JP2015218115A - Cosmetic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cosmetic composition which has no stickiness when using while being thickened, has an excellent moist and smooth feeling, and has a long-lasting effect thereof without being removed by washing or sweating.SOLUTION: A cosmetic composition contains (i) polyalkylene oxide degenerative material obtained by reacting a polyalkylene oxide compound, diol compound, and diisocyanate compound, and (ii) polyhydric alcohol, wherein 0.5-20 mass% of the polyalkylene oxide degenerative material is contained.

Description

  The present invention relates to a cosmetic composition. More specifically, a cosmetic composition containing a modified polyalkylene oxide, having an excellent moisturizing effect and gloss, imparting high smoothness to the skin and hair after drying, and maintaining a moist but smooth feel. About.

Conventionally, cosmetics using a carboxyl vinyl polymer and a polyhydric alcohol have been widely used as transparent cosmetics with excellent moisture retention (Patent Document 1).
However, when a large amount of polyhydric alcohol is added to impart moisture retention, there is a problem that stickiness increases.

  In order to reduce stickiness, the addition of silicone has also been studied, but there are problems such as insufficient moisturizing properties and increased spread during application (Patent Document 2).

  In order to solve these problems, an example of adding an acidic heteropolysaccharide derived from a callus of a plant belonging to the polyantes group (Patent Document 3), a specific saccharide, dimethylpolysiloxane, water-soluble structure for imparting a gloss A cosmetic containing a film polymer and an oil is also proposed (Patent Document 4). A cosmetic containing an alkylene oxide derivative and a surfactant is proposed as a cosmetic having an emollient effect in addition to a moisturizing effect. (Patent Document 5).

  However, in these cosmetics, the main component is water-soluble, so even when applied to the skin, the active ingredients will flow out when dissolved by moisture in the air or washed with running water, and the effect will not last long was there.

  In order to solve these problems, a cosmetic composition has also been proposed in which a water-absorbing polyalkyleneoxide modified product is dissolved in a lower alcohol to form a film on the skin (Patent Document 6). However, since the composition obtained by this method has a low viscosity, it falls off when applied to the skin and the feeling of adhesion decreases.

  Moreover, although it may use together with a carboxyl vinyl polymer etc. in order to raise a viscosity, the sustainability of the film | membrane formed may worsen. Further, the lower alcohol has a problem that the moisturizing effect is lowered because sebum is also dissolved.

Japanese Unexamined Patent Publication No. 63-270614 Japanese Patent Laid-Open No. 1-132680 Japanese Patent Laid-Open No. 5-331038 JP 2009-2335026 JP 2013-100214 A WO2013 / 137290 Publication

  An object of the present invention is to provide a cosmetic composition which has no stickiness during use while being thickened, is excellent in moist feeling and smooth feeling, and the effect continues for a long time even by washing and sweating.

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition comprising a specific polyalkylene oxide-modified product and an aqueous polyhydric alcohol solution has an appropriate viscosity and is applied to skin and hair and dried. In this case, it was found that there was no stickiness, excellent moisture retention, and a smooth feeling continued, and the present invention was completed through further research.

That is, the present invention includes, for example, the subject matters described in the following sections.
Item 1.
(I) a polyalkylene oxide compound, a diol compound, and a polyalkylene oxide modified product obtained by reacting a diisocyanate compound, and (ii) a polyhydric alcohol,
The polyalkylene oxide modified product is contained in an amount of 0.5 to 20% by mass,
Cosmetic composition.
Item 2.
Item 2. The cosmetic composition according to Item 1, wherein the polyhydric alcohol is a divalent to tetravalent alcohol.
Item 3.
Item 3. The cosmetic composition according to Item 1 or 2, wherein the polyhydric alcohol is an alkyl polyhydric alcohol having 2 to 6 carbon atoms.
Item 4.
Polyalkylene oxide compounds are polyethylene oxide, polypropylene oxide, polybutylene oxide, ethylene oxide / propylene oxide copolymer, ethylene oxide / butylene oxide copolymer, propylene oxide / butylene oxide copolymer, and ethylene oxide / propylene oxide / butylene oxide copolymer. Item 4. The cosmetic composition according to any one of Items 1 to 3, which is at least one selected from the group consisting of polymers.
Item 5.
The diol compound is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, Item 5. The cosmetic composition according to any one of Items 1 to 4, which is at least one selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol.
Item 6.
The diisocyanate compound is 4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4′-diisocyanate (HMDI), 3-isocyanatomethyl-3,5 , 5-trimethylcyclohexyl isocyanate (IPDI), 1,8-dimethylbenzole-2,4-diisocyanate, and 2,4-tolylene diisocyanate (TDI). Item 6. A cosmetic composition according to any one of Items 1 to 5.
Item 7.
Cosmetics obtained using the cosmetic composition according to any one of Items 1 to 6.

