (C11,13,15) Sulfate Amine (2), alkyl (C12-15) triethanolamine sulfate, alkyl (C12-14) triethanolamine sulfate, alkyl (12,13) ​​sodium sulfate, polyoxyethylene alkyl ether triethanolamine sulfate (3E.O.) solution, (C11-15) pareth-3 sodium sulfate, (C12,13) ​​pareth-3 sodium sulfate, (C12-15) pareth-3 sodium sulfate, (C12,13) ​​pareth-3 TEA sulfate, (C12,13) ​​pareth-3 sulfate (TEA / Na), PEG-3 coconut fatty acid amide MEA sodium sulfate, PEG- 5 Coconut Fatty Acid Amide MEA Phosphate, PEG-5 Lauryl Citrate Sulfosuccinate Disodium, PEG-5 Ceteth-10 Phosphate, PEG-25 Butyl Phosphate, Sodium Alkyl (C14-18) Sulfonate, Alkyl (C20-22) Phosphate, Isolaureth-4 Phosphate, Undecylenoyl Glycine, Potassium Olive Fatty Acid, Oleyl Sarcosine, Sodium Oleyl Methyl Taurate, Oleth-3 Phosphate, Oleth-4 Phosphate, Oleth-5 Phosphate, Oleth-10 Phosphate, Oleth-20 Phosphate, Sodium Oleth-7 Phosphate, Sodium Oleth-8 PhosphateSodium olefin (C14-16) sulfonate, capryloyl glycine, sodium cocoyl amino acids, cocoyl alanine triethanolamine, sodium cocoyl isethionate, ammonium cocoyl isethionate, potassium cocoyl glycinate, sodium cocoyl glycinate, cocoyl glutamine triethanolamine, cocoyl glutamic acid, disodium cocoyl glutamate, cocoyl glutamate salts such as potassium cocoyl glutamate, cocoyl sarcosine, sodium cocoyl sarcosine, triethanolamine cocoyl sarcosine, Sodium cocoyl taurate, cocoyl methyl alanine, sodium cocoyl methyl alanine, methyl cocoyl taurine, potassium methyl cocoyl taurate, magnesium methyl cocoyl taurate, sodium methyl cocoyl taurate, sodium cocoyl apple amino acids, sodium coceth sulfate, di(C11-15) pareth-2 phosphate, di(C12-15) pareth-4 phosphate, di(C12-15) pareth-8 phosphate, di(C12-15) pareth-10 phosphate, dioleyl phosphate, sodium dioleth-8 phosphate, sodium dioleth-8 phosphate, dicocoyl Ethylenediamine PEG-15 Sodium Sulfate, Sodium Dilaureth-10 Phosphate, Steareth-2 Phosphate, Steareth-3 Phosphate, Calcium Stearoyl Lactylate, Sodium Stearoyl Lactylate, Undecylenamide MEA-2Na Sulfosuccinate, Lauramide MEA-2Na Sulfosuccinate, Disodium Laureth Sulfosuccinate, DEA Cetyl Phosphate, Potassium Cetyl Phosphate, Sodium Cetearyl Sulfate, Ceteth-10 Phosphate, Ceteth-20 Phosphate, Triceteareth-4 Phosphate, Tricedes-4 Phosphate, Tricedes-8 Phosphate, Tricedes-8 Phosphate Sodium Tricedes-4 Carboxylate, Sodium Tricedes-7 Carboxylate, Sodium Tricedes-3 Acetate, Potassium Tricedes-7 Phosphate, Trilaureth-4 Phosphate, Oleyl Lactate, Sodium Palmitate Glutamate, Magnesium Palmitoyl Glutamate, Sodium Palmitoyl Sarcosinate, Palmitoyl Proline, Sodium Palmitoyl Proline, Sodium Palmitoyl Methyl Taurate, Potassium Myristoyl Glutamate, Sodium Myristoyl Glutamate, Sodium Myristoyl Sarcosinate, Sodium Myristoyl Methyl Taurate,Potassium cocoate, triethanolamine cocoate, arginine cocoate, sodium lauraminodiacetate, sodium lauryl glycol acetate, laureth-5 carboxylic acid, laureth-6 carboxylic acid, laureth-11 carboxylic acid, sodium laureth-5 carboxylic acid, sodium laureth-6 carboxylic acid, sodium laureth-11 carboxylic acid, laureth-5 carboxylic acid, laureth-6 carboxylic acid, sodium laureth-11 carboxylic acid, laureth-5 acetic acid, laureth-6 acetic acid, laureth, Anionic surfactants such as potassium laureth-4,5 acetate, sodium laureth-3 acetate, sodium laureth-4 acetate, sodium laureth-5 acetate, sodium laureth-6 acetate, sodium laureth-11 acetate, MIPA laureth sulfate, sodium laureth sulfate, triethanolamine laureth sulfate, ammonium laureth-2 sulfate, ammonium laureth-3 sulfate, laureth-1 phosphate, laureth-2 phosphate, laureth-4 phosphate, sodium lauroyl aspartate, sodium lauroyl oat amino acid, sodium lauroyl lactylate, potassium lauroyl methyl alanine, triethanolamine lauroyl methyl alanine, dicetyl phosphate, cetyl phosphate, lauryl trimethyl ammonium chloride, dicocoyl dimethyl ammonium chloride, myristyl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium chloride, lauryl pyridinium chloride, cetyl pyridinium chloride, benzethonium chloride, stearyl trimethyl ammonium chloride, benzalkonium chloride, benzalkonium chloride solution, lauryl amine oxide, alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride Cetyl ammonium, stearyl dimethyl benzyl ammonium chloride, dimethylstearyl ammonium chloride treated hectorite, benzyl dimethyl stearyl ammonium chloride treated hectorite, distearyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride treated bentonite, dialkyl dimethyl ammonium chloride, tri(polyoxyethylene)stearyl ammonium chloride (5E.O.), di(polyoxyethylene)oleyl methyl ammonium chloride (2E.O.), stearoyl cholaminoformyl methyl pyridinium chloride, polyoxypropylene methyl diethyl ammonium chloride, alkyl diaminoethyl glycine hydrochloride solution, alkyl isoquinolinium bromide solution, lauryl trimethyl ammonium bromide, cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium bromide, cetyl trimethyl ammonium saccharin, stearyl trimethyl ammonium saccharin, polyethylene glycol-epichlorohydrin-coconut oil alkylamine-dipropylene triamine condensate, polyethylene glycol-epichlorohydrin-beef tallow alkylamine-dipropylene triamine condensateLanolin Ethyl Sulfate Fatty Acid Aminopropylethyldimethylammonium (1), (2), Behenyl Trimethylammonium Bromide, Behenic Acid Amidopropyldimethylhydroxypropylammonium Chloride, Stearic Acid Diethylaminoethylamide, Stearic Acid Dimethylaminopropylamide, Lanolin Derivative Quaternary Ammonium Salt, PEG-5 Oleamine, PEG-2 Oleammonium Chloride, PEG-2 Cocamine, PEG-3 Cocamine, PEG-5 Cocamine, PEG-10 Cocamine, PEG-15 Cocamine, PEG-2 Dimeadowfoam Amidoethylmonium methosulfate, alkyl (C12,14)oxyhydroxypropylarginine hydrochloride, alkyl (C16,18)trimonium chloride, isoalkyl (C10-40)amidopropylethyldimonium ethosulfate, isostearylethylimidazolinium ethosulfate, caesalpinia spinosa hydroxypropyltrimonium chloride, quaternium-33, quaternium-91, cocamidopropyl PG dimonium chloride, cocamidopropyl betaine amide MEA chloride, cocoyl arginine Ethyl PCA, Cocotrimonium Methosulfate, Fenugreek Hydroxypropyltrimonium Chloride, Myristamide / Palmitamide Butylguanidine Acetate, Dialkyl (C12-18) Dimonium Chloride, Dicocoyl Ethyl Hydroxyethylmonium Methosulfate, Dicocodimonium Chloride, Distearyldimonium Chloride, Distearoyl Ethyl Hydroxyethylmonium Methosulfate, Dicetyldimonium Chloride, Dipalmitoyl Ethyl Hydroxyethylmonium Methosulfate, Dihydroxypropyl PEG-5 Linoleate Ammonium chloride, dimethyl PABA amidopropyl laurdimonium tosylate, dimethylstearamine, stearamidoethyl diethylamine, stearamidopropyl dimethylamine, stearalkonium chloride, stearyltrimonium saccharin, steartrimonium chloride, steartrimonium bromide, stearoxypropyltrimonium chloride, cetalkonium chloride, cetylpyridinium chloride, cetrimonium chloride, cetrimonium bromide, cetrimonium methosulfate, soytrimonium chloride,Palmitamidopropyltrimonium chloride, panthenyl hydroxypropyl steardimonium chloride, hydroxyethyl cetyldimonium phosphate, hydroxypropyltrimonium honey, hydroxypropyl bishydroxyethyldimonium chloride, behenamidopropyl dimethylamine, behenamidopropyl dimethylamine, behentrimonium chloride, behentrimonium methosulfate, poloxamine 701, poloxamine 702, poloxamine 704, malonic acid bishydroxyethyl cetylamide, coconut oil alkyl PG di Cationic surfactants such as sodium monium chloride phosphate, lauryltrimonium chloride, laurylpyridinium chloride, linoleamidopropyl PG dimonium chloride phosphate, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, undecyl-N-hydroxyethyl-N-carboxymethyl imidazolium betaine, coconut oil alkyl betaine, coconut oil fatty acid amidopropyl betaine, stearyl dihydroxyethyl betaine, stearyl dimethylaminoacetic acid Acid betaine, bis(stearyl-N-hydroxyethylimidazoline) chloroacetic acid complex, coconut oil fatty acid hydrolyzed collagen, oleoyl hydrolyzed collagen, hydrolyzed collagen hexadecyl, lauric acid amidopropyl betaine solution, myristoyl hydrolyzed collagen solution, alkylaminoethylglycine hydrochloride solution, lecithin and other carboxybetaine types, amidobetaine type, sulfobetaine type, hydroxysulfobetaine type, amidosulfobetaine type, phosphobetaine type, aminocarboxylate type, imidazoline derivative type, amidoamine type, PEG- 3 Lauramine Oxide, Oleamine Oxide, Oleyl Betaine, (Capryl / Capramido) Propyl Betaine, Cocoamine Oxide, Sodium Cocoamphoacetate, Sodium Cocoamphodiacetate, Disodium Cocoamphodiacetate, Sodium Cocoamphopropionate, Dihydroxyethyl Lauramine Oxide, Stearamine Oxide, Stearyl Betaine, Sodium Palm Kernel Amidoethyl Hydroxyethylaminopropionate, Palm Kernel Amidopropyl Betaine, Hydroxyalkyl (C12,14) Hydroxyethylalanine,Examples of the surfactant include amphoteric surfactants such as heptadecyl hydroxyethyl carboxylate methyl imidazolinium chloride / heptadecyl bishydroxyethyl imidazolinium, myristamidopropyl betaine, myristamine oxide, myristyl betaine, lauramidopropylamine oxide, lauramidopropyl hydroxysultaine, lauramidopropyl betaine, sodium lauraminopropionate, lauramine oxide, sodium lauriminodipropionate, lauryl hydroxysultaine, lauryl betaine, sodium lauroamphoacetate, and lauroyl lysine; escin, sodium surfactin, saponin, hydroxylated lecithin, hydrogenated lysolecithin, hydrogenated lecithin, cephalin, phosphatidylserine, and water-soluble collagen. One surfactant may be used alone, or two or more may be used in combination.

