Gel-type cosmetics

Abstract

To provide a gel-like cosmetic which gives a moist feeling, gives a thick feeling when applied with less stickiness and gives a sense of continuing the thickness.SOLUTION: There is provided a gel-like cosmetic which comprises 0.5 mass% to 10 mass% of an alkylene oxide addition derivative, 1 mass% to 20 mass% of a di- to tri-hydric alcohol having 3 to 6 carbon atoms, 0.005 mass% to 0.5 mass% of a (meth)acrylic copolymer and 0.1 mass% to 1.2 mass% of one or two or more selected from the group consisting of a carboxyvinyl polymer and an alkyl-modified carboxyvinyl polymer.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a gelled cosmetic, and more particularly to a gelled cosmetic that gives a moist feeling, has little stickiness, gives a feeling of thickness when applied, and gives a feeling that the thickness persists.

Background Art

[0002] The skin has an important function of preventing the loss of moisture from the body and blocking external stimuli. To maintain the original function of the skin, it is important to maintain the moisture of the skin in an appropriate amount through skin care and maintain smooth and healthy skin. Skin care generally starts with replenishing moisture with lotion, and by using cosmetics containing oily components such as emulsion and cream, a method is taken to prevent the evaporation of moisture from the skin and protect the skin from drying. On the other hand, among some consumers, the adverse effects of oxidized oily components on the skin have been recognized, and there are cases where stickiness is felt when using cosmetics containing oily components, and so-called oil-free cosmetics are being demanded.

[0003] Gelled cosmetics generally have few oily components and are skin care cosmetics characterized by a fresh feeling. Among gelled cosmetics, in particular, water-based gelled cosmetics with a very small amount or no oil content at all tend to be preferred by consumers from the above viewpoints.

[0004] However, gelled cosmetics need to be formulated with a relatively large amount of a polymer thickener to have a high viscosity. The higher the viscosity, the stickier it becomes during use, the more the cosmetic spreads on the skin, and there are drawbacks such as a slimy feeling and a squeaking feeling.

[0005] In order to solve the above problems, Patent Document 1 proposes a gel-like skin cosmetic containing a water-soluble polysaccharide and an acrylic polymer compound, wherein the acrylic polymer compound contains at least one selected from the group consisting of (hydroxyethyl acrylate / sodium acryloyldimethyltaurate) copolymer, (sodium acrylate / sodium acryloyldimethyltaurate) copolymer, (acrylamide / ammonium acrylate) copolymer, polyacrylate-13, and ammonium polyacrylate. The gel-like cosmetic described in Patent Document 1 has the characteristics of high viscosity, no stickiness, sliminess, or squeakiness, and excellent usability without dripping of the cosmetic on the skin. On the other hand, it was insufficient in terms of thickness feeling.

[0006] Therefore, Patent Document 2 proposes a gel-like cosmetic in which a composition containing (hydroxyethyl acrylate / sodium acryloyldimethyltaurate) copolymer and glycerin is combined with one or more polyhydric alcohols selected from sorbitol, maltitol, and diglycerin. The gel-like cosmetic described in Patent Document 2 has the effect of imparting a feeling of thickness when applied, and various improvements have been made.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] On the one hand, recently, there has been an increase in users who are concerned about dryness during sleep, especially female users, etc., and the demand for night packs has been increasing. When using a gelled cosmetic as a night pack, a high pack effect can be obtained by the thickness when applied before going to bed being maintained until the next morning, and the skin tends to feel protected from dryness during sleep. Therefore, a feeling of use in which the thickness persists for a relatively long time is required, but it has been difficult to achieve such a feeling of use with a gelled cosmetic.

[0009] An object of the present invention is to provide a gelled cosmetic that gives a moist feeling, has little stickiness, gives a feeling of thickness when applied, and gives a feeling that the thickness persists.

Means for Solving the Problems

[0010] The present inventors repeated research to solve the above problems, and found that by containing (a) an alkylene oxide addition derivative, (b) a di- or trihydric alcohol having 3 to 6 carbon atoms, (c) a structural unit having a side chain containing a urethane bond and a glycerol skeleton and a structural unit having a long-chain alkyl chain at the end of the side chain in a specific quantitative ratio, and (d) one or more selected from the group consisting of carboxyvinyl polymer and alkyl-modified carboxyvinyl polymer in specific content ranges, the above problems can be solved, and the present invention has been completed.

