JP2009242340A - Cleansing cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleansing cosmetic which is excellent in make-up removal, is free from the whitening after wiping, has excellent rinse feeling and is useful both for wiping and washing off. <P>SOLUTION: The cleansing cosmetic comprises (a) 1-20 mass% of a volatile silicone oil, (b) 1-20 mass% of a volatile hydrocarbon oil (e.g. isododecane, isohexadecane etc.), (c) 1-3 mass% of a nonvolatile silicone oil, (d) 0.5-4 mass% of a hydrophilic ionic surfactant, (e) 0.01-2 mass% of an acrylic polymer (e.g. an alkyl modified carboxyvinyl polymer, a carboxyvinyl polymer etc.), and (f) the rest of water. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a cleansing cosmetic. More particularly, the present invention relates to a cleansing cosmetic that is excellent in make-up removal, does not become white after wiping, has a good rinsing feeling after rinsing, and can be used for both wiping and rinsing.

  As a makeup cleansing having a high detergency, there is a cleansing cosmetic mainly composed of an oil component having a high make dissolving power.

  For example, Japanese Patent Application Laid-Open No. Sho 62-135406 (Patent Document 1) describes that 2 to 20% by weight of one or more low-boiling solvents selected from low-boiling isoparaffins and low-boiling silicone oils are added to a polyacrylic resin. A makeup remover dispersed in an aqueous phase with a viscous agent is disclosed, but this makeup remover has a problem that the rinsing feeling during washing is not good. The publication does not describe the blending of non-volatile silicone oil or surfactant.

  Japanese Patent Application Laid-Open No. 2002-255787 (Patent Document 2) describes a skin cleansing composition containing a carboxyvinyl polymer, hydroxyethyl cellulose, and a nonionic surfactant in a skin cleansing composition containing cyclic dimethylpolysiloxane. Yes. However, this publication does not describe the blending of volatile hydrocarbon oil and non-volatile silicone oil.

  JP-A-8-245357 (Patent Document 3) describes at least one moisturizing agent selected from polyhydric alcohols and organic acid salts, and linear and / or cyclic silicone oils having a viscosity at 25 ° C. of 10 cSt or less. And a cosmetic comprising an alkyl-modified carboxyvinyl polymer. However, the cosmetics described in this document are not described for those using an active agent in combination. Further, the cosmetic was not excellent in the rinse-off feeling.

  In JP-A-8-231336 (Patent Document 4), about 1 to 50% by weight of water, about 1 to 60% by weight of a polyhydric alcohol having 2 to 6 carbon atoms, about 1 to 50% by weight of poly ( A transparent cold cream cosmetic composition containing a C2-4 alkoxylate) polymer, about 0.1-40% by weight C10-20 hydrocarbon, and an effective amount of a silicone emollient is described. Yes. However, the composition of the publication is a W / O base and cannot be washed away.

JP-A-62-135406 JP 2002-255787 A JP-A-8-245357 JP-A-8-231336

  The present invention has been made in view of the above circumstances, and its purpose is to provide a cleansing cosmetic that is excellent in removing makeup, does not become white after wiping, has a good rinsing feeling during washing, and can be used for both wiping and washing. It is in. Until now, no cleansing cosmetics have these effects.

  In order to solve the above problems, the present invention provides (a) 1 to 20% by mass of volatile silicone oil, (b) 1 to 20% by mass of volatile hydrocarbon oil, and (c) 1 to 10% of nonvolatile silicone oil. 10% by mass, (d) 0.1 to 4% by mass of a hydrophilic nonionic surfactant, (e) 0.01 to 2% by mass of an acrylic polymer, and (f) the remainder of water. Provide cleansing cosmetics.

  Moreover, this invention provides the said cleansing cosmetics whose (a) component / (b) component is 0.5-6 (mass ratio).

  Moreover, this invention provides the said cleansing cosmetics whose (b) component is isododecane and / or isohexadecane.

  The present invention also provides the cleansing cosmetic, wherein the component (e) is a combination of an alkyl-modified carboxyvinyl polymer and a carboxyvinyl polymer.