  The cosmetic composition of the present invention has an appropriate viscosity, an excellent moisturizing effect and gloss, imparts high smoothness to the skin and hair after application and drying, and continues to feel smooth and smooth. Taking advantage of this feature, it can be preferably used for cosmetics used for the purpose of washing, activating, skin conditioning, hair conditioning or protection of the face, hands, neck, hair or other whole body.

The surface of the artificial leather used for the slip evaluation of the present invention is shown (surface photograph of artificial leather (× 100)). The white bar represents 1000 μm. The surface of the artificial leather which apply | coated and dried the cosmetic composition of this invention is shown (surface photograph (* 100) of artificial leather which applied the cosmetic composition of Example 1). The white bar represents 1000 μm. The schematic which calculates | requires an average friction coefficient (MIU) from the monitoring result of a friction coefficient is shown. The schematic which calculates | requires the fluctuation | variation (MMD) of an average friction coefficient from the monitoring result of a friction coefficient is shown.

  The cosmetic composition of the present invention contains a modified polyalkylene oxide and an aqueous polyhydric alcohol solution. The modified polyalkylene oxide is a compound obtained by reacting a polyalkylene oxide compound, a diol compound, and a diisocyanate compound. The cosmetic composition of the present invention includes a cosmetic composition in which the polyalkylene oxide-modified product is contained in a polyhydric alcohol aqueous solution. The cosmetic composition of the present invention can be, for example, liquid, gel, cream, etc., but is preferably a liquid cosmetic composition.

  The cosmetic composition of the present invention contains 0.5 to 20% by mass of the modified polyalkylene oxide. As a minimum, Preferably it is 1 mass% or more, More preferably, 1.5 mass% or more is contained. Moreover, as an upper limit, Preferably it is 17 mass% or less, More preferably, it is contained 15 mass% or less. In particular, the content is preferably 1 to 17% by mass, more preferably 1.5 to 15% by mass. When the content of the polyalkylene oxide-modified product is less than 0.5% by mass, the resulting cosmetic composition has a low viscosity. This is not preferable because the moisture retention effect and the emollient effect are reduced. When the content of the polyalkylene oxide-modified product exceeds 20% by mass, the resistance at the time of application to the skin / hair increases, and at the same time, the stickiness after drying of the obtained cosmetic increases, which is not preferable. In the present specification, “mass%” indicates “mass / mass%” unless otherwise specified.

The modified polyalkylene oxide is preferably water-absorbing (that is, having a water-absorbing ability). When the polyalkylene oxide-modified product is a water-absorbing polyalkylene oxide-modified product, the water absorption capacity is preferably 10 to 40 g / g, more preferably 15 to 35 g / g. When the water-absorbing ability of the water-absorbing polyalkylene oxide-modified product is 10 g / g or more, a smooth feeling after coating and drying can be preferably obtained. Moreover, durability after application | coating of the cosmetics obtained by the water absorption ability of a water absorbing polyalkylene oxide modified material being 40 g / g or less improves more. In the present invention, the water absorption ability refers to gelation by weighing 1 g of a polyalkylene oxide modified product (A [g]) and then immersing it in 100 mL of ion-exchanged water at room temperature (22 ° C.) for 24 hours. The mass (B [g]) of the gel as a residue (residue) after the gel is filtered through a wire mesh of 200 mesh (pore size: 75 μm), and a value (A is calculated by the following equation) Since it is 1, it is the same as B).
Water absorption capacity (g / g) = B / A = B / 1 = B