[0011] That is, the present invention relates to the following. A gelled lotion containing 0.5% by mass to 10% by mass of the following component (a), 1% by mass to 20% by mass of component (b), 0.005% by mass to 0.5% by mass of component (c), and 0.1% by mass to 1.2% by mass of component (d), wherein the total value of the content of component (a) and the content of component (b) is 5 to 22% by mass, and the ratio of the content of component (a) to the content of component (b) is 1 / 12 to 4. (a) An alkylene oxide addition derivative represented by the following formula (1), An alkylene oxide addition derivative in which the ratio (Mz / Mw) of the weight average molecular weight (Mw) to the z average molecular weight (Mz) calculated from a chromatogram obtained using a differential refractive index meter by gel permeation chromatography satisfies the relationship of the following formula (2) Z-[O-(PO) a -{(PO) b / (EO) c}-H] n ····(1) (In formula (1), Z represents a residue obtained by removing all hydroxyl groups from a compound having 1 to 24 carbon atoms and 1 to 6 hydroxyl groups, n represents a number from 1 to 6, PO represents an oxypropylene group, EO represents an oxyethylene group, a and b each represent the number of moles of added oxypropylene groups represented by PO, a is 0 to 100, and b is 1 to 100, c represents the number of moles of added oxyethylene groups represented by EO, c is 1 to 100, a + b + c ≧ 10 and b / c = 1 / 5 to 5 / 1, (PO) b / (EO) c indicates that the oxypropylene group represented by PO and the oxyethylene group represented by EO are randomly added, and the randomness ratio x of the oxypropylene group and the oxyethylene group is 0.5 ≦ x ≦ 0.97.) 20 ≦ Mz / Mw ≦ 60 ····(2) (b) A di- or trihydric alcohol having 3 to 6 carbon atoms (c) A (meth)acrylic copolymer containing a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4), and the molar ratio ((3) / (4)) of the structural unit represented by the following formula (3) to the structural unit represented by the following formula (4) is 90 / 10 to 30 / 70

Chemical formula

Chemical formula

Advantages of the Invention

[0012] According to the present invention, it is possible to provide a gelled cosmetic that gives a moist feeling, has less stickiness, gives a feeling of thickness when applied, and gives a feeling that the thickness persists.

Brief Description of the Drawings

[0013]

Figure 1

Modes for Carrying Out the Invention

[0014] Hereinafter, embodiments of the present invention will be described. In this specification, a numerical range described using the symbol "~" shall include the numerical values at both ends (upper limit and lower limit) of the symbol "~". For example, "2~5" means 2 or more and 5 or less.

[0015] The gelled cosmetic of the present invention contains (a) an alkylene oxide addition derivative, (b) a di- to trihydric alcohol having 3 to 6 carbon atoms, (c) a (meth)acrylic copolymer containing a structural unit having a side chain containing a urethane bond and a glycerol skeleton and a structural unit having a long-chain alkyl chain at the end of the side chain in a specific quantitative ratio, and (d) one or more selected from the group consisting of carboxyvinyl polymer and alkyl-modified carboxyvinyl polymer. Each component will be described below.

[0016] [(a) Alkylene oxide addition derivative] The alkylene oxide addition derivative contained as the component (a) in the lotion of the present invention is represented by the following formula (1) and is a compound in which the ratio (Mz / Mw) of the weight average molecular weight (Mw) and the z average molecular weight (Mz) calculated from the chromatogram obtained using a differential refractometer by gel permeation chromatography satisfies the relationship of the following formula (2). Z-[O-(PO) a -{(PO) b / (EO) c}-H] n ····(1) (In formula (1), Z represents a residue obtained by removing all hydroxyl groups from a compound having 1 to 24 carbon atoms and 1 to 6 hydroxyl groups, n represents a number from 1 to 6, PO represents an oxypropylene group, EO represents an oxyethylene group, a and b each represent the added molar number of the oxypropylene group represented by PO, a is 0 to 100, and b is 1 to 100, c represents the added molar number of the oxyethylene group represented by EO, c is 1 to 100, a + b + c ≧ 10 and b / c = 1 / 5 to 5 / 1, (PO) b / (EO) c indicates that the oxypropylene group represented by PO and the oxyethylene group represented by EO are randomly added, and the randomization ratio x of the oxypropylene group and the oxyethylene group is 0.5 ≦x≦ 0.97 .) 20 ≦Mz / Mw≦60 ····(2)

[0017] Examples of the compound (Z(OH)n) having a residue represented by Z and 1 to 6 hydroxyl groups are as follows: when n = 1, monohydric alcohols such as methanol, ethanol, and butanol; when n = 2, dihydric alcohols such as ethylene glycol, propylene glycol, and hexylene glycol; when n = 3, trihydric alcohols such as glycerin and trimethylolpropane; when n = 4, tetritols such as erythritol and pentaerythritol, cyclic sugar alcohols such as sorbitan, diglycerin, alkyl glucoside; when n = 5, pentitols such as xylitol and arabinitol; when n = 6, hexitols such as dipentaerythritol, sorbitol, and mannitol, and cyclitols such as inositol. The residue represented by Z may be the residue of a mixture of compounds having 1 to 6 hydroxyl groups. Also, n is preferably 1 to 4, more preferably 1 to 3.

[0018] In formula (1), the residue represented by Z may be a residue of a monohydric alcohol represented by ROH (in this case, n = 1). In such a case, R represents a hydrocarbon group having 1 to 24 carbon atoms. Examples of the hydrocarbon group having 1 to 24 carbon atoms represented by R include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Preferably, it is an alkyl group or an alkenyl group, more preferably an alkyl group or an alkenyl group having 1 to 12 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be either a linear alkyl or a branched alkyl, but a linear alkyl is more preferred. Examples of the linear alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, hexyl groups, and the like.

[0019] The hydrocarbon group having 1 to 24 carbon atoms represented by R may be only one kind or a mixture of two or more kinds. In formula (1), for the number of moles a of the added oxypropylene group represented by PO, the number of moles b of the added oxyethylene group represented by EO, and the number of moles c of the added oxyethylene group represented by EO, a = 0 to 100, b = 1 to 100, c = 1 to 100, and a + b + c ≧ 10.