[0087] (fragrance) Fragrances include benzaldehyde, cinnamic aldehyde, cyclamen aldehyde, citral, citronellal, 2-methyl-3-(4-methylphenyl)-propanal, undecenal, methylnonylacetaldehyde, 3,7-dimethyl-1-octanal, hydroxycitronellal, methoxycitronellal, perillaldehyde, myrtenal, caryophyllenic aldehyde, n-hexal, 2-methylbutanal, isovaleraldehyde, n-valeraldehyde, acetaldehyde, n-heptanal, and n-octanal. nal, n-nonanal, 2-methyloctanal, 3,5,5-trimethylhexanal, 1-decanal, undecanal, dodecanal, 2-methyldecanal, 2-methylundecanal, tridecanal, tetradecanal, 2-pentenal, cis-3-hexenal, trans-2-hexenal, trans-2-heptenal, 4-heptenal, trans-2-octenal, trans-2-nonenal, cis-6-nonenal, 2,6-dimethyl-5-heptenal, trans-4-decenal, cis-4-decenal, trans-2-decenal, 2,5,6-trimethyl-4-heptenal, 10-undecenal, trans-2-undecenal, trans-2-dodecenal, 3-dodecenal, trans-2-tridecenal, 2,6,10-trimethyl-9-undecen-1-al, 2,4-hexadienal, 2,4-heptadienal, 2,4-octadienal, 2,4-nonadienal, 2,6-nonadienal, 2,4-decadienal, 2,4-undecadienal, 2,4-dodecadienal ol, 5,9-dimethyl-4,8-decadienal, 3,7,9-trimethyl-2,6-decadien-1-al, 2,6,10-trimethyl-5,9-undecadienal, α-methylenecitronellal, campholenaldehyde, cyclocitral, isocyclocitral, 2,6,6-trimethyl-1,3-cyclohexadiene-1-carboxaldehyde, 6,10-dimethyl-3-oxa-9-undecenal, geranyloxyacetaldehyde, dimethyltetrahydrobenzaldehyde, 3-propylbicyclo[2,2,1]-5-heptene-2-carboxaldehyde, methoxydicyclopentadienecarboxaldehyde, 4-tricyclodecylidenebutanal, 4-(4-methyl-3-cyclohexenylidene-1)pentanal, 4(3)-(4-methyl-3-penten-1-yl)-3-cyclohexene-1-carboxaldehyde, cetanoal, inonal, terrestral, p-tolyl aldehyde, phenylacetaldehyde, 3-phenylbutanal, cumin aldehyde, p-methylphenylacetal Aldehyde, p-isopropylphenylacetaldehyde, hydratropaldehyde, p-methylhydratropaldehyde, p-isopropylhydratropaldehyde, phenylpropionaldehyde, β-methylhydrocinnamic aldehyde, jasmolandi, bourgeonal, florarozone, suzalal, salicylic aldehyde, anisaldehyde, o-methoxybenzaldehyde, o-methoxycinnamic aldehyde, canthoxal, vanillin, ethyl vanillin, methyl vanillin (3,4-Dimethoxybenzaldehyde), Helional, Phenoxyacetaldehyde, p-Methylphenoxyacetaldehyde, Furfural, 5-Methylfurfural, 5-Hydroxymethyl-2-furfural, Furyl acrolein, Lyral, Bernaldehyde, Homomylac aldehyde, Juniperle, Vertral, Lilial, Meflanal, Eglantal, Cocal, α-Methylcinnamic aldehyde, α-Butylcinnamic aldehyde, α-Amylcinnamic aldehyde, α-Hexylcinnamic aldehyde, Formylethyltetramethyltetralin and other aldehydes, Terpinel acetate, Vetiveryl acetate, Benzyl acetate, Linalyl acetate, Isopentyl salicylate butyl, benzyl salicylate, hexyl salicylate, cis-3-hexenyl salicylate, ethyl formate, cis-3-hexenyl formate, linalyl formate, citronellyl formate, geranyl formate, benzyl formate, phenylethyl formate, ethyl acetate, butyl acetate, isoamyl acetate, methyl cyclopentylideneacetate, hexyl acetate, cis-3-hexenyl acetate, trans-2-hexenyl acetate, isononyl acetate, citronellyl acetate, lavandulyl acetate, geranyl acetate, myrcenyl acetate, terpinyl acetate, menthyl acetate, menthanyl acetate, nopyr acetate, n-bornyl acetate, isobornyl acetate, pt-butylcyclohexyl acetate, ot-butylcyclohexyl acetate, tricyclodecenyl acetate, 2,4-Dimethyl-3-cyclohexene-1-methanil, phenylethyl acetate, styrallyl acetate, dimethylbenzylcarbinyl acetate, cinnamyl acetate, anisyl acetate, paracresyl acetate, heliotropyl acetate, acetyleugenol, acetylisoeugenol, guaiyl acetate, cedryl acetate, ethyl propionate, isoamyl propionate, citronellyl propionate, geranyl propionate, linalyl propionate, terpinyl propionate, benzyl propionate, cinnamyl propionate, cyclohexyl allyl propionate, propionyl Tricyclodecenyl isobutyrate, Ethyl butyrate, Ethyl 2-methylbutyrate, Butyl butyrate, Isoamyl butyrate, Hexyl butyrate, Linalyl butyrate, Geranyl butyrate, Citronellyl butyrate, Benzyl butyrate, cis-3-hexenyl isobutyrate, Citronellyl isobutyrate, Geranyl isobutyrate, Linalyl isobutyrate, Benzyl isobutyrate, Phenylethyl isobutyrate, Tricyclodecenyl isobutyrate, Ethyl isovalerate, Propyl valerate, Citronellyl isovalerate, Geranyl isovalerate, Benzyl isovalerate, Cinnamyl isovalerate, Phenylethyl isovalerate, Ethyl caproate, Capron Allyl enanthate, ethyl enanthate, allyl enanthate, ethyl caprate, citronellyl tiglate, methyl benzoate, ethyl benzoate, isobutyl benzoate, isoamyl benzoate, geranyl benzoate, linalyl benzoate, benzyl benzoate, phenylethyl benzoate, methyl phenylacetate, ethyl phenylacetate, isobutyl phenylacetate, isoamyl phenylacetate, geranyl phenylacetate, benzyl phenylacetate, phenylethyl phenylacetate, p-cresyl phenylacetate, methyl cinnamate, ethyl cinnamate, benzyl cinnamate, cinnamyl cinnamate, cinnamic acid Phenylethyl cinnamate, methyl salicylate, ethyl salicylate, isobutyl salicylate, amyl salicylate, hexyl salicylate, cis-3-hexenyl salicylate, phenylethyl salicylate, methyl jasmonate, methyl dihydrojasmonate, fultate, allyl 2-pentyloxyglycolate, ethyl 3-methyl-3-phenylglycidate, ethyl 2-pentanoate, 4-acetoxy-3-amyltetrahydropyran, cyclohexyl salicylate, ethyl 2-cyclohexylpropionate, ethyl tricyclo[5.2.1.02,6] Decane-2-carboxylate, 2-methylpentyl 2-methylpentylate and other esters, γ-undecalactone, pentalide (cyclopentadecanolide), habanolide (oxacyclohexadecen-2-one), ambretolide, cyclohexadecanolide, 10-oxahexadecanolide, 11-oxahexadecanolide, 12-oxahexadecanolide, ethylene dodecanedioate, γ-butyrolactone, γ-valerolactone, angelicalactone, γ-hexalactone, γ-heptalactone, γ-octalactone, γ-nonalactone, 3-methyl- 4-Octanolide, γ-Decalactone, γ-Dodecalactone, γ-Jasmolactone, Jasmine lactone, cis-jasmone lactone, lactojasmone, jasmolactone, menthalactone, n-butylphthalide, propylidenephthalide, butylidenephthalide, δ-hexalactone, δ-octalactone, trivalone, δ-nonalactone, δ-decalactone, δ-2-decenolactone, δ-undecalactone, δ-dodecalactone, δ-tridecalactone, δ-tetradecalactone, lactoscatone (decahyde) Lactones such as 4,α-hydroxy-2,8,8-trimethylnaphthalene-2-carboxy acid-δ-lactone, coumarin, dihydrocoumarin, cyclohexyl lactone, 6-methylcoumarin, ε-decalactone, ε-dodecalactone, acetylcaryophyllene, carvone, pulegone, piperitenone, piperitone, camphor, isolongifolaone, nootkatone, 2-heptanone, 2-pentanone, 3-hexanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 2-octanone Nanon, 3-nonanone, 2-undecanone, 2-tridecanone, methyl isopropyl ketone, ethyl isoamyl ketone, mesityl oxide, butylideneacetone, methylheptadienone, methylheptenone, dimethyloctenone, 4-methylene-3,5,6,6-tetramethyl-2-heptanone, geranylacetone, farnesylacetone, acetoin, 5-hydroxy-4-octanone, methyl lavender ketone, diacetyl, 2,3-pentanedione, 2,3-hexadione, 3,4-hexadione, 2,3-Heptadione, acetyl isovaleryl, amyl cyclopentanone, amyl cyclopentenone, 2-cyclopentyl cyclopentanone, hexyl cyclopentanone, 2-n-heptyl cyclopentanone, cis-jasmone, dihydrojasmone, isojasmone, trimethylpentyl cyclopentanone, sedamone (2-butylidene-3,5,5(3,3,5)-trimethylcyclopentanone), Sandex, Cyclotene, 3,5-dimethyl-1,2-cyclopentadione, methylcholiron, 2-tert-butylcyclohexanone, p-t ert-Butylcyclohexanone, 3,3-dimethylcyclohexyl methyl ketone, 2-sec-butylcyclohexanone, Artemon, Celery ketone, Krypton, p-tert-pentylcyclohexanone, Methylcyclocitrone, Neron, 4-cyclohexyl-4-methyl-2-pentanone, Havanol, Maltol, Ethyl maltol, Oxide ketone, Emoxifurone, Homofuron, Sotolon, Furaneol, Acetyldimethylfuran, Furfuralacetone, 2-Acetyl-5-methylfuran, 2-Acetylfuran, Methyltet Hydrofuranone, dibenzyl ketone, benzophenone, methyl naphthyl ketone, 4-damascol, 4-methyl-4-phenyl-2-pentanone), α-methylanisalacetone, heliotropylacetone, anisylideneacetone, anisylacetone, p-methoxyphenylacetone, raspberry ketone, lavandone, benzylideneacetone, p-methoxyacetophenone, p-methylacetophenone, propiophenone, acetophenone, isodamascone, α-dynascone, iritone, ionone, pseudoionone, methylionone, methylionone Lithon, 2,4-di-tert-butylcyclohexanone, allylionone, 2,6,6-trimethyl-2-cyclohexene-1,4-dione, 2-acetyl-3,3-dimethylnorbornane, Florex, Plicatone, Oxocedrane, Vertofix, Verbenone, Fenchone, Karone, Trimofix O, Epitone, Atrinone, Cashmeran, 3-methylcyclopentadecanone-1, cycloheptadecanone-9-en-1-one, cyclopentadecanone, cyclohexadecenone, phantolide, 4-acetyl-6-tert-butyl-1,Ketones such as 1-dimethylindan, traseolide, tonalide, vitalide, dihydrocarvone, diosphenol, zingerone, Iso E Super, phenylacetic acid, sandalole, linalool, musk ketone, methyl ionone, iris oil, iron, indole, ylang-ylang oil, estragole, oakmoss, opoponax resinoid, eugenol, aurantiol, galacsolid, carvacrol, L-carvone, camphor, Canon, carrot seed oil, clove oil, geraniol, geranyl nitrile, sandalwood oil, cyclopentadecanolide, dihydromyrcenol, jasmine absolute, cinnamon bark oil, 1,8-cineole, styrax resinoid, cedarwood oil, cedrene, cedrol, celery seed oil, thyme oil, damascone, damascenone, thymol, tuberose absolute, decalactone, terpineol, gamma-terpinene, triplal, 2,6-nonadienol, nonalactone, patchouli alcohol, patchouli oil, phenethyl alcohol , Petitgrain Oil, cis-3-Hexenol, Balsam of Peru, Vetiver Oil, Vetiverol, Peppermint Oil, Pepper Oil, Heliotropin, Bergamot Oil, Borneol, Myrrhizinoids, Menthol, L-Menthol, L-Menthone, Eucalyptus Oil, β-Ionone, Lime Oil, Lavender Oil, D-Limonene, Lemon Oil, Rose Absolute, Rose Oxide, Rose Oil, Rosemary Oil, Asafoetida Resinoids, Ajowan Oil, Star Anise Oil, Abies Oil, Amyris Oil, Ambrette Seed Oil, Ambergris Tincture, Ylang Ylang Absolute , Iris resinoid, Iris absolute, Wintergreen oil, Elemi oleoresin, Elemi resinoid absolute, Elemi tincture, Oakmoss concrete, Oakmoss absolute, Oakmoss resin, Oakmoss resinoid, Ocotea oil, Osmanthus absolute, Osmanthus concrete, Opopanax resinoid, Opopanax absolute, Opopanax oil, Olibanum resinoid, Olibanum absolute, Olibanum oil, Allspice oil, Oregano oil, Oregano resin, Orange flower absolute Orange flower concrete, cananga oil, gājun balsam, gājun balsam oil, cascari bark oil, castoreum absolute, cassi absolute, cassi flower oil, cassia oil, gardenia absolute, carnation absolute, cabreuva oil, chamomile oil, cardamom oil, galbanum oil, galbanum resin, galbanum resinoid, caraway seed oil, guaiac wood oil, guaiac resin, guaiac concrete, camphor oil, cubeba oil, cumin oil, cumin absolute, cumin oleoresin,Clary sage oil, grapefruit oil, costus oil, copaiba balsam, copaiba balsam oil, copaiba balsam resin, coriander oil, sassafras oil, genet absolute, perilla oil, citronella oil, jasmine concrete, juniper berry oil, civet absolute, civet tincture, jonquil absolute, agarwood oil, ginger oil, cinnamon oil, cinnamon leaf oil, cedar oil, styrax oil, spearmint oil, savory oil, sage oil, cedar oil, cedar leaf oil, taget oil, tarragon oil, dill oil, tea tree oil, Leaf Absolute, True Balsam, Nutmeg Oil, Narcissus Absolute, Neroli Oil, Violet Leaf Absolute, Pine Oil, Basil Oil, Parsley Leaf Oil, Parsley Seed Oil, Parsley Herb Oil, Mint Oil, Vanilla Absolute, Honeysuckle Absolute, Palmarosa Oil, Valerian Oil, Bitter Orange Oil, Hyssop Oil, Hiba Oil, Hyacinth Absolute, Fennel Oil, Fig Absolute, Buchu Oil, Pennyroyal Oil, Peppermint Oil, Benzoin Tincture, Benzoin Resinoid, Bois Drosera Oil, Hosho Oil, Hop oil, hop concrete, hop absolute, marjoram oil, mandarin oil, orange oil, mimosa concrete, mimosa absolute, mimosa oil, mill absolute, mill oil, musk absolute, musk tincture, yuzu oil, artemisia oil, labdanum oil, labdanum resinoid, lavender absolute, lavandin oil, lavandin absolute, linaloe oil, lemongrass oil, rose concrete, lovage oil, laurel oil, laurel leaf oil, wormwood oil, musk, spirit cat incense, dragon's oak, beaver incense, musk Chibata, alpha-pine Hydrocarbons such as acetonitrile, β-pinene, camphene, myrcene, terpineol, terpinolene, ocimene, γ-terpinene, α-phellandrene, p-cymene, β-caryophyllene, β-farnesene, 1,3,5-undecatriene, diphenylmethane, anise alcohol, cinnamic alcohol, phenylpropyl alcohol, dimethylbenzyl carbinol, phenylethyl methylethyl carbinol, 3-methyl-5-phenylpentanol, orcinol monomethyl ether, isoeugenol, santalol, isobornylcyclohexanol,Sandalore, Bagdanol, Sandalmysolkha, Brahmanol, Evanol, Polysanthol, 2-Ethoxy-4-methoxymethylphenol, Trans-2-Hexenol, Cis-3-Hexenol, 3-Octanol, 1-Octen-3-ol, 2,6-Dimethyl-2-Heptanol, 9-Decenol, 4-Methyl-3-Decen-5-ol, 10-Undecenol, Trans-2-Cis-6-Nonadienol, Nerol, Citronellol, Rhodinol, Myrcenol, Lavanduol, Tetrahydrogeraniol, Tetrahydrolinalool , Hydroxycitronellol, Alloocimenol, Terpinen-4-ol, Isopulegol, Nopol, Farnesol, Nerolidol, Bisabolol, Patchouli Alcohol, 2,4-Dimethyl-3-cyclohexene-1-methanol, 4-Isopropylcyclohexanol, 4-Isopropylcyclohexanemethanol 1-(4-Isopropylcyclohexyl)-ethanol, 2,2-Dimethyl-3-(3-methylphenyl)-propanol, pt-Butylcyclohexanol, ot-Butylcyclohexanol, Ambrinol, Benzyl Alcohol Alcohols such as phenylethyl alcohol, phenoxyethanol, styrallyl alcohol, methyl dihydrojasmonate, tetrahydrofurfuryl 3-mercaptopropionate, Cobanol, geranium oil, birch oil, alumoise oil acetyl cedrene, amyl cinnamaldehyde, allyl amyl glycolate, β-ionone, isobutylquinoline, nerol oxide, miloxide, rose oxide, rimetol, menthofuran, linalool oxide, butyldimethyldihydropyran, acetoxyamyltetrahydropyran, Cedryl methyl ether, methoxycyclododecane, 1-methyl-1-methoxycyclododecane, ethoxymethyl cyclododecyl ether, tricyclodecenyl methyl ether, Lubofix, Cedroxide, Ambroxan, Grisalva, Voisilis, Anisole, Dimethylhydroquinone, Paracresyl methyl ether, Acetanisole, Anethole, Dihydroanethole, Diphenyloxide, Methyleugenol, Methylisoeugenol, Benzylisoeugenol, Phenylethylisoamyl ether, δ-Naphthyl methyl ether,Examples of the fragrance include ethers such as δ-naphthyl ethyl ether, δ-naphthyl isobutyl ether, 2,4-dimethyl-4-phenyltetrahydrofuran, galaxolide, and 2,2,5,5-tetramethyl-4-isopropyl-1,3-dioxane, various essential oils, and other synthetic and natural fragrances, as well as various blended fragrances. The fragrances may be used alone or in combination of two or more.