The water elution content of the modified polyalkylene oxide is preferably 10 to 40% by mass, more preferably 15 to 35% by mass. When the water elution content of the polyalkylene oxide-modified product is 10% by mass or more, the smooth feeling after coating and drying of the obtained cosmetic can be improved. The water elution content of the polyalkylene oxide-modified product is 40% by mass or less, whereby the durability during water washing can be further improved. In the present invention, the amount of water elution is determined by weighing the weight of the gel after measuring the water absorption capacity after drying for 8 hours in a hot air dryer at 50 ° C. (C [g]). Value.
Water elution (%) = {(AC) / A} × 100 = 100 (1-C)

  Examples of the polyalkylene oxide compound include polyethylene oxide, polypropylene oxide, polybutylene oxide, ethylene oxide / propylene oxide copolymer, ethylene oxide / butylene oxide copolymer, propylene oxide / butylene oxide copolymer, and ethylene oxide / propylene oxide / butylene. An oxide copolymer etc. can be illustrated. A polyalkylene oxide compound can be used individually by 1 type or in combination of 2 or more types. Here, “/” is a symbol used to indicate a copolymer of each oxide. For example, an ethylene oxide / propylene oxide copolymer represents a copolymer of ethylene oxide and propylene oxide.

  As said polyalkylene oxide compound, the polyalkylene oxide compound which has 90 mass% or more of ethylene oxide groups is preferable, and the polyalkylene oxide compound which has 95 mass% or more of ethylene oxide groups is more preferable. When the ethylene oxide group is 90% by mass or more, the sticky feeling after coating and drying of the resulting cosmetic composition can be preferably suppressed.

  Although not particularly limited, a polyalkylene oxide compound having a number average molecular weight of 5,000 to 50,000 is preferable, and a polyalkylene oxide compound having a number average molecular weight of 10,000 to 30,000 is more preferable. When the number average molecular weight is 5000 or more, the smooth feeling after coating and drying the obtained cosmetic composition can be further improved. Moreover, the durability of the cosmetic composition obtained as the number average molecular weight is 50000 or less can be further improved.

  In addition, the value of a number average molecular weight here is a value calculated | required by the measuring method described next. Number average molecular weight measurement method: A dimethylformamide solution having a polyalkylene oxide modified product concentration of 1% by mass is prepared and measured using a high performance liquid chromatograph. Then, a molecular weight marker (polyethylene oxide) having a known molecular weight is measured under the same conditions, a calibration curve is created, and a number average molecular weight (Mn) is calculated. Measurement conditions are as follows.

Measuring instrument: HLC-8220 (manufactured by Tosoh Corporation)
Column: Tosoh Corporation TSK GEL Multipore HXL-M
Column temperature: 40 ° C
Eluent: Dimethylformamide Flow rate: 0.6 ml / min

  Examples of the diol compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, and 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and the like. Among these diol compounds, ethylene glycol and / or 1,4-butanediol is preferably used from the viewpoint that the cosmetic composition using the resulting polyalkylene oxide-modified product improves the familiarity with skin and hair. It is done. A diol compound can be used individually by 1 type or in combination of 2 or more types.

  The use ratio of the diol compound is preferably 0.8 to 2.5 mol, more preferably 1.0 to 2.0 mol, with respect to 1 mol of the polyalkylene oxide compound. The number of moles of the polyalkylene oxide compound can be determined by dividing its mass by the number average molecular weight.

  The diisocyanate compound is not particularly limited as long as it is a compound having two isocyanate groups (—NCO) in the same molecule. For example, 4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate ( HDI), dicyclohexylmethane-4,4′-diisocyanate (HMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI), 1,8-dimethylbenzool-2,4 -Diisocyanate, 2,4-tolylene diisocyanate (TDI), etc. are mentioned. Among these diisocyanate compounds, dicyclohexylmethane-4,4'-diisocyanate (HMDI) and 1,6-hexamethylene diisocyanate (HDI) are preferably used. These diisocyanate compounds may be used alone or in combination of two or more.

  The ratio of each of the polyalkylene oxide compound, diol compound, and diisocyanate compound used is the ratio of the number of moles of isocyanate groups of the diisocyanate compound to the total number of moles of terminal hydroxyl groups of the polyalkylene oxide compound and hydroxyl groups of the diol compound [R value. = (-NCO group / -OH group)] is preferably 0.7 to 1.2, more preferably 0.8 to 1.05. When the R value is 0.7 or more, the durability of the cosmetic composition containing the resulting polyalkylene oxide-modified product can be further improved. Further, when the R value is 1.2 or less, the water-absorbing ability of the resulting polyalkylene oxide modified product is increased, and the smoothness of the cosmetic composition containing the polyalkylene oxide modified product can be further improved.