[0020] If a + b + c is less than 10, the effect of feeling that the thickness persists may be insufficient. From such a viewpoint, a + b + c needs to be 10 or more, preferably 30 or more, and more preferably 45 or more. Also, since the viscosity increases as a + b + c increases, from the viewpoint of the ease of dispersion and blending of the alkylene oxide addition derivative into the lotion, a + b + c is preferably 100 or less, and more preferably 80 or less.

[0021] Also, the total number of moles [n×(a + b + c)] of the added oxypropylene group and the added oxyethylene group is preferably 30 or more, more preferably 45 or more, and even more preferably 50 or more. On the other hand, the total number of moles [n×(a + b + c)] of the added oxypropylene group and the added oxyethylene group is preferably 100 or less, and more preferably 80 or less.

[0022] In formula (1), (PO) b / (EO) c represents a polyoxyalkylene group formed by random addition of oxypropylene groups and oxyethylene groups. The molar ratio (b / c) of oxypropylene groups to oxyethylene groups in such a polyoxyalkylene group is 1 / 5 to 5 / 1, and the randomness ratio x of oxypropylene groups to oxyethylene groups is 0.1 ≦ x ≦ 1. When the molar ratio (b / c) of oxypropylene groups to oxyethylene groups is less than 1 / 5, there may be a feeling of stickiness. On the other hand, when b / c exceeds 5 / 1, the solubility in water may deteriorate.

[0023] The randomness ratio x of oxypropylene groups to oxyethylene groups is determined by the following formula (5). x = (b + c) / (a + b + c) ···(5)

[0024] The randomness ratio x determined by formula (5) is 0.5 as follows. 0.97 as follows. When the randomness ratio x is 0.5 less than, the effect of feeling that the thickness persists may become insufficient. The randomness ratio x determined by formula (5) is preferably 0.5 or more, more preferably 0.8 or more, and even more preferably 0.9 or more. On the other hand, the randomness ratio x determined by formula (5) is even more preferably 0.97 or less.

[0025] In the alkylene oxide addition derivative contained as component (a) in the lotion of the present invention, in gel permeation chromatography (GPC), the ratio (Mz / Mw) of the weight average molecular weight (Mw) to the z average molecular weight (Mz) obtained from the chromatogram obtained using a differential refractometer, that is, the graph showing the relationship between the refractive index intensity and the elution time, is 20 60 or less.

[0026] If Mz / Mw is 20 less than a certain value, the effect of feeling that the thickness persists may be insufficient. On the other hand, if Mz / Mw exceeds 60, the bias on the high molecular weight side in the molecular weight distribution becomes large, an increase in viscosity and the like are observed, and it may become difficult to disperse and blend into a lotion preparation. From the viewpoint of the effect of feeling that the thickness persists, it is more preferable that Mz / Mw is 40 or more.

[0027] Here, Mw and Mz are respectively obtained from GPC by the following formulas.

Equation

[0028] However, N is the number of polymer molecules, M is the molecular weight, and C is the sample concentration. Mw is the weight-average using the molecular weight as the weight, and Mz is the weight-average using the square of the molecular weight as the weight. Mw is affected by the presence of high molecular weight, and Mz is more affected by the presence of high molecular weight than Mw. Therefore, the alkylene oxide derivative of the present invention gives Mw and Mz as shown in the chromatogram of FIG. 1.

[0029] In the present invention, Mz / Mw of the alkylene oxide addition derivative can be determined, for example, as gel permeation chromatography (GPC), using the SH ODEX (registered trademark) GPC101 GPC dedicated system and BORWIN GPC calculation program to obtain a chromatogram represented by refractive index intensity and elution time. <Configuration and Conditions of SHODEX (registered trademark) GPC101 GPC Dedicated System> Differential refractometer: SHODEX RI-71s Guard column: SHODEX KF-G Column: SHODEX KF804L (mounted continuously in 3 pieces) Column temperature: 40 ° C Developing solvent: Tetrahydrofuran Flow rate: 1 mL / min Sample: 0.1 mass% tetrahydrofuran solution Sample injection volume: 0.1 mL

[0030] When producing the above alkylene oxide addition derivative, preferably, in the presence of a double metal cyanide complex catalyst (hereinafter abbreviated as "DMC catalyst"), an initiator and an alkylene oxide having 3 carbon atoms, that is, propylene oxide, are subjected to ring-opening addition. That is, an initiator having at least 1 hydroxyl group in the molecule and a DMC catalyst are added into a reaction vessel, and propylene oxide is continuously or intermittently added and subjected to addition polymerization under stirring in an inert gas atmosphere. Propylene oxide may be added under pressure or may be added under atmospheric pressure.

[0031] At this time, the average supply rate of propylene oxide is not particularly limited, but it is desirable to change it according to the charged amount of propylene oxide. Specifically, when the rate (supply amount per unit time) during supplying 5 mass% to 20 mass% of the total supply amount of propylene oxide is V1, the rate during supplying 20 mass% to 50 mass% of the total supply amount of propylene oxide is V2, and the rate during supplying 50 mass% to 100 mass% of the total supply amount of propylene oxide is V3, it is preferable to control the average supply rate of propylene oxide so that V1 / V2 = 1.1 to 2.0 and V2 / V3 = 1.1 to 1.5.