  According to the present invention, there is provided a cleansing cosmetic that is excellent in removing makeup, does not become white after wiping, has a good rinsing feeling during rinsing, and can be used for both wiping and rinsing.

  Hereinafter, the present invention will be described in detail.

The volatile silicone oil as the component (a) of the present invention refers to a silicone oil that volatilizes at room temperature (25 ° C.) and normal pressure (1 atm. 9.8 × 10 ⁴ Pa). Specifically, for example, chain silicone oil (chain polysiloxane) such as decamethyltetrasiloxane, hexamethyldisiloxane, dodecamethylpentasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopenta Examples thereof include cyclic silicone oils (cyclic polysiloxane) such as siloxane and methylpolycyclosiloxane. In particular, it is preferable to use a cyclic polysiloxane from the viewpoint of feeling after use. (A) A component can use 1 type (s) or 2 or more types.

  (A) The compounding quantity of a component is 1-20 mass% in this invention cleansing cosmetics, Preferably it is 5-20 mass%. If the blending amount is less than 1% by mass, a sufficient make-up removal effect cannot be obtained.

The volatile hydrocarbon oil component (b) is a hydrocarbon oil component that volatilizes at room temperature (25 ° C.) and normal pressure (1 atm. 9.8 × 10 ⁴ Pa). Specifically, for example, isodecane, isododecane, isohexadecane, and combinations thereof are preferable examples. Of these, isodecane and isohexadecane are preferably used from the viewpoint of the make-up removal effect. (B) A component can use 1 type (s) or 2 or more types.

  (B) The compounding quantity of a component is 1-20 mass% in this invention cleansing cosmetics, Preferably it is 5-20 mass%. If the blending amount is less than 1% by mass, a sufficient make-up removal effect cannot be obtained.

  In this invention, it is preferable to make it the total compounding quantity of (a) component and (b) component be 5-40 mass%, More preferably, it is 5-25 mass%. If the total blending amount is less than 5% by mass, a sufficient makeup-removing effect is not observed. On the other hand, if it exceeds 40% by mass, separation occurs, making formulation difficult.

  Moreover, in this invention, it is preferable that (a) component / (b) component (mass ratio) is 0.5-6 from the point of the makeup removal effect.

  The nonvolatile silicone oil component (c) is a silicone oil that is liquid at room temperature (25 ° C.), specifically, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane; polyether-modified silicone, Modified silicone oils such as alkyl-modified silicones, higher fatty acid ester-modified silicones, higher alkoxy-modified silicones, phenol-modified silicones, fluorine-modified silicones, cross-linked organopolysiloxanes; dimethylsiloxane methyl (perfluoroalkyl ethoxypropylene) siloxane copolymers, etc. Can be mentioned. Of these, dimethylpolysiloxane, methylphenylpolysiloxane and the like are preferably used.

  (C) The compounding quantity of a component is 1-10 mass% in this invention cleansing cosmetics, Preferably it is 1-3 mass%. If the blending amount is less than 1% by mass, the skin becomes white after wiping, while if it exceeds 10% by mass, the rinse-off feeling is not good.

  The hydrophilic nonionic surfactant as component (d) is blended from the viewpoints of stability of emulsification and excellent rinse feeling. Specifically, for example, sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan sesquiisostearate; glycerin fatty acid esters such as glycerol monooleate and glycerol monoisostearate; diglyceryl monooleate, decaglyceryl diisostearate and the like Polyglycerin fatty acid ester of polyoxyethylene sorbitan monooleate (6E.O.), polyoxyethylene sorbitan monooleate (20E.O.), etc .; polyoxyethylene sorbitan monooleate (6E.O.) O.), polyoxyethylene sorbite fatty acid esters such as polyoxyethylene sorbite tetraoleate (40E.O.); polyoxyethylene glyceryl monooleate (5E.O.), polyoxyethylene Polyoxyethylene glycerin fatty acid esters such as glyceryl monooleate (15E.O.); Polyethylene glycol fatty acid esters such as polyoxyethylene monoisostearate (10E.O.) and polyoxyethylene monooleate (6E.O.) Polyethylene glycol difatty acid esters such as polyoxyethylene diisostearate (8E.O.) and polyoxyethylene diisostearate (12E.O.); polyoxyethylene oleyl ether (7E.O.), polyoxy Polyoxyethylene alkyl ethers such as ethylene oleyl ether (10E.O.); polyoxyethylene polyoxypropylene alkyl ethers such as polyoxyethylene (1) polyoxypropylene (4) alkyl ether; polyoxyethylene castor oil (20E.O.) .), Examples thereof include polyoxyethylene castor oil such as polyoxyethylene hydrogenated castor oil (40E.O.) and hydrogenated castor oil. However, it is not limited to these examples. (D) 1 type (s) or 2 or more types can be used for a component.