[0088] (dye) Pigments include annatto, crocin, capsanthin, shisonin, hibiscus pigment, grapeskin extract, safflor yellow, cocoa pigment, laccaic acid, carminic acid, curcumin, betanin, monascorubrin, brazilin, caramel, safflower pigment, gardenia pigment, lithospermum root pigment, and cochineal pigment, as well as anthraquinone, anthocyanin, chalcone, carotenoid, flavonoid, flavin, quinone, porphyrin, diketone, and pentacyanidin pigments. Natural coloring agents, photosensitizers such as Photosensitizer No. 101, Photosensitizer No. 201, Photosensitizer No. 301, Photosensitizer No. 401, Red No. 2, Red No. 3, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Red No. 201, Red No. 202, Red No. 203, Red No. 204, Red No. 205, Red No. 206, Red No. 207, Red No. 208, Red No. 213, Red No. 214, Red No. 215, Red No. 218, Red No. 219, Red No. 220, Red No. 221, Red No. 223, Red No. 225, Red No. 226, Red No. 227, Red No. 228, Red No. 23 No. 0, Red 231, Red 232, Orange 201, Orange 203, Orange 204, Orange 205, Orange 206, Orange 207, Yellow 4, Yellow 5, Green 3, Green 201, Green 202, Green 204, Green 205, Yellow 201, Yellow 202, Yellow 203, Yellow 204, Yellow 205, Yellow 401, Yellow 402, Yellow 403, Yellow 404, Yellow 405, Yellow 406, Yellow 407, Green 401, Green 402, Blue 403, Purple 401, Black 401, Blue 404 Examples of suitable pigments include organic pigment powders such as zirconium, barium, or aluminum lakes of Red No. 401, Red No. 404, Red No. 405, Red No. 501, Red No. 502, Red No. 503, Red No. 504, Red No. 506, Orange No. 401, Orange No. 402, Orange No. 403, Red No. 505, and Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 202, Blue No. 203, Blue No. 204, Blue No. 205, Brown No. 201, and Purple No. 201, as well as pigments obtained by blending the above organic powders with natural pigments such as Lithospermum rhizome pigments and safflower pigments, or organic synthetic pigments. One pigment may be used alone, or two or more pigments may be used in any combination ratio.