[0032] Also, the reaction temperature is preferably 50°C to 150°C, and more preferably 70°C to 110°C. If the reaction temperature is higher than 150°C, the catalyst may be deactivated. On the other hand, if the reaction temperature is lower than 50°C, the reaction rate may be slow and the productivity may be poor.

[0033] As the initiator used in the production of the alkylene oxide addition derivative, from the above formula (1), a compound represented by Z(OH)n having 1 to 24 carbon atoms and the number of hydroxyl groups n being 1 to 6, or a compound obtained by adding propylene oxide to these compounds can be used. Examples of such initiators include butanol, butylpropylene glycol, polyoxypropylene glycol, polyoxypropylene glyceryl ether, and the like. When Z is the residue of the above-mentioned ROH, a monohydric alcohol (ROH) having a hydrocarbon group with 1 to 24 carbon atoms represented by R can be used as the initiator.

[0034] The amount of trace water contained in the initiator and propylene oxide is not particularly limited, but the amount of water contained in the initiator is desirably 0.5% by mass or less, and the amount of water contained in propylene oxide is desirably 0.01% by mass or less.

[0035] The amount of the DMC catalyst used is not particularly limited, but it is preferably 0.0001% by mass to 0.1% by mass, and more preferably 0.001% by mass to 0.05% by mass, based on the amount of the alkylene oxide addition derivative to be produced. The introduction of the DMC catalyst into the reaction system may be carried out all at once first, or may be carried out sequentially in portions. After the polymerization reaction is completed, the DMC catalyst is removed. The removal of the catalyst can be carried out by known methods such as filtration, centrifugation, and adsorption treatment with a synthetic adsorbent.

[0036] As the DMC catalyst, known ones can be used, and for example, it can be represented by the following formula (6). Md[M’y(CN)z]e(H2O)f·(R’)g ···(6) (In formula (6), M and M’ represent metal ions, R’ represents an organic ligand, d, e, y, and z are positive integers that vary depending on the valence and coordination number of the metal, and f and g are positive integers that vary depending on the coordination number of the metal.)

[0037] In formula (6), examples of the metal ion represented by M include zinc (Zn)(II), iron (Fe)(II), iron (Fe)(III), cobalt (Co)(II), nickel (Ni)(II), aluminum (Al)(III), strontium (Sr)(II), manganese (Mn)(II), chromium (Cr)(III), copper (Cu)(II), tin (Sn)(II), lead (Pb)(II), molybdenum (Mo)(IV), molybdenum (Mo)(VI), tungsten (W)(IV), tungsten (W)(VI), etc. Among them, zinc (Zn)(II) is preferably used.

[0038] In formula (6), examples of the metal ion represented by M' include iron (Fe)(II), iron (Fe)(III), cobalt (Co)(II), cobalt (Co)(III), chromium (Cr)(II), chromium (Cr)(III), manganese (Mn)(II), manganese (Mn)(III), nickel (Ni)(II), vanadium (V)(IV), vanadium (V)(V), etc. Among them, iron (Fe)(II), iron (Fe)(III), cobalt (Co)(II), cobalt (Co)(III) are preferably used.

[0039] In formula (6), examples of the organic ligand represented by R' include alcohol, ether, ketone, ester, etc. Alcohol is preferred. Moreover, a water-soluble organic ligand is more preferred. Specifically, tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, N,N-dimethylacetamide, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), etc. are included. tert-Butyl alcohol is even more preferred. Particularly preferred DMC catalysts include Zn3[Co(CN)6]2(H2O)4((CH3)3COH) 2 are included.

[0040] In the gelled cosmetic of the present invention, as the component (a), the alkylene oxide addition derivative can be contained alone or in combination of two or more. When the total amount of the gelled cosmetic of the present invention is 100% by mass, the content of the component (a) is 0.5% by mass to 10% by mass, preferably 1% by mass to 8% by mass, more preferably 2% by mass to 6% by mass. When the content of the component (a) is less than 0.5% by mass, the effect of imparting a moist feeling to the applied site may be reduced, or the thickness feeling and the persistence of the thickness during application may be insufficient. When the content of the component (a) exceeds 10% by mass, stickiness may be felt.

[0041] [(b) Divalent to trivalent alcohol having 3 to 6 carbon atoms] Examples of the divalent to trivalent alcohol having 3 to 6 carbon atoms contained as the component (b) in the lotion of the present invention include divalent alcohols such as 1,3-propanediol, propylene glycol, 1,3-butylene glycol, pentylene glycol, hexylene glycol, isoprene glycol, dipropylene glycol, and trivalent alcohols such as glycerin. Among these, glycerin, 1,3-propanediol, 1,3-butylene glycol, pentylene glycol, and dipropylene glycol are preferably used.

[0042] In the present invention, the divalent to trivalent alcohol having 3 to 6 carbon atoms can be synthesized and used according to a production method known per se, but products commercially available for cosmetics, quasi-drugs, etc. can be used.