  (D) The compounding quantity of a component is 0.1-4 mass% in this invention cleansing cosmetics, Preferably it is 0.5-3 mass%. When the blending amount is less than 0.1% by mass, the stability of emulsification is poor.

  Preferred examples of the acrylic polymer as component (e) include alkyl-modified carboxyvinyl polymers and carboxyvinyl polymers. (E) A component is mainly mix | blended in order to emulsify silicone oil.

  The carboxyvinyl polymer used in the present invention is an acidic polymer mainly composed of an acrylic acid polymer, and a commercially available product can be used. Specifically, for example, Hibiswako 103, 104, 105 (Wako Pure Chemical Industries, Ltd.), carbopol series carbopol 934, 940, 941, 980, 981, 2984, 5984, etc. (manufactured by NOVEON), Junlon PW-series of Junlon PW-110, PW-111 (manufactured by Nippon Seiyaku Co., Ltd.), syntalen of Synthalen series (manufactured by 3V SIGMA) K, L, M and the like.

  The alkyl-modified carboxyvinyl polymer used in the present invention is known as a (polyacrylic acid / alkyl acrylate) copolymer, an (acrylic acid / alkyl methacrylate) copolymer, etc., and as a commercial product, for example, carbopol ( Carbopol) 1342, 1382, ETD2020, Ultrez21, Ultrez20 polymer, Pemulen TR-1, and TR-2 (manufactured by NOVEON), and the like can be preferably used.

  In the present invention, it is preferable to use an alkyl-modified carboxyvinyl polymer and a carboxyvinyl polymer in combination. When used in combination, the alkyl-modified carboxyvinyl polymer / carboxyvinyl polymer (mass ratio) is preferably 0.5-2.

  (E) The compounding quantity of a component is 0.01-2 mass% in this invention cleansing cosmetics, Preferably it is 0.5-1 mass%. When the blending amount is less than 0.01% by mass, emulsification of the silicone oil is not sufficient, while when it exceeds 2% by mass, the viscosity is increased, which is not preferable in the product process.

  (F) A component is water and the remainder is mix | blended.

  The cleansing cosmetic composition of the present invention containing the above components (a) to (f) is an oil-in-water emulsifying cleansing cosmetic composition, and is used as a skin or hair wash in the cosmetics field, quasi-drug field, and pharmaceutical field. can do. It is particularly preferable to use it as a makeup cleaning agent. The cleansing cosmetic of the present invention is especially wiped away from makeup cosmetics such as mascara and lipstick that contain a silicone resin, and makeup cosmetics that could not be sufficiently removed with conventional cleansing cosmetics, In any use mode of washing away, it is possible to exert an extremely excellent make-up removal effect that is excellent in usability and can be surely removed.

  The manufacturing method of the cleansing cosmetic composition of the present invention is not particularly limited and can be manufactured by a conventional method. That is, for example, it can be prepared by adding oil and other oil-soluble components, surfactant, water and other water-soluble components in this order with stirring at room temperature or under heating.