  As a method of reacting the polyalkylene oxide compound, the diol compound, and the diisocyanate compound, a known method can be used. For example, a method of reacting these by dissolving or dispersing them in a reaction solvent such as toluene, xylene, or dimethylformamide; a method of uniformly mixing these in powder or solid form and then reacting them by heating to a predetermined temperature; Etc. From the viewpoint of industrial implementation, a method in which each raw material is continuously supplied in a molten state and mixed and reacted in a multi-screw extruder is preferable. In this case, the reaction temperature is preferably 70 to 210 ° C.

  Moreover, when producing a modified polyalkylene oxide, a catalyst may be added to the reaction system from the viewpoint of promoting the reaction. For example, an appropriate amount of triethylamine, triethanolamine, dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate, triethylenediamine, or the like can be added as a catalyst.

  By such a method, a modified polyalkylene oxide can be obtained. According to such a method, the polyalkylene oxide-modified product is usually obtained in the form of, for example, a pellet, a sheet, or a film. In the present invention, the dissolution time can be shortened by pulverizing them into a range of 30 to 150 μm using a pulverizer or the like. The pulverization method is not particularly limited, but it is preferable to freeze and pulverize with liquid nitrogen in order to prevent fusion due to shearing heat generation during pulverization.

  When the polyalkylene oxide modified product is used after being pulverized, the median diameter (also referred to as median diameter or 50% particle size) of the pulverized polyalkylene oxide modified product is preferably 30 to 150 μm, more preferably 50 to 50 μm. 100 μm. That is, the polyalkylene oxide-modified product is preferably used in the cosmetic composition of the present invention, preferably as a powder having a median diameter in this range. When the median diameter is 30 μm or more, the durability can be further improved. Further, when the median diameter is 150 μm or less, the resistance at the time of application is hardly increased, and a smooth feeling can be achieved more preferably. In the present invention, the median diameter refers to a median diameter determined by a dry sieving method (JIS Z8815). Specifically, it refers to a median diameter obtained by weighing 50 g of a polyalkylene oxide-modified product, sieving it using a JIS standard sieve (JISZ8801), and weighing each sieve.

  As the polyhydric alcohol, a 2, 3 or tetravalent alcohol is preferable. Moreover, a C2-C6 alkyl polyhydric alcohol is preferable, and a C2, C3 or C4 alkyl polyhydric alcohol is more preferable. Particularly, a 2, 3 or 4 valent alkyl alcohol having 2 to 6 carbon atoms is preferable, and a 2, 3 or 4 valent alkyl alcohol having 2 to 3 or 4 carbon atoms is more preferable. Specific examples include propylene glycol, glycerin, polyethylene glycol, 1,3 butylene glycol, diethylene glycol, ethylene glycol, triethylene glycol, polypropylene glycol, polyglycerin, dipropylene glycol, tripropylene glycol, hexylene glycol and the like. . A polyhydric alcohol can be used individually by 1 type or in combination of 2 or more types. In particular, 1,3-butylene glycol, propylene glycol, and dipropylene glycol are preferably used from the viewpoints of drying speed and stickiness. By using these polyhydric alcohols, it is possible to obtain a cosmetic material that does not contain a highly irritating alcohol (for example, ethanol) and has a light tactile sensation.

  In addition, 40-90 mass% is preferable, for example, content of the polyhydric alcohol in the cosmetic composition of this invention has more preferable 45-85 mass%, and 50-80 mass% is further more preferable.

  When the polyhydric alcohol is 40% by mass or more, the moisture retention performance is further enhanced and the continuity of the smooth feeling can be further enhanced. When the content ratio of the polyhydric alcohol is 90% by mass or less, the stability of the aqueous solution is further improved, and the stickiness after coating and drying of the cosmetic composition can be reduced.

  In the cosmetic composition of the present invention, when the polyalkylene oxide-modified product content is 1 part by mass, the polyhydric alcohol content is preferably about 2 to 50 parts by mass, and 3 to 40 parts by mass. More preferably, it is about.