[0043] In the gelled cosmetic of the present invention, as the component (b), the divalent to trivalent alcohol can be contained alone or in combination of two or more. When the total amount of the gelled cosmetic of the present invention is 100% by mass, the content of the component (b) is 1% by mass to 20% by mass, preferably 2% by mass to 18% by mass, more preferably 3% by mass to 16% by mass, and particularly preferably 3% by mass to 12% by mass. When the content of component (b) is less than 1% by mass, there may be cases where the moist feeling decreases or the thickness persistence is insufficient, and when the content of component (b) exceeds 20% by mass, stickiness may be felt.

[0044] [(Meth)acrylic copolymer containing a urethane bond, a structural unit having a side chain containing a glycerol skeleton, and a structural unit having a long-chain alkyl chain at the end of the side chain in a specific quantitative ratio] The lotion of the present invention contains, as component (c), a (meth)acrylic copolymer containing a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

Chem.

Chem.

[0045] In formula (3), R 1 represents a hydrogen atom or a methyl group, and a methyl group is preferred from the viewpoint of the stability of the copolymer. R 2 represents -(CH2) n -, and n is an integer from 1 to 4. That is, R 2is preferably any one of -(CH2)-, -(CH2)2-, -(CH2)3-, -(CH2)4-, and -(CH2)2- is more preferable in terms of availability.

[0046] Specific examples of the structural unit of formula (3) include, for example, glycerol-1-methacryloyloxyethylene urethane, glycerol-1-methacryloyloxypropylene urethane, etc. Glycerol-1-methacryloyloxyethylene urethane is preferable in terms of ease of synthesis.

[0047] As a method for synthesizing the monomer that becomes the structural unit of formula (I), for example, a compound obtained by subjecting a cyclic ketal and a (meth)acryloyloxyalkylene isocyanate to a urethanization reaction by the method described in JP-A-2007-119374 or a method analogous thereto is subjected to a ring-opening reaction with water in a water-containing solvent in the presence of a urethanization reaction catalyst.

[0048] In formula (4), in the formula, R 3 represents a hydrogen atom or a methyl group, and a methyl group is preferable from the viewpoint of the stability of the copolymer. L 1 represents phenylene, cyclohexylene, -C(=O)-O-, -O-, -C(=O)-NH-, -O-C(=O)-, or -O-C(=O)-O-, and among them, -O- is preferable. L 2 represents a linear or branched alkyl group having 10 to 22 carbon atoms, and examples thereof include a hexadecyl group, a heptadecyl group, an octadecyl group, etc. That is, examples of the monomer that becomes the structural unit of formula (I) include hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, etc., and among them, octadecyl (meth)acrylate is preferable from the effects of imparting thickness persistence and a moist feeling.

[0049] (c) component, the molar ratio of the structural unit of formula (3) to the structural unit of formula (4) (structural unit of formula (3) / structural unit of formula (4)) is 90 / 10 to 30 / 70. If the proportion of the structural unit of formula (3) is more than this range, the feeling of the thickness being sustained tends to be insufficient, and if the proportion of the structural unit of formula (4) is more, in addition to the poor solubility in water, the moist feeling at the applied part tends to be insufficient. From the viewpoint of the effect of imparting the sustainability of the thickness and the moist feeling, the molar ratio ((3) / (4)) is preferably 70 / 30 to 40 / 60, more preferably 60 / 40 to 50 / 50.

[0050] (c) component may contain structural units other than the structural unit of formula (3) and the structural unit of formula (4). Examples of such other structural units include isobornyl methacrylate, ethyltrimethylammonium methacrylate chloride, etc. When the copolymer contains other structural units in addition to the structural unit of formula (3) and the structural unit of formula (4), the content of the other structural units in the copolymer is 10 mol% or less with respect to the total amount of the structural unit of formula (3) and the structural unit of formula (4).

[0051] (c) component may be a random copolymer or a block copolymer, but a random copolymer is preferred. (c) component preferably has a weight average molecular weight (Mw) of 5,000 to 500,000 from the viewpoints of the effect of giving a feeling of the thickness being sustained and ease of blending, and more preferably 10,000 to 200,000. In addition, for ease of handling of (c) component, those diluted with polyhydric alcohols such as glycerin and 1,3-butylene glycol can be used. Here, the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) method (in terms of polyethylene glycol). The weight average molecular weight by the GPC method can be calculated using a sample solution with a methanol / chloroform mixed solvent (6 / 4 (volume ratio)) containing 0.5 mass% lithium bromide and a calibration curve of standard polyethylene glycol.

[0052] (c) component can be prepared by polymerizing a monomer composition containing at least a monomer that becomes a structural unit of formula (3) and a monomer that becomes a structural unit of formula (4) in the presence of a radical polymerization initiator under conditions that satisfy the molar ratio ((3) / (4)) of the above structural units by a known method such as solution polymerization in an inert gas atmosphere such as nitrogen. Also, commercially available products can be used. Examples of commercially available products include the product with the trade name "CERACUTE-L" [manufactured by NOF Corporation]. This commercially available product (trade name "CERACUTE-L") is a product in which the (c) component is diluted with glycerin and 1,3-butylene glycol.

[0053] When the total amount of the lotion of the present invention is 100% by mass, the content of the (c) component is 0.005% by mass to 0.5% by mass, preferably 0.01% by mass to 0.4% by mass, more preferably 0.05% by mass to 0.3% by mass, and particularly preferably 0.05 to 0.2% by mass. When the content of the (c) component is less than 0.005% by mass, the moist feeling and the persistence of the thickness at the applied site may decrease. Also, when the content of the (c) component exceeds 0.5% by mass, stickiness may occur.