  The cleansing cosmetic composition of the present invention can optionally contain any component that is usually blended in a cleaning material within a range that does not impair the purpose and effect of the present invention, in addition to the above-described blending components. As such components, for example, liquid natural fats and oils, solid fats and oils, waxes, ester oils, hydrocarbon oils, sterols, humectants, various extracts, ultraviolet absorbers, sequestering agents, neutralizing agents and pH adjusters, Antioxidants, antibacterial agents, drug components and the like can be mentioned. However, it is not limited to these.

  Liquid natural oils include linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, sage oil, kyounin oil, cinnamon oil, jojoba oil, grape oil , Sunflower oil, almond oil, rapeseed oil, sesame oil, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, tea seed oil, evening primrose oil, egg yolk oil, liver oil and the like.

  Examples of solid fats include bonito fat, coconut oil, palm oil, palm kernel oil, hardened oil, hardened castor oil, mole, and shea butter.

  Examples of waxes include beeswax, gandelilla wax, cotton wax, carnauba wax, bayberry wax, ibotarou, montan wax, nukarou, lanolin, reduced lanolin, hard lanolin, kapok wax, sugar cane wax, jojoba wax, shellac wax and the like.

  Ester oils include octanoic esters such as cetyl octanoate, lauric esters such as hexyl laurate, myristate esters such as isopropyl myristate and octyldodecyl myristate, palmitate esters such as octyl palmitate, isocetyl stearate, etc. Stearic acid ester, isostearic acid ester such as isopropyl isostearate, isopalmitic acid ester such as octyl isopalmitate, oleic acid ester such as isodecyl oleate, adipic acid diester such as diisopropyl adipate, sebacic acid such as diethyl sebacate Diester, diisostearyl malate, glyceryl trioctanoate, triglyceride such as glyceryl triisostearate, trimethylol triisostearate Trimethylolpropane fatty acid esters of bread, etc., pentaerythritol fatty acid esters such as tetra octanoate pentaerythritol.

  Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, squalene, pristane, paraffin, isoparaffin, ceresin, petrolatum, microcrystalline wax and the like.

  Examples of sterols include cholesterol, sitosterol, phytosterol, and lanosterol.

  Examples of the humectant include glycerin, propylene glycol, 1,3-butylene glycol, dipropylene glycol, sodium lactate, sodium pyrrolidonecarboxylate, and sodium hyaluronate.

  Various extract liquids include Dokudami Extract, Oat Extract, Merilot Extract, Oyster Extract, Licorice Extract, Peonies Extract, Soap Extract, Loofah Extract, Kina Extract, Yakinoshita Extract, Clara Extract, Kouhon Extract, Fennel Extract, Primrose Extract, Rose Extract , Ginger extract, Lemon extract, Shikon extract, Aloe extract, Ginger root extract, Eucalyptus extract, Horsetail extract, Sage extract, Thyme extract, Tea extract, Seaweed extract, Cucumber extract, Clove extract, Raspberry extract, Melissa extract, Carrot extract, Carrot extract , Horse chestnut extract, peach extract, peach leaf extract, mulberry extract, cornflower extract, sea cucumber extract, placenta extract, thymus extract, silk extract, button pi extract There is a liquid and the like.

  Examples of UV absorbers include benzoic acid UV absorbers such as paraaminobenzoic acid, anthranilic acid UV absorbers such as methyl anthramylate; salicylic acid UV absorbers such as octyl salicylate, phenyl salicylate, and homomethyl salicylate; Isopropyl acid, octyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, [4-bis (trimethylsiloxy) methylsilyl-3-methylbutyl] -3 , 4,5, -trimethoxycinnamic acid ester and other cinnamic acid UV absorbers; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfone Acid, 2-hydroxy Benzophenone ultraviolet absorbers such as sodium 4-methoxybenzophenone-5-sulfonate; urocanic acid, ethyl urocanate, 2-phenyl-5-methylbenzoxazole, 2- (2′-hydroxy-5′-methylphenyl) Examples include benzotriazole and 4-tert-butyl-4′-methoxybenzoylmethane.

  Examples of the sequestering agent include alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, phosphoric acid and the like.

  Examples of neutralizers and pH adjusters include 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, potassium hydroxide, sodium hydroxide, triethanolamine, carbonic acid Examples include sodium, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, d1-malic acid and the like.