[0089] (Antiseptic or disinfectant)Examples of preservatives or disinfectants include alkyl parahydroxybenzoates such as phenol, parachlorophenol, parachlorometacresol, parachlorometaxylenol, resorcinol, resorcinol monoacetate, orthophenylphenol, isobutylparaben, ethylparaben, sodium ethylparaben, butylparaben, sodium butylparaben, propylparaben, sodium propylparaben, methylparaben, and sodium methylparaben, phenoxyethanol, thymol, cresol, hinokitiol, and hydroxybenzathiol. Phenols such as benzoic acid and its salts, salicylic acid and its salts, sorbic acid and its salts, dehydroacetic acid and its salts, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, halogenated bisphenols such as hexachlorophene, bithionol, and dichlorophen, amides such as 3,4,4'-trichlorocarbanilide, 3-trifluoromethyl 4,4'-dichlorocarbanilide, 3,4',5-tribromosalicylanilide, p-aminobenzenesulfonamide, and undecylenic acid monoethanolamide, and benzalkonium chloride. , quaternary ammonium compounds such as alkylisoquinolinium bromide, benzethonium chloride, cetylpyridinium chloride, dequalinium chloride, alkyltrimethylammonium chloride, etc., zwitterionic surfactants such as alkylaminoethylglycine chloride, sodium stearyl hydroxyethyl betaine chloride, etc., chlorhexidine gluconate, tetramethylthiuram disulfide, photosensitizers such as photosensitizer No. 101, photosensitizer No. 201, photosensitizer No. 301, photosensitizer No. 401, photosensitizer NK-143, etc., 1-hydroxypyridine-2-thione (zinc pyrithione), imidazolidinyl urea, N-trichloromethyl mercapto-4-cyclohexene 1,2-dicarboximide, lysozyme chloride, chlorphenesin, chlorobutanol, 2-bromo-2-nitro-1,3-propanediol, anise oil, sea lion oil, citronellol, eugenol, benzyl alcohol, ethanol, 1,3-butylene glycol, hexylene glycol, dipropylene glycol, glycerin, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol (pentylene glycol), 1,2-hexanediol, 1,Alcohols such as 2-heptanediol, 1,2-octanediol, 1,2-nonanediol, and 1,2-decanediol, parachlormetacresol, chlorhexidine chloride, zinc bis(2-pyridylthio-1-oxide), thianthol, isopropylmethylphenol, 6-acetoxy-2,4-dimethyl-m-dioxane, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, chlorine, sodium hypochlorite, bleaching powder, iodine, formaldehyde, and glutar Examples of antibacterial agents include aldehydes, diethyl pyrocarbonate, ethylene oxide, β-propiolactone, hydrogen peroxide, sulfur, potassium gluconate, DMDM ​​hydantoin, alkyl (C12-14) diethylaminoethylglycine hydrochloride, quaternium-80, quaternium-87, chloramine T, cymen-5-ol, propyl iodide butylcarbamate, polyaminopropyl biguanide, methylisothiazolinone, methylchloroisothiazolinone, dimethylaminostyrylheptylmethylthiazolium iodide, etc. In addition, plant extracts such as echinacea leaf extract, Phellodendron bark extract, olive leaf extract, orange juice, artemisia capillaris extract, licorice flavonoids, kumazasa extract, grapefruit extract, chlorphenesin, honeysuckle extract, phenoxyethanol, saxifrage extract, and burnet extract can also be advantageously used as antibacterial agents. The preservatives or disinfectants may be used alone or in combination of two or more.

[0090] (antioxidant) Examples of antioxidants include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, butyl gallate, octyl gallate, dodecyl gallate, nordihydrogallic acid, butylhydroxyanisole, dibutylhydroxytoluene, ascorbic acid, ascorbic acid-2-glucoside, ergothioneine, vitamin E, catechins, flavonoids, and derivatives thereof. The content thereof can also be changed as desired.

[0091] (ultraviolet absorber) Examples of ultraviolet absorbers include para-aminobenzoic acid-based ultraviolet absorbers such as para-aminobenzoic acid, para-aminobenzoic acid monoglycerin ester, N,N-dipropoxypara-aminobenzoic acid ethyl ester, N,N-diethoxypara-aminobenzoic acid ethyl ester, N,N-dimethylpara-aminobenzoic acid ethyl ester, and N,N-dimethylpara-aminobenzoic acid butyl ester; anthranilic acid-based ultraviolet absorbers such as homomenthyl-N-acetylanthranilate; cinnamic acid; and oxybenzone-3 benzophenone derivatives such as oxybenzone-4, oxybenzone-5, and oxybenzone-9; sugar-based UV absorbers in which sugar or sugar alcohol is bound to a 1,3-propanedione derivative; salicylic acid-based UV absorbers such as salicylic acid and its sodium salts, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, and dipropylene glycol salicylate; Acetate, octyl cinnamate, ethyl 4-isopropyl cinnamate, methyl 2,5-diisopropyl cinnamate, ethyl 2,4-diisopropyl cinnamate, methyl 2,4-diisopropyl cinnamate, propyl p-methoxycinnamate, isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate, 2-ethoxyethyl p-methoxycinnamate (cinoxate), cyclohexyl Cinnamic acid-based UV absorbers such as 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,Benzophenone-based ultraviolet absorbers such as 4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, and 4-hydroxy-3-carboxybenzophenone; 3-(4'-methylbenzylidene)-d,l-camphor; Dibenzoyl compounds such as 3-benzylidene-d,l-camphor, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenylbenzotriazole, dibenzalazine, dianisoylmethane, 5-(3,3-dimethyl-2-norbornylidene)-3-pentan-2-one, 4-methoxy-4'-t-butyldibenzoylmethane, and 4-t-butylmethoxydibenzoylmethane methylmethane derivatives, octyl triazone, urocanic acid derivatives such as urocanic acid and ethyl urocanate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 1-(3,4-dimethoxyphenyl)-4,4-dimethyl-1,3-pentanedione, hydantoin derivatives such as dimethoxybenzylidene dioxoimidazolidinepropionate octyl, dimethoxybenzylidene dioxoimidazolidinepropionate 2-ethylhexyl, phenylbenzimidazolazole sulfonic acid, terephthalidene dicamphor sulfonic acid, dromedine ... Examples of ultraviolet absorbers include metrizole trisiloxane, methyl anthranilate, rutin and its derivatives, oryzanol and its derivatives, octyl dimethyl para-aminobenzoate, titanium oxide, zinc oxide, kaolin, talc, ethylhexyl triazone, octocrylene, dimethyl PABA octyl, homosalate, methylene bisbenzotriazolyl tetramethylbutylphenol, ethylhexyl methoxycinnamate, and octyl methoxycinnamate. One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.