[0054] [One or more selected from the group consisting of (d) carboxyvinyl polymer and alkyl-modified carboxyvinyl polymer] The carboxyvinyl polymer used as the (d) component in the present invention is a polymer of acrylic acid crosslinked with allyl ether of pentaerythritol, allyl ether of sucrose, or allyl ether of propylene. Also, the alkyl-modified carboxyvinyl polymer used as the (d) component in the present invention is a copolymer of acrylic acid and an alkyl acrylate or alkyl methacrylate having 10 to 30 carbon atoms in the alkyl group, crosslinked with allyl ether of sucrose or allyl ether of pentaerythritol.

[0055] In the present invention, as the component (d), one or more selected from the group consisting of carboxyvinyl polymer and alkyl-modified carboxyvinyl polymer can be used. For the purpose of the present invention, it is preferable to use a carboxyvinyl polymer as the component (d).

[0056] In the present invention, as the carboxyvinyl polymer and the alkyl-modified carboxyvinyl polymer, those produced by methods known per se can be used. As the carboxyvinyl polymer, "CARBOPOL ULTREZ20", "CARBOPOL ULTREZ21", "PEMULEN TR-1", "PEMULEN TR-2", "CARBOPOL ETD2020" (manufactured by Lubrizol Advanced Materials), "Syntalen L" (manufactured by Wako Pure Chemical Industries, Ltd.), "AQUPEC HV-505E" (manufactured by Sumitomo Seika Chemicals Co., Ltd.), "CARBOPOL940", "CARBOPOL941" (manufactured by Lubrizol Advanced Materials), and as the alkyl-modified carboxyvinyl polymer, commercially available products such as "AQUPEC HV-501ER", "AQUPEC SER W-300C" (manufactured by Sumitomo Seika Chemicals Co., Ltd.) can also be used.

[0057] The content of the component (d) in the aqueous gel-like cosmetic of the present invention is 0.1% by mass to 1.2% by mass, preferably 0.2% by mass to 0.8% by mass, and particularly preferably 0.3% by mass to 0.6% by mass. When the content of the component (d) is less than 0.1% by mass, the thickness may be insufficient, and when it exceeds 1.2% by mass, stickiness may occur.

[0058] [Total content of component (a) and component (b)] In the present invention, it is particularly preferable that the total content of component (a) and component (b) is 6% by mass to 20% by mass. When the total content of component (a) and component (b) is within the above range, stickiness is suppressed, and a gelled cosmetic can be obtained in which the moist feeling, the thickness feeling during application, and the persistence of the thickness of the applied part are strongly felt.

[0059] [Ratio of the contents of component (a) and component (b)] In the present invention, the mass ratio (a / b) of the content of component (a) and component (b) is preferably 1 / 10 to 1, more preferably 1 / 4 to 1 / 2. When the mass ratio of the content of component (a) and component (b) is within the above range, a gelled cosmetic in which the persistence of the thickness is strongly felt can be obtained.

[0060] [Water] In addition to the above components (a) to (d), the lotion of the present invention usually contains water. In the lotion of the present invention, as the water, purified water such as ion-exchanged water and distilled water, which is suitable for the production of cosmetics, is used. The content of water in the gelled cosmetic of the present invention is set as an amount based on 100% by mass of the total amount of the gelled cosmetic, but is usually 50% by mass to 98% by mass, preferably 60% by mass to 95% by mass, more preferably 70% by mass to 90% by mass.

[0061] [Other additives] In the lotion of the present invention, within a range not impairing the features of the present invention, in addition to the above components (a) to (d) and water as necessary, other additives generally used in cosmetics can be contained. Such additives include oil agents, lower alcohols, moisturizing agents, thickening agents, surfactants, dispersants, suspending agents, pH adjusters, chelating agents, antioxidants, preservatives, blood circulation promoters, anti-wrinkle agents, anti-inflammatory agents, whitening agents, cell activators, astringents, anti-acne agents, ultraviolet absorbers, coloring agents, fragrances, and the like. These additives can be selected, one kind or two or more kinds, according to the purpose, and can be contained according to the content usually used in gelled cosmetics.

[0062] The gelled lotion of the present invention can be produced according to the usual production method of gelled cosmetics. For example, it can be produced by sequentially adding the above-mentioned components (a), (b), (c), and the component (d) preliminarily dispersed in water to water together with other additives as necessary, mixing them, and making them uniform.

[0063] The gelled cosmetic of the present invention gives a feeling of thickness when applied, gives a feeling that the thickness persists, has little stickiness, and gives a moist feeling to the applied area.

Examples

[0064] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. Gelled cosmetics of Examples 1 to 13 and Comparative Examples 1 to 5 were prepared by sequentially adding components (a), (a'), (b), (c), (d), (d') and other additives to water in the compositions shown in Tables 1, 2, and 3 and mixing them uniformly. Note that the numerical values corresponding to the respective components in the tables indicate the contents (mass %) of the respective components, and "-" in the tables indicates that the component is not contained. In addition, the content of the component (c) in Tables 1, 2, and 3 indicates the content of the specific methacrylic copolymer itself.