  Examples of the antioxidant include ascorbic acid, α-tocopherol, dibutylhydroxytoluene, butylhydroxyanisole and the like.

  Antibacterial agents include benzoic acid, salicylic acid, coalic acid, sorbic acid, paraoxybenzoic acid ester, parachloromethcresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photosensitizer, phenoxyethanol and the like.

The drug components include vitamin A oil, retinol, retinol palmitate, inosit, pyridoxine hydrochloride, benzyl nicotinate, nicotinamide, nicotinic acid dl-α-tocopherol, magnesium ascorbate phosphate, vitamin D ₂ (ergocassipherol) Vitamins such as dl-α-tocopherol, dl-α-tocopherol acetate, pantothenic acid, biotin, hormones such as estradiol, ethinyl estradiol, arginine, aspartic acid, tranexamic acid, cystine, cysteine, methionine, serine, leucine, tryptophan Amino acids such as allantoin and azulene, whitening agents such as arbutin, astringents such as zinc oxide and tannic acid, refreshing agents such as L-menthol and camphor, sulfur, lysozyme chloride, Acid pyridoxine, there is a γ- oryzanol and the like.

  The cleansing cosmetic composition of the present invention can be in the form of a liquid, emulsion, paste, gel or the like.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Unless otherwise specified, the blending amount is expressed in mass% with respect to the system in which the component is blended. Cosmetic raw materials are sold by dilution with water because they are easy to use, but all the compounding amounts shown here are pure.

  Prior to the examples, test methods and evaluation criteria for each evaluation used in this example will be described.

[Make-up effect, feeling of use, etc.]
The tester (2 persons) evaluated the make-up removal effect, feeling of use, etc. by wiping use and washing off use.

1. Cosmetics for make-off test In order to evaluate the make-off effect, a mascara (a silicone resin-containing mascara) having the following composition was used as a make-up cosmetic.
(Test cosmetic: mascara)
Light isoparaffin 47
Decamethylcyclopentasiloxane 10
Trimethylsiloxysilicic acid 10
Microcrystalline wax 10
Dextrin palmitate 15
Dimethylpolysiloxane polyethylene glycol copolymer 5
Triisostearic acid POE hydrogenated castor oil (20.EO) 1
1,3-butylene glycol 1
Purified water 1

2. Makeup evaluation test method (i) Wiping use The above mascara (test cosmetic) is applied to the inner side of the forearm, and after 1 hour, the cleansing cosmetic (sample) is blended with cotton to remove the mascara (makeup removal effect). ) Was evaluated according to the evaluation criteria shown in Table 1 below. Furthermore, the usability when wiping with cotton and the skin after wiping were evaluated according to the evaluation criteria shown below.
(ii) Use of washing off Apply the above mascara (test cosmetic) on the inner side of the forearm, and after 1 hour, apply the cleansing cosmetic (sample) to the applied mascara, and then wash off to remove the mascara effect (make-up) The dropping effect) and the rinsing feeling were evaluated according to the following evaluation criteria.

3. Evaluation Criteria Each tester evaluated based on the evaluation criteria shown below, and based on that, two testers made a comprehensive evaluation.

(I) Wiping use [Mascara removal (make-up removal)]
A: It falls very well B: It falls well C: It falls a little D: It does not fall so much [feeling of use (fresh feeling)]
A: Very good (very refreshing)
B: Good (excellent refreshing feeling)
C: Not very good (not very refreshing)
D: Bad (no refreshing feeling)
[Does not turn white after use]
A: Does not turn white after wiping B: Does not turn white after wiping C: Becomes slightly white after wiping D: Turns white after wiping

(Ii) Washing out [Mascara removal (make-up removal)]
A: It falls very well B: It falls well C: It falls a little D: It does not fall so much [Rinse feeling]
A: Not sticky B: Not sticky C: Sticky D: Sticky