  The polyhydric alcohol can be prepared and used in an aqueous solution. Examples of the polyhydric alcohol aqueous solution include a mixed solution of polyhydric alcohol and water. Although the content rate in particular of the polyhydric alcohol in the said aqueous solution is not restrict | limited, For example, it is preferable to contain 60-90 mass%, and 60-80 mass% is more preferable.

  Examples of the method for producing the cosmetic composition of the present invention include a method of mixing the polyalkylene oxide-modified product, the polyhydric alcohol, and, if necessary, water and other components. Specifically, after the polyalkylene oxide modified product (preferably powder) is dispersed in a predetermined amount of polyhydric alcohol (which may be used after being prepared in a polyhydric alcohol aqueous solution) at room temperature, 70 to The method of heating and mixing at 80 ° C. is exemplified. The mixing method is not particularly limited as long as a known method is adopted. For example, a propeller mixer, a high speed mixer, a homogenizer and the like are optimally used.

  It is preferable that water is contained in the cosmetic composition of the present invention. The amount of water contained is preferably, for example, 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 40% by mass.

  In the cosmetic composition of the present invention, when the polyalkylene oxide modified product content is 1 part by mass, the water content is preferably about 1 to 15 parts by mass, and 1.5 to 10 parts by mass. More preferably, it is about.

  As long as the effects of the present invention are not impaired, the cosmetic composition of the present invention may contain other components. Other ingredients include aluminum hydroxychloride, tannic acid, zinc sulfate, zinc oxide, etc. as antiperspirants, coloring agents, surfactants (anionic, nonionic, amphoteric or cationic), other perfumes, antioxidants, An ultraviolet absorber, a plant extract, an ascorbic acid derivative and the like can be appropriately blended.

  Moreover, it is also possible to use together a carboxyl vinyl polymer, hydroxyethyl cellulose, etc. as a conventional thickener.

The cosmetic composition of the present invention preferably has a viscosity of 300 to 30000 mPa · s, more preferably 400 to 20000 mPa · s, and still more preferably 500 to 16000 mPa · s. The viscosity is a value measured under the following conditions.
Viscometer: B-type viscometer Temperature: 20 ° C
Rotor: No.6
Rotation speed: 20rpm

In addition, the cosmetic composition of the present invention is excellent in moisture retention, and therefore has a small mass loss after storage for a certain period of time. More specifically, 10 g of the cosmetic composition was stored for 24 hours under conditions of 25 ° C. and 35% RH (relative humidity), and the amount of decrease when the mass was Bg:
Reduction amount [%] = (1−B / 10) × 100
Is preferably less than 5%, more preferably 4.5% or less, and even more preferably 4% or less.

  The cosmetic composition of the present invention may be used as it is as a cosmetic or as a raw material for cosmetics. The dosage form as a cosmetic is arbitrary, and can be applied by a preparation impregnated or applied to a sheet such as a nonwoven fabric, or by spraying. Product forms include facial cosmetics such as lotions, emulsions, creams, packs, makeup cosmetics such as foundations, lipsticks and eye shadows, body cosmetics, aromatic cosmetics, makeup removers, body shampoos, shaving gels, etc. Examples thereof include skin cleansing agents, hair setting agents, and hair cosmetics such as shampoos.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[Evaluation method]
With respect to the polyalkylene oxide-modified products produced in the following production examples, (1) water absorption capacity, (2) water elution, and (3) median particle diameter were measured according to the following methods. Further, (4) viscosity (5) moisturizing property, (6) slipperiness (7) gloss (film-forming effect) of the cosmetic composition prepared in the following examples was measured according to the following method.

(1) Water absorption capacity 1 g of polyalkylene oxide-modified product was weighed (A [g]), and then immersed in 100 mL of ion-exchanged water measured in a 200 mL beaker at room temperature (22 ° C.) for 24 hours. And gelled. Thereafter, the gel was filtered with a wire mesh of 200 mesh (pore diameter: 75 μm), the mass (B [g]) was measured, and the water absorption capacity was calculated according to the following formula.
Water absorption capacity (g / g) = B / A

(2) Water elution content The gel after measuring the water absorption capacity was weighed (C [g]) after drying for 8 hours with a hot air dryer at 50 ° C., and the water elution content was determined by the following equation. .
Water elution (mass%) = (AC) / A × 100