[0065] Note that the raw materials used in the preparation of the lotions of the Examples and Comparative Examples are as follows. (a) Alkylene oxide addition derivative (In formula (1), Z = CH3CH2CH2CH2-, a = 4, b = 24, c = 35, a + b + c = 63, b + c = 59, b / c = 0.69, x = 0.94, n = 1, molecular weight calculated from hydroxyl value = 3,507, Mz / Mw = 42.3): n-butanol as an initiator, Zn3[Co(CN)6]2(H2O)4((CH3)3COH) as a DMC catalyst 2 It was produced and used by the method described above. (a') Alkylene oxide addition derivative (In formula (1), Z = CH3CH2CH2CH2-, a = 4, b = 24, c = 35, a + b + c = 63, b + c = 59, b / c = 0.69, x = 0.94, n = 1, molecular weight calculated from the hydroxyl value = 3,507, Mz / Mw = 0.94): The one produced using n-butanol as the initiator and potassium hydroxide as the catalyst was used. (b-1) 1,3-Butylene glycol: Commercially available raw materials were used. (b-2) Glycerin: Commercially available raw materials were used. (c) A (meth)acrylic copolymer containing a structural unit having a side chain containing a urethane bond and a glycerol skeleton and a structural unit having a long-chain alkyl chain at the end of the side chain in a specific quantitative ratio, 5% by mass, glycerin 66.5% by mass, 1,3-butylene glycol 28.5% by mass: "Ceracute-L" manufactured by NOF Corporation (R in formula (3) 1 is a methyl group, and a methacrylic copolymer containing 60 mol% of the structural unit where n is 2 and R in formula (4) 3 is a methyl group, L 1 is -O-, L 2 is an octadecyl group and contains 40 mol% of the structural unit (weight average molecular weight 50,000)) was used. (d) Carboxyvinyl polymer: "ULTREZ 10" manufactured by Sumitomo Seika Chemicals Co., Ltd. was used. (d’) Xanthan gum: "Grinsted Xanthan Clear 80" manufactured by Danisco Japan Co., Ltd. was used.

[0066] For each of the gelled lotion products in the examples and comparative examples, the thickness feeling, moist feeling, non-stickiness, and thickness persistence when applied as follows were evaluated. The evaluation was performed by a sensory evaluation with 20 women (aged 21 to 59) as panelists. (1) Thickness feeling when applied Each of the gelled cosmetic products in the examples and comparative examples was applied to the face of each panelist, and the thickness feeling when spread over the entire face was evaluated according to the following evaluation criteria and scored. The total of the 20 evaluation scores was obtained, and the thickness feeling of the gelled cosmetic product was determined according to the following determination criteria. <Evaluation criteria> 2 points: When feeling a very strong sense of thickness 1 point: When feeling a sense of thickness 0 point: When feeling not much sense of thickness <Judgment criteria> ◎: The total score is 35 points or more; it is a gel-like cosmetic with a very strong sense of thickness. 〇: The total score is 30 points or more and less than 35 points; it is a gel-like cosmetic with a sense of thickness. △: The total score is 20 points or more and less than 30 points; it is a gel-like cosmetic with a slightly insufficient sense of thickness. ×: The total score is less than 20 points; it is a gel-like cosmetic without a sense of thickness.

[0067] (2) Moist feeling For the moist feeling when each gel-like cosmetic of the examples and comparative examples was applied to the face of each panelist and made to fit the entire face, it was evaluated according to the following evaluation criteria and scored. The total of the evaluation scores of 20 panelists was obtained, and the moist feeling of the gel-like cosmetic was judged according to the following judgment criteria. <Evaluation criteria> 2 points: When feeling a very strong moist feeling 1 point: When feeling a moist feeling 0 point: When feeling not much moist feeling <Judgment criteria> ◎: The total score is 35 points or more; it is a gel-like cosmetic with a very strong moist feeling. 〇: The total score is 30 points or more and less than 35 points; it is a gel-like cosmetic with a moist feeling. △: The total score is 20 points or more and less than 30 points; it is a gel-like cosmetic with a slightly insufficient moist feeling. ×: The total score is less than 20 points; it is a gel-like cosmetic without a moist feeling.

[0068] (3) Non-stickiness For each gel-like cosmetic of the examples and comparative examples applied to the face of each panelist, after 10 minutes from the application, the non-stickiness was evaluated according to the following evaluation criteria and scored. The total of the evaluation scores of 20 panelists was obtained, and the non-stickiness of the gel-like cosmetic was judged according to the following judgment criteria. <Evaluation Criteria> 2 points: When it is felt that there is no stickiness at all. 1 point: When it is felt that there is almost no stickiness. 0 point: When it is felt sticky. <Judgment Criteria> ◎: The total score is 35 points or more; it is a gel-like cosmetic with very little stickiness. 〇: The total score is 30 points or more and less than 35 points; it is a gel-like cosmetic with no stickiness. △: The total score is 20 points or more and less than 30 points; it is a gel-like cosmetic with a little stickiness. ×: The total score is less than 20 points; it is a gel-like cosmetic with stickiness.