[0092] (sequestering agent) Examples of sequestering agents (chelating agents) include ethylenediaminetetraacetic acid (EDTA), ethylenediaminetetraacetate salts such as EDTA2Na, EDTA3Na, and EDTA4Na, hydroxyethylethylenediaminetriacetate salts such as hydroxyethylethylenediaminetriacetate trisodium salt, tripolyphosphate, diethylenetriaminepentaacetate salts, phosphonic acids such as phytic acid and salts thereof such as sodium salts, polyamino acids such as sodium oxalate, polyaspartic acid, and polyglutamic acid, sodium polyphosphate, sodium metaphosphate, phosphoric acid, pyrophosphate, hexametaphosphate, sodium citrate, citric acid, alanine, dihydroxyethylglycine, gluconic acid, succinic acid, and tartaric acid. One sequestering agent may be used alone, or two or more may be used in combination.

[0093] (buffering agent) Examples of buffers (pH adjusters) include citric acid, sodium citrate, lactic acid, sodium lactate, glycolic acid, succinic acid, acetic acid, sodium acetate, potassium acetate, malic acid, tartaric acid, fumaric acid, phosphoric acid, hydrochloric acid, sulfuric acid, boric acid, borax, nitrilotriethanol, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, arginine, ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, potassium hydrogen phosphate, aqueous ammonia, guanidine carbonate, ammonium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, magnesium oxide, calcium oxide, ammonium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, magnesium phosphate, calcium phosphate, sodium borate, sodium metaborate, and potassium citrate. The buffering agent may be used alone or in combination of two or more.

[0094] (antioxidant)Antioxidants include vitamin A such as retinol, dehydroretinol, retinol acetate, retinol palmitate, retinal, retinoic acid, vitamin A oil, and their derivatives and salts; carotenoids such as α-carotene, β-carotene, γ-carotene, cryptoxanthin, astaxanthin, fucoxanthin, and their derivatives; vitamin B such as pyridoxine, pyridoxal, pyridoxal-5-phosphate ester, pyridoxamine, and their derivatives and salts; ergocalciferol, cholecalciferol, Vitamin Ds such as luciferol and 1,2,5-dihydroxy-cholecalciferol, their derivatives and salts, vitamin Es such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, α-tocotrienol, β-tocotrienol, γ-tocotrienol, δ-tocotrienol, tocopherol acetate, tocopherol nicotinate, their derivatives and salts, trolox, its derivatives and salts, dihydroxytoluene, butylhydroxytoluene, butylhydroxytoluene hydroxyanisole, dibutylhydroxytoluene, α-lipoic acid, dehydrolipoic acid, glutathione, its derivatives and their salts, uric acid, erythorbic acid, sodium erythorbate and other erythorbic acids, its derivatives and their salts, gallic acid, propyl gallate and other gallic acids, its derivatives and their salts, rutin, α-glycosyl-rutin and other rutins, its derivatives and their salts, tryptophan, its derivatives and their salts, histidine, its derivatives and their salts, N-acetylcysteine, N-acetylhomocysteine cysteine ​​derivatives such as cysteine, N-octanoylcysteine, and N-acetylcysteine ​​methyl ester, and salts thereof; cystine derivatives such as N,N'-diacetylcystine dimethyl ester, N,N'-dioctanoylcystine dimethyl ester, and N,N'-dioctanoylhomocystine dimethyl ester, and salts thereof; carnosine and its derivatives and salts; homocarnosine and its derivatives and salts; anserine and its derivatives and salts; carcinine and its derivatives and salts;Dipeptide or tripeptide derivatives containing histidine and / or tryptophan and / or histamine and their salts, flavanones, flavones, anthocyanins, anthocyanidins, flavonols, quercetin, quercitrin, myricetin, fisetin, hamamelitannin, flavonoids such as catechin, epicatechin, gallocatechin, epigallocatechin, epicatechin gallate, and epigallocatechin gallate, tannic acid, caffeic acid, ferulic acid, protocatechuic acid, chalcone, oryzanol, carnosol, sesamol, sesamin, sesamolin, zingerone, curcumin, tetrahydrocurcumin, clovamide, deoxyclovamide, shogaol, capsaicin, vanillylamide, ellagic acid, bromophenol, flavones, melanoidins, riboflavins, Examples of antioxidants include riboflavin butyrate, flavin mononucleotide, flavin adenine nucleotide, ubiquinone, ubiquinol, mannitol, bilirubin, cholesterol, ebselen, selenomethionine, ceruloplasmin, transferrin, lactoferrin, albumin, superoxide dismutase, catalase, glutathione peroxidase, metallothionein, thioredoxin, thiotaurine, O-phosphono-pyridoxylidenerhodamine, N-(2-hydroxybenzyl)amino acid, its derivatives and salts thereof, N-(4-pyridoxylmethylene)amino acid, its derivatives and salts thereof, lysine, l-methionine, proline, silymarin, tea extract, grape bark / seed extract, melanin, rosemary extract, etc. One type of antioxidant may be used alone, or two or more types may be used in combination.

[0095] (pigment) Examples of pigments include extender pigments such as talc, kaolin, mica, sericite, calcium carbonate, magnesium carbonate, magnesium silicate, and silicic anhydride; white pigments such as titanium oxide and zinc oxide; colored pigments such as yellow iron oxide, red iron oxide, black iron oxide, ultramarine, ferric iron oxide, chromium oxide, chromium hydroxide, and carbon black; pearl pigments such as fish scale foil, bismuth oxychloride, titanium mica, and titanium colored mica; and powder pigments such as magnesium, calcium, and aluminum stearates, zinc salts of lauric acid, palmitic acid, and myristic acid, starch powder, silk powder, nylon powder, polymethyl methacrylate powder, and polyethylene powder. One type of pigment may be used alone, or two or more types may be used in combination.

[0096] In addition to the above, the cosmetic additive of the present invention can be used in appropriate combination with known cosmetic raw materials, for example, as described in "Japanese Cosmetic Raw Materials Collection 2007" (published by the Japan Cosmetic Industry Association).

[0097] The formulation of the cosmetic composition may be an aqueous cosmetic composition consisting of only an aqueous phase, an oil-in-water (O / W) type emulsion cosmetic composition, or a water-in-oil (W / O) type emulsion cosmetic composition. Of these, the cosmetic composition is preferably an aqueous or oil-in-water emulsion system. In the case of an emulsion system, it is preferable that the cosmetic additive is contained in the aqueous phase.

[0098] The method for producing the cosmetic composition is not particularly limited, and a general production method can be used. In the case of an aqueous cosmetic composition, the components are mixed uniformly simultaneously or in any order. In the case of an oil-in-water emulsion or water-in-oil emulsion cosmetic composition, the aqueous phase component and the oil phase component are mixed uniformly, independently, while heating as necessary. The heating temperature can be, for example, 60 to 90°C. When a cosmetic additive is contained in the aqueous phase, it is preferable to allow it to swell during mixing of the aqueous phase components.

[0099] The form of the cosmetic composition is not particularly limited, and may be, for example, skin care cosmetics such as gel cream, lotion, emulsion, serum, and pack; hair care cosmetics such as shampoo, conditioner, and hair styling product; body care cosmetics such as pack, face wash, body soap, and hand cream; or makeup cosmetics such as foundation, lipstick, lip balm, and lip gloss.

[0100] The viscosity of the cosmetic composition can be adjusted appropriately depending on its form. In the case of a gel cream or the like, the viscosity measured with a Brookfield viscometer is preferably 2,000 to 30,000 mPa·s. The viscosity measured with a rheometer (shear rate ω 4 rad / s) is preferably 3,000 to 200,000 mPa·s.

[0101] For lotions and the like, the viscosity measured with a B-type viscometer is preferably 10 to 2000 mPa·s, and the viscosity measured with a rheometer (shear rate ω4 rad / s) is preferably 100 to 10,000 mPa·s. [Example]

[0102] The present invention will be described below with reference to examples, but is not limited to these examples. Hereinafter, "parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

[0103] (1) Preparation of crosslinked water-soluble polymer (1-1) Partial Decomposition of Starch (Manufacturing Examples 1 and 2) Tapioca starch was suspended in city water to a concentration of 45% (w / w), and then a 1N calcium chloride solution was added. Then, a 1N sodium hydroxide solution was added to adjust the pH to 6.0 to obtain starch milk. To this starch milk, an amylomaltase enzyme solution was added at 3.0 units per gram of starch solids, and the mixture was stirred at room temperature for 30 minutes. The mixture was then allowed to react at 80°C for 6 hours with stirring to produce liquefied starch. The resulting partial starch hydrolyzate had a weight-average molecular weight of 5.48 million and a dispersity of 14.73.