(3) Median particle diameter 50 g of resin was weighed and sieved using a JIS standard sieve, and then weighed for each sieve. Based on the result, the median particle diameter at which the cumulative mass was 50% was Calculated by the formula.
Median particle size = {(50−W) / (Z−W)} × (Y−X) + X

  In the formula, W is the integrated value (g) when the integrated mass is sequentially calculated from the coarser particle size distribution, and the integrated mass is less than 50% and the integrated value at the point closest to 50% is obtained, X is the mesh opening (μm) when the integrated value is obtained. Z is the integrated value (g) when the integrated mass is calculated in order from the coarser particle size distribution and the integrated mass is 50% or more and the integrated value at the point closest to 50% is obtained. , Y is the sieve opening (μm) when the integrated value is obtained.

(4) Viscosity The viscosity of the cosmetic compositions obtained in Examples and Comparative Examples was measured under the following conditions.
Viscosity measurement condition B type viscometer: Bismetron VS-1H manufactured by Shibaura System Co., Ltd.
Temperature: 20 ° C
Rotor: No.6
Rotation speed: 20rpm

  If it has a viscosity of 300 [mPa · s] or more, it is considered that it does not sag.

  When the viscosity is higher than 30000 [mPa · s], the coating becomes difficult.

(5) Moisturizing property About 10 g of the cosmetic composition obtained in Examples and Comparative Examples was collected in an aluminum cup (upper diameter 60 mm, lower diameter 54 mm, depth 16 mm, capacity 54 ml) (A [g]). The mass (B [g]) after storing this for 24 hours in a thermo-hygrostat set to 25 ° C. × 35% RH was measured, and the reduction amount was determined.
Reduction amount [%] = (1−B / A) × 100

  If the amount of decrease is less than 5%, it can be determined that it has moisture retention.

(6) Sliding property 0.1 mL of the cosmetic composition obtained by Examples and Comparative Examples was dropped on artificial leather (suprale made by Idemitsu Technofine) cut into 2 cm (W) × 5 cm (L), It was smeared on the belly of the finger and dried. Thereafter, the friction coefficient μ was monitored using a friction tester (Kato Tech Co., Ltd., model: KES-SE) under the following test conditions. And the average friction coefficient (MIU) and the fluctuation | variation (MMD) of the average friction coefficient were calculated | required.

<Friction tester conditions>
Sensor: 10 mm square piano wire Load: 50 [g]
Speed: 10 [mm / sec]

(I) Average friction coefficient (MIU)
The average coefficient of friction correlates with the ease of slipping and the difficulty of sliding when rubbing the surface. The larger the value, the less slippery.

  FIG. 3 shows a schematic diagram for obtaining the average friction coefficient (MIU) from the monitoring result of the friction coefficient μ.

  As shown in FIG. 3, the surface of the measurement sample is scanned to monitor the friction coefficient μ of the surface. Next, the coefficient of friction μ is integrated in the monitor width of 20 mm (shaded area in FIG. 3). The average friction coefficient (MIU) is obtained by dividing the integral value by the monitor width (20 mm).

  When the MIU value is 0.3 or less, it can be said that the slipperiness is good.

  The MIU of the artificial leather itself was measured and found to be 0.37.

(Ii) Change in average friction coefficient (MMD)
The average coefficient of friction has a correlation with the smoothness and roughness that is felt when rubbing the surface. The larger this value, the rougher the surface.

  FIG. 4 shows a schematic diagram for obtaining the average friction coefficient variation (MMD) from the friction coefficient monitoring results.

  As shown in FIG. 4, in the monitor width of 20 mm, the absolute value of the difference between the average friction coefficient (MIU) and the friction coefficient μ is integrated (shaded area in FIG. 4). By dividing the integrated value by the monitor width (20 mm), the variation of the average friction coefficient (MMD) is obtained.

  When the value of MMD is 0.015 or less, it can be said that the smoothness of the surface is good.

  The MMD of the artificial leather itself was measured and found to be 0.02.

(Iii) Experiment under running water (endurance test)
Artificial leather coated with 0.1 mL of cosmetic material was placed at a rate of 100 mL / min for 2 minutes after being tilted 30 degrees with respect to the horizontal plane, and then placed on the surface with a paper towel. After wiping off the water and drying the sheet in an oven set at 50 ° C. for 1 hour, the friction coefficient μ was monitored under the same conditions as above, and the average friction coefficient (MIU) And, the variation (MMD) of the average friction coefficient was obtained.