[0069] (4) Durability of Thickness The gel-like cosmetics of the examples and comparative examples were applied to the faces of each panelist. About 8 hours after the application, the durability of the thickness was evaluated according to the following evaluation criteria and scored. The total of the evaluation scores of 20 panelists was obtained, and the durability of the thickness of the gel-like cosmetic was determined according to the following judgment criteria. <Evaluation Criteria> 2 points: When there is very high durability of thickness. 1 point: When there is durability of thickness. 0 point: When there is no durability of thickness. <Judgment Criteria> ◎: The total score is 35 points or more; it is a gel-like cosmetic with very high durability of thickness. 〇: The total score is 30 points or more and less than 35 points; it is a gel-like cosmetic with durability of thickness. △: The total score is 20 points or more and less than 30 points; it is a gel-like cosmetic with somewhat insufficient durability of thickness. ×: The total score is less than 20 points; it is a gel-like cosmetic with no durability of thickness. The results of the evaluations in (1) to (4) above were shown together in Tables 1 to 3.

[0070]

Table 1

[0071]

Table 2

[0072]

Table 3

[0073] As shown in Table 1 and Table 2, each of the gel-like cosmetics of Examples 1 to 13 was evaluated as having a thickness feeling when applied, a moist feeling, suppression of stickiness, and persistence of thickness. In particular, in the gel-like cosmetic of Example 1 containing 4% by mass of component (a), 10% by mass of component (b-1), 0.1% by mass of component (c), and 0.5% of component (d), and with the total content of component (a) and component (b) being 14% by mass, very good evaluations (evaluations of "◎") were obtained in all evaluation items.

[0074] On the other hand, among the gel-like cosmetics of Comparative Examples 1 to 5, there was no case where good evaluations of "○" or above were obtained in all evaluation items. Specifically, in the gel-like cosmetic of Comparative Example 1 that does not contain component (a), the thickness feeling, moist feeling, and persistence of thickness when applied were evaluated as being somewhat insufficient. In the gel-like cosmetic of Comparative Example 2 containing an alkylene oxide addition polymer with Mz / Mw = 4.2 instead of component (a), the persistence of thickness was evaluated as being somewhat insufficient. In the gel-like cosmetic of Comparative Example 3 that does not contain component (b), the moist feeling and persistence of thickness were evaluated as being somewhat insufficient. In the gel-like cosmetic of Comparative Example 4 that does not contain component (c), the moist feeling and persistence of thickness were evaluated as being somewhat insufficient. In the gel-like cosmetic of Comparative Example 5 containing xanthan gum instead of component (d), the thickness feeling when applied was somewhat insufficient, and it was evaluated as being inferior in the persistence of thickness.

Claims

【Claim 1】 It contains 0.5% to 10% by mass of the following component (a), 1% to 20% by mass of component (b), 0.005% to 0.5% by mass of component (c) and 0.1% to 1.2% by mass of component (d), the total value of the content of the component (a) and the content of the component (b) is 5 to 22% by mass, and the ratio of the content of the component (a) to the content of the component (b) is 1 / 12 to 4. A gelled lotion characterized by that. (a) An alkylene oxide addition derivative represented by the following formula (1), An alkylene oxide addition derivative in which the ratio (Mz / Mw) of the weight average molecular weight (Mw) and the z average molecular weight (Mz) calculated from the chromatogram obtained using a differential refractometer in gel permeation chromatography satisfies the relationship of the following formula (2) Z-[O-(PO) ａ -{ (PO) ｂ / (EO) ｃ}-H] ｎ ・・・・(1) (In formula (1), Z represents the residue obtained by removing all hydroxyl groups from a compound having 1 to 24 carbon atoms and 1 to 6 hydroxyl groups, n represents a number from 1 to 6, PO represents an oxypropylene group, EO represents an oxyethylene group, a and b each represent the added molar number of the oxypropylene group represented by PO, a is 0 to 100, and b is 1 to 100, c represents the added molar number of the oxyethylene group represented by EO, and c is 1 to 100, a + b + c ≧ 10 and b / c = 1 / 5 to 5 / 1, (PO) ｂ / (EO) ｃ indicates that the oxypropylene group represented by PO and the oxyethylene group represented by EO are randomly added, The random ratio x of the oxypropylene group and the oxyethylene group is 0.5 ≦ x ≦ 0.97.) 20 ≦ Mz / Mw ≦ 60 ···· (2) (b) A di- to trihydric alcohol having 3 to 6 carbon atoms (c) It contains a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4), and the molar ratio ((3) / (4)) of the structural unit represented by the following formula (3) and the structural unit represented by the following formula (4) is 90 / 10 to 30 / 70. A (meth)acrylic copolymer 【Chemical 1】 In formula (3), R １ represents a hydrogen atom or a methyl group, R ２ represents -(CH ２ )n- and n is an integer from 1 to 4, * represents a bonding site with other structural units.) 【Chemical 2】 In formula (4), R ３ represents a hydrogen atom or a methyl group, L １ represents phenylene, cyclohexylene, -C(=O)-O-, -O-, -C(=O)-NH-, -O-C(=O)-, or -O-C(=O)-O-; L ２ represents a linear or branched alkyl group having 10 to 22 carbon atoms, * represents a bonding site with other structural units.) (d) One or more selected from the group consisting of carboxyvinyl polymer and alkyl-modified carboxyvinyl polymer

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