[0104] (Manufacturing Examples 3, 6, and 8) Tapioca starch was suspended in city water to a concentration of 45% (w / w), and then a 1N calcium chloride solution was added. Then, a 1N sodium hydroxide solution was added to adjust the pH to 6.0, yielding starch milk. To this starch milk, an amylomaltase enzyme solution was added at 8.0 units per gram of starch solids, and the mixture was stirred at room temperature for 30 minutes. The mixture was then allowed to react at 85°C for 1 hour with stirring to produce liquefied starch. The resulting partial starch hydrolyzate had a weight-average molecular weight of 2.79 million and a dispersity of 7.84.

[0105] (Production Example 4) Tapioca starch was suspended in city water to a concentration of 45% (w / w), and then a 1N calcium chloride solution was added. Then, a 1N sodium hydroxide solution was added to adjust the pH to 6.0, yielding starch milk. To this starch milk, an amylomaltase enzyme solution was added at 6.0 units per gram of starch solids, and the mixture was stirred at room temperature for 30 minutes. The mixture was then allowed to react at 85°C for 1 hour with stirring to produce liquefied starch. The weight-average molecular weight of the resulting starch partial hydrolyzate was 3.77 million.

[0106] (Manufacturing Examples 5 and 7) Tapioca starch was suspended in city water to a concentration of 45% (w / w), and then a 1N calcium chloride solution was added. Then, a 1N sodium hydroxide solution was added to adjust the pH to 6.0, yielding starch milk. To this starch milk, an amylomaltase enzyme solution was added at 6.0 units per gram of starch solids, and the mixture was stirred at room temperature for 30 minutes. The mixture was then allowed to react at 85°C for 1 hour with stirring to produce liquefied starch. The weight-average molecular weight of the resulting starch partial hydrolyzate was 3.7 million.

[0107] (Production Example 9) Cornstarch was suspended in city water to a concentration of 30% (w / w), and then a 1N calcium chloride solution was added. Then, a 1N sodium hydroxide solution was added to adjust the pH to 6.0, yielding starch milk. To this starch milk, an amylomaltase enzyme solution was added at 6.0 units per gram of starch solids, and the mixture was stirred at room temperature for 30 minutes. The mixture was then allowed to react at 85°C for 1 hour with stirring to produce liquefied starch. The weight-average molecular weight of the resulting starch partial hydrolyzate was 3.8 million.

[0108] (1-2) Introduction of acidic groups (Manufacturing Examples 1-2) 2,160 g of a 45 wt% aqueous solution of tapioca starch-derived partial starch hydrolysate (17.6 mol of hydroxyl groups in the partial starch hydrolysate) was charged into a 3 L separable flask equipped with a stirrer, thermometer, and condenser. Next, 1,272 g of 48.8% aqueous sodium hydroxide (15.5 mol, 0.88 mol equivalents per mol of hydroxyl groups in the partial starch hydrolysate) was charged and stirred at 60°C or below until the solution became completely homogeneous. After confirming that the solution was homogeneous, an aqueous solution of 698 g of monochloroacetic acid (7.39 mol, 0.42 mol equivalents per mol of hydroxyl groups in the partial starch hydrolysate) in 175 g of ion-exchanged water was added dropwise over 30 minutes at 50-60°C. After charging the aqueous monochloroacetic acid solution, the temperature was adjusted to 45-50°C and the mixture was stirred for 3 hours. The reaction was terminated when the chloride ion content in the reaction solution was measured by potentiometric titration using a 0.01N silver nitrate solution, and reached 98% or more of the calculated chloride ion content of 6.1% when all the monochloroacetic acid had reacted. In this production example, the chloride content was 6.1%.

[0109] (Manufacturing Examples 3, 4, 6, and 8) 2160 g of a 45 wt% aqueous solution of tapioca starch-derived partial starch hydrolysate (17.6 mol of hydroxyl groups in the partial starch hydrolysate) was placed in a 3 L separable flask equipped with a stirrer, thermometer, and condenser. Next, 273 g of 48.8% aqueous sodium hydroxide (3.3 mol, 0.19 mol equivalents per mol of hydroxyl groups in the partial starch hydrolysate) was added and stirred at 60°C or below until the solution became completely homogeneous. After confirming that the solution was homogeneous, an aqueous solution of 150 g of monochloroacetic acid (1.58 mol, 0.09 mol equivalents per mol of hydroxyl groups in the partial starch hydrolysate) in 37 g of ion-exchanged water was added dropwise over 30 minutes at 50-60°C. After adding the monochloroacetic acid aqueous solution, the temperature was adjusted to 45-50°C and the mixture was stirred for 3 hours. The reaction was terminated when the chloride ion content in the reaction solution was measured by potentiometric titration using a 0.01N silver nitrate solution, and reached 98% or more of the calculated chloride ion content of 2.2% when all the monochloroacetic acid had reacted. In this production example, the chloride content was 2.2%.

[0110] (Manufacturing Examples 5 and 7) 2,160 g of a 45 wt% aqueous solution of tapioca starch-derived partial starch hydrolysate (17.6 mol of hydroxyl groups in the partial starch hydrolysate) was charged into a 3 L separable flask equipped with a stirrer, thermometer, and condenser. Next, 701 g of 48.8% aqueous sodium hydroxide solution (8.87 mol, 0.50 mol equivalents per mol of hydroxyl groups in the partial starch hydrolysate) was charged and stirred at 60°C or below until the solution became completely homogeneous. After confirming that the solution was homogeneous, an aqueous solution of 399 g of monochloroacetic acid (4.22 mol, 0.24 mol equivalents per mol of hydroxyl groups in the partial starch hydrolysate) dissolved in 100 g of ion-exchanged water was added dropwise over 30 minutes at 50-60°C. After charging the aqueous monochloroacetic acid solution, the temperature was adjusted to 45-50°C and the mixture was stirred for 3 hours. The reaction was terminated when the chloride ion content in the reaction solution was measured by potentiometric titration using a 0.01N silver nitrate solution, and reached 98% or more of the calculated chloride ion content of 4.5% when all the monochloroacetic acid had reacted. In this production example, the chloride content was 4.5%.

[0111] (Production Example 9) 3240 g of an aqueous solution of partial starch hydrolysate derived from cornstarch (17.6 mol of hydroxyl groups in the partial starch hydrolysate) was placed in a 3 L separable flask equipped with a stirrer, thermometer, and condenser. Next, 1285 g of 48.8% aqueous sodium hydroxide (15.7 mol, 0.88 mol equivalents per mol of hydroxyl groups in the partial starch hydrolysate) was added and stirred at 60°C or below until the solution became completely homogeneous. After confirming that the solution was homogeneous, an aqueous solution of 706 g of monochloroacetic acid (7.47 mol, 0.42 mol equivalents per mol of hydroxyl groups in the partial starch hydrolysate) in 176 g of ion-exchanged water was added dropwise over 30 minutes at 50-60°C. After adding the aqueous solution of monochloroacetic acid, the temperature was adjusted to 45-50°C and the mixture was stirred for 3 hours. The reaction end point was determined by sampling the reaction solution and measuring the chloride ion content in the reaction solution by potentiometric titration using a 0.01N silver nitrate aqueous solution, and the condition was that the chloride ion content reached 98% or more of the calculated value of 4.9% when all the monochloroacetic acid had reacted. In this production example, the chloride content was 4.9%.

[0112] (1-3) Reprecipitation of water-soluble polymers (Manufacturing Examples 1 to 8) After the reaction was completed, 233 g of the reaction solution was diluted with 467 g of ion-exchanged water. The diluted reaction solution was added to a mixed solvent of 2,394 mL of ethanol and 266 mL of propylene glycol over approximately 30 minutes, and the water-soluble polymer was precipitated and reprecipitated. After all the reaction solution was added, the mixture was stirred for 30 minutes, and the water-soluble polymer dispersed in the mixed solvent of ethanol and propylene glycol was subjected to solid-liquid separation by vacuum filtration.

[0113] (Production Example 9) After the reaction was completed, 233 g of the reaction solution was diluted with 467 g of ion-exchanged water. The diluted reaction solution was added to 2,660 mL of methanol solvent over approximately 30 minutes, and the water-soluble polymer was precipitated and reprecipitated. After all the reaction solution was added, the mixture was stirred for 30 minutes, and the water-soluble polymer dispersed in the methanol solvent was subjected to solid-liquid separation by vacuum filtration.

[0114] (1-4) Washing of water-soluble polymers (Manufacturing Examples 1 and 2) Next, to remove the sodium chloride contained in the water-soluble polymer, the recovered water-soluble polymer was redispersed in 887 mL of an aqueous solvent consisting of a 9:1 ethanol / propylene glycol (volume ratio) / 80:20 water mixture, stirred at room temperature for 30 minutes, washed, and then subjected to solid-liquid separation by vacuum filtration. The water-soluble polymer was then recovered again. The chlorine content of the recovered water-soluble polymer was measured by potentiometric titration using a 0.01 N silver nitrate solution. The washing process was repeated until the chlorine content was less than 1%. The total acid value of the resulting water-soluble polymer was 179 mg KOH / g, and the degree of etherification calculated from the total acid value was 0.69.

[0115] (Manufacturing Examples 3, 4, and 6) Next, to remove the sodium chloride contained in the water-soluble polymer, the recovered water-soluble polymer was redispersed in 887 ml of an aqueous solvent (ethanol / water 80 / 20 (volume ratio)), stirred at room temperature for 30 minutes, washed, and then subjected to solid-liquid separation by vacuum filtration. The water-soluble polymer was recovered again. The chlorine content of the recovered water-soluble polymer was measured by potentiometric titration using 0.01 N aqueous silver nitrate solution. The washing process was repeated until the chlorine content was less than 1%. The total acid value of the resulting water-soluble polymer was 60 mg KOH / g, and the degree of etherification calculated from the total acid value was 0.19.