[Stability]
The appearance of the cleansing cosmetic (sample) after standing at 50 ° C. for 4 weeks was visually observed and evaluated according to the following evaluation criteria.
A: No abnormality is observed B: Some liquid separation is observed on the surface C: Some separation is observed D: Separation is observed

(Examples 1-9, Comparative Examples 1-9)
Cleansing cosmetics having the compositions shown in Tables 1 and 2 below were produced. The manufacturing method is in accordance with a conventional method. That is, among the components shown in the table, the water-soluble polymer raw material was uniformly mixed and dissolved, and the surfactant dissolved in ethanol was stirred and dissolved therein. Furthermore, the oil phase component in which each oil was mixed was stirred and mixed to emulsify, and potassium hydroxide was added to obtain a gel or cream cleansing cosmetic.

The cleansing cosmetics shown in Tables 1 and 2 thus obtained were used as samples, and the make-up removal, usability, and the like were evaluated according to the above evaluation methods and evaluation criteria. The results are shown in Tables 1-2.
In Tables 1 and 2, the following compounds used the following products.

(Acrylic acid / acrylic acid (C _10-30 ) alkyl) copolymer ^{(* 1)} : "Pemulen TR-1" (NOVEON)
Carboxy vinyl polymer ^{(* 2)} : “Sintalen K” (manufactured by 3V SIGMA)
Polyoxyethylene hydrogenated castor oil ^{(* 3)} : “Nikkor HCO-60” (manufactured by Nippon Surfactant Kogyo Co., Ltd.)
Monoisostearate polyoxyethylene glyceryl (60E.O.) ^{(* 4)} : "Emalex GWIS-160N" (Nippon Emulsion Co., Ltd.)
Dimethylpolysiloxane ^{(* 5)} : “Silicone KF-96” (nonvolatile silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.)

As is clear from the results of Tables 1 and 2, the effects of the present invention were obtained with the samples of Examples 1 to 9, but the effects of the present invention were not obtained with the samples of Comparative Examples 1 to 9.
Further formulation examples are shown below.

(Example 10: Makeup cleansing cosmetic)
(Mixed component) (mass%)
Octamethylcyclotetrasiloxane 10
Isododecane 10
(Acrylic acid / alkyl acrylate (C _10-30 )) copolymer 0.5
Carboxyvinyl polymer 0.5
Dimethylpolysiloxane (nonvolatile silicone oil) 5
Polyoxyethylene hydrogenated castor oil (60E.O.) 0.5
Potassium hydroxide 0.5
EDTA · 3Na · 2H ₂ O 0.1
Xylitol 1
Fragrance 0.1
Water balance

(Example 11: Makeup cleansing cosmetic)
(Mixed component) (mass%)
Octamethylcyclotetrasiloxane 20
Isododecane 10
α-olefin oligomer 5
Liquid paraffin 5
Grape seed oil 0.1
(Acrylic acid / alkyl acrylate (C _10-30 )) copolymer 0.5
Carboxyvinyl polymer 0.5
Dynamite Glycerin 1
Dimethylpolysiloxane (nonvolatile silicone oil) 3
Polyoxyethylene hydrogenated castor oil (60E.O.) 0.5
Potassium hydroxide 0.5
EDTA · 3Na · 2H ₂ O 0.1
Methyl isothiazolinone solution 0.1
Fragrance 0.1
Water balance

Claims (4)

  (A) 1-20 mass% of volatile silicone oil, (b) 1-20 mass% of volatile hydrocarbon oil, (c) 1-10 mass% of non-volatile silicone oil, (d) hydrophilic nonionic A cleansing cosmetic comprising 0.1 to 4% by weight of a surfactant, (e) 0.01 to 2% by weight of an acrylic polymer, and (f) the balance of water.   The cleansing cosmetic according to claim 1, wherein component (a) / component (b) is 0.5 to 6 (mass ratio).   The cleansing cosmetic according to claim 1 or 2, wherein the component (b) is isododecane and / or isohexadecane.   The cleansing cosmetic according to any one of claims 1 to 3, wherein the component (e) is a combination of an alkyl-modified carboxyvinyl polymer and a carboxyvinyl polymer.