(7) Gloss 0.1 mL of the cosmetic composition 0.1 ml obtained in Examples and Comparative Examples is dropped on artificial leather (suprale made by Idemitsu Technofine) cut into 2 cm (W) × 5 cm (L). After coating with the finger pad and drying, the gloss value was measured using a gloss meter (Nippon Denshoku Co., Ltd., model: VG7000) (A). Furthermore, the dry surface was rubbed 10 times with tissue paper, and the gloss value was measured (B).

  The amount of gloss change = BA. The gross value of the artificial leather is 1.1 [%].

  When the gloss value was 1.2% or more and the change value after 10 wears was 0.1% or less, it was judged to have a sustained gloss.

  Next, production examples will be described. In the production examples, the R value represents the ratio of the number of moles of isocyanate groups of the diisocyanate compound to the total number of moles of terminal hydroxyl groups of the polyalkylene oxide compound and hydroxyl groups of the diol compound (-NCO group / -OH group). Moreover, regarding an extruder, L / D shows the ratio of the effective length (L) of a screw, and a screw diameter (D).

Production Example 1 Production of Modified Polyalkylene Oxide In a storage tank A equipped with a stirrer kept at 80 ° C., 100 parts by mass of sufficiently dehydrated polyethylene oxide having a number average molecular weight of 20,000, 1,4-butanediol, 9 parts by mass and 0.1 parts by mass of dioctyltin dilaurate were added and stirred under a nitrogen gas atmosphere to obtain a uniform mixture. Separately, dicyclohexylmethane-4,4′-diisocyanate was charged into storage tank B kept at 30 ° C. and stored in a nitrogen gas atmosphere.

  Using a metering pump, set the mixture in storage tank A at a rate of 500 g / min and dicyclohexylmethane-4,4′-diisocyanate in storage tank B at a rate of 19.4 g / min. Continuously fed to the twin-screw extruder (R value = 1.00), mixed and reacted in the extruder, a strand was taken out from the outlet of the extruder, pelletized by a pelletizer, and modified polyalkylene oxide Got.

  The resulting polyalkylene oxide-modified product had a water absorption capacity of 25 g / g and a water elution content of 19%. The obtained pellets were immersed in liquid nitrogen and then pulverized to a median particle diameter of 60 μm for use in evaluation and examples.

Production Example 2 Production of Modified Polyalkylene Oxide Ethylene glycol obtained by heating an ethylene oxide / propylene oxide (mass ratio: 90/10) copolymer having a number average molecular weight of 15,000 at a rate of 250 g / min and 40 ° C. Were fed to a 40 mmφ single screw extruder (L / D = 40, set temperature: 90 ° C.) at a speed of 2.1 g / min, and both were melt mixed.

  A mixture obtained from the discharge port (discharged in a uniform molten state and analyzed by LC and confirmed to be mixed at a charging ratio) was mixed with a 30 mmφ twin-screw extruder (L / D = 41. 5) was continuously supplied to the hopper port (set temperature: 80 ° C.). At the same time, dioctyltin dilaurate was supplied to the hopper port of the twin-screw extruder at a rate of 0.5 g / min.

  Separately, dicyclohexylmethane-4,4′-diisocyanate adjusted to 30 ° C. is supplied at a rate of 12.4 g / min to the screw barrel portion located downstream of the hopper port of the twin-screw extruder. (R value = 0.95), the reaction was continued under a nitrogen atmosphere (set temperature: 180 ° C.). The strand obtained from the twin-screw extruder outlet was cooled and then pelletized with a pelletizer to obtain a polyalkylene oxide-modified product.

  The water-absorbing polyalkylene oxide modified product obtained had a water absorption capacity of 20 g / g and a water elution content of 15%. The obtained pellets were immersed in liquid nitrogen and then pulverized to a median particle diameter of 100 μm for evaluation and examples.

Example 1
The polyalkylene oxide-modified product powder obtained in Production Example 1 was added to 80% by mass of 1,3-butylene glycol aqueous solution so as to be 2% by mass, and heated and mixed at 70 ° C. to prepare a cosmetic composition. The evaluation results are shown in Table 1.