[0116] (Manufacturing Examples 5 and 7) Next, to remove the sodium chloride contained in the water-soluble polymer, the recovered water-soluble polymer was redispersed in 887 ml of an aqueous solvent (ethanol / water 80 / 20 (volume ratio)), stirred at room temperature for 30 minutes, washed, and then subjected to solid-liquid separation by vacuum filtration. The water-soluble polymer was recovered again. The chlorine content of the recovered water-soluble polymer was measured by potentiometric titration using a 0.01 N silver nitrate solution. The washing process was repeated until the chlorine content was less than 1%. The total acid value of the resulting water-soluble polymer was 135 mg KOH / g, and the degree of etherification calculated from the total acid value was 0.48.

[0117] (Production Example 8) Next, to remove the sodium chloride contained in the water-soluble polymer, the recovered water-soluble polymer was redispersed in 887 mL of an aqueous solvent (ethanol / water 80 / 20 (volume ratio)), stirred at room temperature for 30 minutes, washed, and then subjected to solid-liquid separation by vacuum filtration while additional washing with 100% ethanol was performed. The water-soluble polymer was then recovered again. The additional washing was performed using 100% ethanol to remove water and facilitate the thermal crosslinking reaction. The chlorine content of the recovered water-soluble polymer was measured by potentiometric titration using 0.01 N silver nitrate aqueous solution, and the washing process was repeated until the chlorine content was less than 1%. The total acid value of the resulting water-soluble polymer was 62 mg KOH / g, and the degree of etherification calculated from the total acid value was 0.20.

[0118] (Production Example 9) Next, to remove the sodium chloride contained in the water-soluble polymer, the recovered water-soluble polymer was redispersed in 887 ml of an aqueous solvent (80 / 20 volume ratio of methanol / water), stirred at room temperature for 30 minutes, washed, and then subjected to solid-liquid separation by vacuum filtration. The water-soluble polymer was recovered again. The chlorine content of the recovered water-soluble polymer was measured by potentiometric titration using a 0.01 N silver nitrate solution. The washing process was repeated until the chlorine content was less than 1%. The total acid value of the resulting water-soluble polymer was 169 mg KOH / g, and the degree of etherification calculated from the total acid value was 0.64.

[0119] (1-5) Crosslinking of water-soluble polymers (Production Example 1) 333 g of water-soluble polymer (wet product of aqueous ethanol / propylene glycol, wet ratio 65%) was placed in a 2,000 ml beaker, and 1,643 ml of an aqueous solvent consisting of a mixed solvent of ethanol and propylene glycol (9:1) / water (volume ratio 80 / 20) was added to disperse the water-soluble polymer. While stirring with a magnetic stirrer, 22 ml of 1 N aqueous hydrochloric acid solution was measured using a measuring cylinder and gradually added. After adding the hydrochloric acid, the mixture was stirred for 5 minutes and subjected to vacuum suction filtration to recover the water-soluble polymer that had been partially neutralized to free acid. The recovered water-soluble polymer was wet crystals containing aqueous alcohol. The wet crystals were transferred to a tray, placed in a vacuum dryer set at 75°C, and dried under reduced pressure for 20 hours to perform a crosslinking treatment.

[0120] (Production Example 2) 333 g of water-soluble polymer (wet product of aqueous ethanol / propylene glycol, wet ratio 65%) was placed in a 2,000 ml beaker, and 1,598 ml of an aqueous solvent consisting of a mixed solvent of ethanol and propylene glycol (9:1) / water (volume ratio 80 / 20) was added to disperse the water-soluble polymer. While stirring with a magnetic stirrer, 67 ml of 1 N aqueous hydrochloric acid solution was measured using a measuring cylinder and gradually added. After adding the hydrochloric acid, the mixture was stirred for 5 minutes and subjected to vacuum suction filtration to recover the water-soluble polymer that had been partially neutralized to free acid. The recovered water-soluble polymer was wet crystals containing aqueous alcohol. The wet crystals were transferred to a tray, placed in a vacuum dryer set at 75°C, and dried under reduced pressure for 20 hours to perform a crosslinking treatment.

[0121] (Production Example 3) 333 g of water-soluble polymer (wet product with aqueous ethanol, wet ratio 65%) was placed in a 2,000 ml beaker, and 1,643 ml of an aqueous solvent of 80 / 20 ethanol / water (volume ratio) was added to disperse the water-soluble polymer. While stirring with a magnetic stirrer, 23 ml of 20% aqueous phosphoric acid solution was measured using a measuring cylinder and gradually added. After adding the phosphoric acid, the mixture was stirred for 1 hour and subjected to vacuum suction filtration to recover the water-soluble polymer that had been partially neutralized to free acid. The recovered water-soluble polymer was wet crystals containing aqueous alcohol. The wet crystals were transferred to a tray, placed in a vacuum dryer set at 75°C, and dried under reduced pressure for 20 hours to perform a crosslinking treatment.

[0122] (Production Example 4) 333 g of water-soluble polymer (wet product with aqueous ethanol, wet ratio 65%) was placed in a 2,000 ml beaker, and 1,643 ml of an aqueous solvent of 80 / 20 ethanol / water (volume ratio) was added to disperse the water-soluble polymer. While stirring with a magnetic stirrer, 25 ml of 20% aqueous phosphoric acid solution was measured using a measuring cylinder and gradually added. After adding the phosphoric acid, the mixture was stirred for 1 hour and subjected to vacuum suction filtration to recover the water-soluble polymer that had been partially neutralized to free acid. The recovered water-soluble polymer was wet crystals containing aqueous alcohol. The wet crystals were transferred to a tray, placed in a vacuum dryer set at 75°C, and dried under reduced pressure for 20 hours to perform a crosslinking treatment.

[0123] (Manufacturing Examples 5 and 7) 333 g of water-soluble polymer (wet product with aqueous ethanol, wet ratio 65%) was placed in a 2,000 ml beaker, and 1,643 ml of an aqueous solvent of 80 / 20 ethanol / water (volume ratio) was added to disperse the water-soluble polymer. While stirring with a magnetic stirrer, 19 ml of 20% aqueous phosphoric acid solution was measured using a measuring cylinder and gradually added. After adding the phosphoric acid, the mixture was stirred for 1 hour and subjected to vacuum suction filtration to recover the water-soluble polymer that had been partially neutralized to free acid. The recovered water-soluble polymer was wet crystals containing aqueous alcohol. The wet crystals were transferred to a tray, placed in a vacuum dryer set at 75°C, and dried under reduced pressure for 20 hours to perform a crosslinking treatment.

[0124] (Production Example 6) 333 g of water-soluble polymer (wet product with aqueous ethanol, wet ratio 65%) was placed in a 2,000 ml beaker, and 1,643 ml of an aqueous solvent of 80 / 20 ethanol / water (volume ratio) was added to disperse the water-soluble polymer. While stirring with a magnetic stirrer, 20 ml of 20% aqueous phosphoric acid solution was measured using a measuring cylinder and gradually added. After adding the phosphoric acid, the mixture was stirred for 1 hour and subjected to vacuum suction filtration to recover the water-soluble polymer that had been partially neutralized to free acid. The recovered water-soluble polymer was wet crystals containing aqueous alcohol. The wet crystals were transferred to a tray, placed in a vacuum dryer set at 75°C, and dried under reduced pressure for 20 hours to perform a crosslinking treatment.

[0125] (Production Example 8) 333 g of water-soluble polymer (ethanol wet product, wet ratio 65%) was placed in a 2,000 ml beaker, and 1,643 ml of 100% ethanol solvent was added to disperse the water-soluble polymer. While stirring with a magnetic stirrer, 10 ml of 20% aqueous phosphoric acid solution was measured using a measuring cylinder and gradually added. After adding the phosphoric acid, the mixture was stirred for 1 hour and subjected to vacuum suction filtration to recover the water-soluble polymer that had been partially neutralized to free acid. The recovered water-soluble polymer was wet crystals containing alcohol. The wet crystals were transferred to a tray, placed in a vacuum dryer set at 150°C, and dried under reduced pressure for 1 hour to undergo a crosslinking treatment.

[0126] (Production Example 9) 333 g of water-soluble polymer (wet product containing hydrous methanol, wet ratio 65%) was placed in a 2,000 ml beaker, and 1,643 ml of a hydrous solvent of 80 / 20 (volume ratio) methanol / water was added to disperse the water-soluble polymer. 38 ml of 1 N hydrochloric acid solution was measured using a measuring cylinder and gradually added while stirring with a magnetic stirrer. After adding the hydrochloric acid, the mixture was stirred for 1 hour and then subjected to vacuum suction filtration to recover the water-soluble polymer that had been partially neutralized to free acid. The recovered water-soluble polymer was wet crystals containing hydrous alcohol. The wet crystals were transferred to a tray, placed in a vacuum dryer set at 75°C, and dried under reduced pressure for 20 hours to perform a crosslinking treatment.

[0127] (1-6) Grinding of cross-linked water-soluble polymer The crosslinked water-soluble polymers obtained in Production Examples 1 to 6 and 8 to 9 were pulverized in a mortar and sieved using a sieve with 40 μm openings to recover crosslinked water-soluble polymer particles with a particle size of less than 40 μm. The crosslinked water-soluble polymer obtained in Production Example 7 was sieved using sieves with 500 μm and 850 μm openings to recover crosslinked water-soluble polymer particles with an average particle size (D50) of approximately 600 μm.