Example 2
The polyalkylene oxide-modified powder obtained in Production Example 1 was added to a 70% by mass dipropylene glycol aqueous solution so as to be 15% by mass, and heated and mixed at 70 ° C. to prepare a cosmetic composition. The evaluation results are shown in Table 1.

Example 3
The polyalkylene oxide-modified product powder obtained in Production Example 2 was added to a 60% by mass propylene glycol aqueous solution so as to be 10% by mass, and heated and mixed at 70 ° C. to prepare a cosmetic composition. The evaluation results are shown in Table 1.

Comparative Example 1
The polyalkylene oxide-modified powder obtained in Production Example 1 was added to 80% by mass of an 1,3-butylene glycol aqueous solution so as to be 0.3% by mass, and heated and mixed at 70 ° C. to obtain a cosmetic composition. Prepared. The evaluation results are shown in Table 1.

Comparative Example 2
The polyalkylene oxide-modified powder obtained in Production Example 1 was added to a 50% by mass dipropylene glycol aqueous solution so as to be 25% by mass, and heated and mixed at 70 ° C. to prepare a cosmetic composition. The evaluation results are shown in Table 1.

Comparative Example 3
The polyalkylene oxide-modified powder obtained in Production Example 2 was added to an 80% by mass ethanol aqueous solution so as to be 10% by mass, and heated and mixed at 70 ° C. to prepare a cosmetic composition. The evaluation results are shown in Table 1.

Comparative Example 4
To add 1.3% by mass of diisopropanolamine after adding to 60% by mass of propylene glycol aqueous solution so that it becomes 1% by mass of ACPEC 505E (manufactured by Sumitomo Seika Co., Ltd.) as a carboxyl vinyl polymer (carbomer). This was added to prepare a cosmetic composition. The evaluation results are shown in Table 1.

  In addition, the moisture retention evaluation of the aqueous alcohol solution itself used in each example is also shown in the column 1) below Table 1. Further, the gloss evaluation result of the artificial leather itself is also shown in the column 2) below Table 1.

  Further, “mass%” is “mass / mass%”. Moreover, the enlarged photograph (x100 times) of the surface of the artificial leather itself used for examination is shown in FIG. Further, FIG. 2 shows an enlarged photograph (× 100 times) when the cosmetic composition of Example 1 was applied to the surface of the artificial leather and then dried. It can be seen from FIG. 2 that the groove on the surface of the artificial leather is filled with the cosmetic composition and is smooth.

  As is apparent from the results shown in Table 1, by applying and drying a cosmetic composition containing 0.5 to 20% by mass of a polyalkylene oxide modified product and a polyhydric alcohol, there is no stickiness after coating. A surface state having good sliding properties and moisture retention (emollient) can be obtained. Moreover, the slipperiness can be continued even after washing with water.

Claims (7)

(I) a polyalkylene oxide compound, a diol compound, and a polyalkylene oxide modified product obtained by reacting a diisocyanate compound, and (ii) a polyhydric alcohol,
The polyalkylene oxide modified product is contained in an amount of 0.5 to 20% by mass,
Cosmetic composition. The cosmetic composition according to claim 1, wherein the polyhydric alcohol is a divalent to tetravalent alcohol. The cosmetic composition according to claim 1 or 2, wherein the polyhydric alcohol is an alkyl polyhydric alcohol having 2 to 6 carbon atoms. Polyalkylene oxide compounds are polyethylene oxide, polypropylene oxide, polybutylene oxide, ethylene oxide / propylene oxide copolymer, ethylene oxide / butylene oxide copolymer, propylene oxide / butylene oxide copolymer, and ethylene oxide / propylene oxide / butylene oxide copolymer. The cosmetic composition according to any one of claims 1 to 3, wherein the cosmetic composition is at least one selected from the group consisting of polymers. The diol compound is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, The cosmetic composition according to any one of claims 1 to 4, which is at least one selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol. The diisocyanate compound is 4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4′-diisocyanate (HMDI), 3-isocyanatomethyl-3,5 , 5-trimethylcyclohexyl isocyanate (IPDI), 1,8-dimethylbenzole-2,4-diisocyanate, and 2,4-tolylene diisocyanate (TDI). The cosmetic composition according to any one of claims 1 to 5. Cosmetics obtained using the cosmetic composition according to any one of claims 1 to 6.

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