[0128] The properties of the crosslinked water-soluble polymers obtained in Production Examples 1 to 9 are shown in Table 1. [Table 1]

[0129] (2) Gel (Examples 1 to 9, Comparative Examples 1 to 4) (2-1) Gel production While stirring the water with a disper, the components of Production Examples 1 to 9 and Thickeners 1 to 3 shown in Table 2 were added. Stirring was continued for 30 minutes to obtain gels of Examples 1 to 6, 8 to 9, and Comparative Examples 1 to 3. Furthermore, while stirring the water by hand with a spatula, the components of Production Example 7 and Thickener 4 shown in Table 2 were added, and the mixture was stirred for 30 minutes to obtain gels of Example 7 and Comparative Example 4. The contents in Table 2 are shown in % by weight.

[0130] [Table 2]

[0131] (2-2) Details of ingredients (Thickener 1) Roquette ST 118: Carboxymethylated starch sodium, manufactured by Roquette Japan Co., Ltd. (Thickener 2) Saranjur 300: sodium acrylate grafted starch (average particle size 300 μm), manufactured by Sanyo Chemical Industries, Ltd. (Thickener 3) Xanthan gum: manufactured by Tokyo Chemical Industry Co., Ltd. (Thickener 4) Sodium polyacrylate: Sigma-Aldrich

[0132] (2-3) Sensory evaluation of gel 1 The feel of the gels of Examples 1 to 6, 8, and 9 and Comparative Examples 1 to 3 was evaluated sensorily according to the following criteria. Seven evaluation panelists applied the gel to their skin and rated the feel (smoothness, moisturizing feeling, ease of spreadability) on a three-point scale: "good," "slightly bad," and "bad." The number of panelists who felt "good" in two or more categories was tallied and rated according to the following criteria. 〇: 6-7 people felt it was good △: 4-5 people felt it was good ×: 3 or fewer people felt it was good

[0133] (2-4) Sensory evaluation of gel 2 The feel of the gels of Example 7 and Comparative Example 4 was evaluated sensorily according to the following criteria. Seven evaluation panelists applied the gel to the skin and then pressed it with their fingers to evaluate the feel (smoothness, moisturizing feeling, ease of spreading) on ​​a three-point scale: "good," "slightly bad," and "bad." The number of panelists who felt "good" in two or more categories was tallied and rated according to the following criteria. 〇: 6-7 people felt it was good △: 4-5 people felt it was good ×: 3 or fewer people felt it was good

[0134] (2-5) Discussion The viscosity of the gel is shown in Table 2, and a photograph of the appearance is shown in Figure 1. Comparative Example 1 had low viscosity and was insufficiently gelled. Comparative Example 2 gelled but felt rough to the touch. Comparative Example 3 had low viscosity and felt sticky to the touch. Examples 1 to 9 gelled, felt smooth to the touch, were easy to spread, and had a moisturizing feel.

[0135] Furthermore, comparing Example 7, which used a crosslinked product with a large particle size (approximately 600 μm), with Comparative Example 4, the crushed particulate gel product of Example 7 yielded a viscous liquid sol when lightly pressed with a finger, and had a smooth feel, was easy to spread, and had a moisturizing feel. On the other hand, the crushed particulate gel product of Comparative Example 4 maintained its crushed particulate shape even when pressed with a finger, and had a rough feel.

[0136] (3) Gel Cream (Example 10, Comparative Examples 5 to 7) (3-1) Manufacturing of gel cream The oil phase components shown in Table 3 were mixed uniformly at 75°C. Similarly, the water phase components were mixed uniformly at 75°C. The contents in Table 3 are shown in weight percent. The water phase was added to the oil phase while stirring with a disper. After emulsification, the mixture was cooled to room temperature while stirring to obtain a gel cream.

[0137] [Table 3]

[0138] (3-2) The feel of the gel cream was evaluated sensorily according to the following criteria. Seven evaluation panelists applied the gel cream to their skin and rated the texture (smoothness, moisturizing feeling, ease of spreadability) on a three-point scale: "good," "slightly bad," and "bad." The number of panelists who felt "good" in two or more categories was tallied and rated according to the following criteria. 〇: 6-7 people felt it was good △: 4-5 people felt it was good ×: 3 or fewer people felt it was good

[0139] (3-3) Discussion The viscosity of the gel cream is shown in Table 3, and a photograph of its appearance is shown in Figure 2. Comparative Example 5 had low viscosity, and emulsification and gelation were insufficient. Comparative Example 6 gelled and maintained an emulsified state, but felt rough to the touch. Comparative Example 7 maintained an emulsified state, but had low viscosity and felt sticky to the touch. Example 10 gelled and maintained an emulsified state, felt smooth to the touch, was easy to spread, and had a moisturizing feel.

[0140] When the crosslinked water-soluble polymer of Production Example 7 was used instead of the crosslinked water-soluble polymer of Production Example 2, the gelation and emulsification state were maintained, and the product had a smooth feel, was easy to spread, and had a moisturizing feel, just like in Example 10.

[0141] (4) Lotion (Example 11, Comparative Examples 8 to 10) (4-1) Manufacturing of lotion The oil phase components shown in Table 4 were mixed uniformly at room temperature. Similarly, the water phase components were mixed uniformly at room temperature. The contents in Table 4 are shown in weight percent. While stirring the oil phase with a disper, the water phase was added and emulsified to obtain a lotion.

[0142] [Table 4]

[0143] (4-2) The feel of the lotion was evaluated sensorily according to the following criteria. Seven evaluation panelists applied the lotion to their skin and rated the feel (smoothness, moisturizing feeling, ease of spreadability) on a three-point scale: "good," "slightly bad," and "bad." The number of panelists who felt "good" in two or more categories was tallied and rated according to the following criteria. 〇: 6-7 people felt it was good △: 4-5 people felt it was good ×: 3 or fewer people felt it was good

[0144] (4-3) Consideration The viscosity of the lotion is shown in Table 4, and a photograph of the appearance is shown in Figure 3. Comparative Example 8 was insufficiently dispersed and separated. Comparative Example 9 had high viscosity, gelled, and felt rough to the touch. Comparative Example 10 felt sticky to the touch. Example 11 felt smooth, was easy to spread, and had a moisturizing feel.

[0145] When the crosslinked water-soluble polymer of Production Example 7 was used instead of the crosslinked water-soluble polymer of Production Example 1, the product had a smooth feel, was easy to spread, and had a moisturizing feel, similar to Example 11.

[0146] The present invention may include, for example, the following aspects. <1> A cosmetic additive comprising a crosslinked product of a water-soluble polymer in which an acidic group has been introduced into a partially hydrolyzed product of starch. <2> Item 2. The cosmetic additive according to Item 1, wherein the crosslinked water-soluble polymer has an average particle size of 5 to 850 μm. <3> Item 3. The cosmetic additive according to Item 1 or 2, wherein the weight-average molecular weight of the partially hydrolyzed starch is 50,000 to 7,500,000. <4> Item 4. The cosmetic additive according to any one of Items 1 to 3, wherein the water-soluble polymer has a total acid value of 50 to 350 mgKOH / g. <5> Item 5. The cosmetic additive according to any one of Items 1 to 4, wherein the water-soluble polymer has a free acid value of 0 to 100 mgKOH / g. <6> Item 6. The cosmetic additive according to any one of Items 1 to 5, which is a thickener, a texture improver, a dispersant, an emulsifier, an emulsion stabilizer, a water retention agent, or a stabilizer. <7> Item 7. A cosmetic composition comprising the cosmetic additive according to any one of items 1 to 6. <8> Item 8. The cosmetic composition according to item 7, which is a water-based or oil-in-water emulsion system. <9> Item 9. The cosmetic composition according to item 7 or 8, which is a skin care cosmetic, a hair care cosmetic, a body care cosmetic, or a makeup cosmetic. <10> a step of introducing an acidic group into a partially hydrolyzed product of starch to obtain a water-soluble polymer; cross-linking the water-soluble polymer; and The crosslinked water-soluble polymer is pulverized to have an average particle size of 5 to 850 μm. A method for producing cosmetic additives.

Claims

1. A cosmetic additive comprising a crosslinked product of a water-soluble polymer in which an acidic group has been introduced into a partially hydrolyzed product of starch.

2. 2. The cosmetic additive according to claim 1, wherein the crosslinked water-soluble polymer has an average particle size of 5 to 850 μm.

3. 3. The cosmetic additive according to claim 1, wherein the weight-average molecular weight of the partially hydrolyzed starch is 50,000 to 7,500,000.

4. 3. The cosmetic additive according to claim 1, wherein the water-soluble polymer has a total acid value of 50 to 350 mgKOH / g.

5. 3. The cosmetic additive according to claim 1, wherein the water-soluble polymer has a free acid value of 0 to 100 mgKOH / g.

6. The cosmetic additive according to claim 1 or 2, which is a thickener, a texture improver, a dispersant, an emulsifier, an emulsion stabilizer, a water-retaining agent, or a stabilizer.

7. A cosmetic composition comprising the cosmetic additive according to claim 1 or 2.

8. The cosmetic composition according to claim 7, which is a water-based or oil-in-water emulsion system.

9. The cosmetic composition according to claim 7, which is a skin care cosmetic, a hair care cosmetic, a body care cosmetic, or a makeup cosmetic.

10. a step of introducing an acidic group into a partially hydrolyzed product of starch to obtain a water-soluble polymer; cross-linking the water-soluble polymer; and a step of pulverizing the crosslinked water-soluble polymer to have an average particle size of 5 to 850 μm; A method for producing cosmetic additives.

Images