JP4993426B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to hair cosmetics, and more specifically, relates to hair cosmetics excellent in stringiness.

Conventionally, in hair gels and hair waxes that are widely used as hair styling agents, for the purpose of giving users a sense of their hair styling, attempts to impart moderate stringiness include, for example, highly polymerized polyethylene glycol, cellulosic polymers, It is performed by blending sodium polyacrylate or the like (for example, Patent Document 1).
JP-A-10-45546

  However, the conventional technology has not yet provided sufficient spinnability to the base material itself, and it has become sticky if it is attempted to increase the spinnability by increasing the blending amount of the spinnage component. There has been a problem in usability such as a feeling of use.

  Therefore, the problem to be solved by the present invention is to provide a hair cosmetic that has sufficient stringiness and is non-sticky.

  The present inventor has now found that the above-described problems can be solved by the following technique.

  That is, this invention is invention which provides the hair cosmetics (henceforth this hair cosmetics) containing the following component (A) and (B).

(A) 0.1-10.0 mass% of the copolymer represented by following formula (1) with respect to hair cosmetics :
R—B—X—B—R (1)
[ Wherein X is polyethylene oxide having an average degree of polymerization of ethylene oxide units in the range of 30 to 6000 , and R is an alcohol ethoxylate group having 10 or more carbon atoms which may be the same or different from each other. B is a divalent linking molecule having a urethane bond that may be the same or different from each other, and the mass ratio of X and R is X: R = 5: 1 to 1000: 1. Yes ]

(B) Dimethylsiloxane methyl (polyoxyethylene) siloxane represented by the following formula (3), wherein the polyoxyethylene modification rate is 60% by mass or more with respect to the copolymer and the HLB is 12 or more. 0.1-10.0% by mass of the copolymer with respect to the hair cosmetic:
[In formula, m, n, and a which show an average degree of polymerization respectively show the number of m being 5-13, n being 4-8, and a being 6-13.]
In addition to the above-mentioned components (A) and (B), the present hair cosmetic contains (C) carboxyvinyl polymer in an amount of 0.01 to 3.0% by mass based on the hair cosmetic. It is possible to suppress a decrease in viscosity at a high temperature of the hair cosmetic.

Moreover, the fall of the stringiness in low temperature conditions can be suppressed by mix | blending 0.001-1.0 mass% of (D) polyacrylate with respect to hair cosmetics .

  According to the present invention, there is provided a hair cosmetic that exhibits sufficient stringiness and is non-sticky.

[ (A) component ]
In the copolymer (1), the mass ratio of the hydrophilic molecule X to the hydrophobic molecule R is preferably in the range of X: R = 5: 1 to 1000: 1. If the mass ratio is out of this range, the stability of the present hair cosmetic containing the same may decrease.

  In the copolymer (1), the hydrophilic molecule X is preferably at least one of polyalkylene oxides such as polymethylene oxide, polyethylene oxide, polypropylene oxide, and particularly preferably polyethylene oxide. . When the hydrophilic molecule X is polyethylene oxide, the degree of polymerization of the ethylene oxide unit is preferably in the range of about 30 to 6000.

  The hydrophobic molecule R is preferably a monovalent hydrocarbon group having 6 or more carbon atoms or a monovalent fluorocarbon group having 4 or more carbon atoms. As a particularly preferred embodiment of R, the alcohol ethoxylate group (2), ie,

R ¹ —O— (CH ₂ CH ₂ O) _p — (2)
[Wherein, R ¹ is preferably a hydrocarbon group having 10 to 40 carbon atoms, and the average degree of polymerization p of the ethylene oxide unit is preferably 10 to 40]

  The binding molecule B is a divalent binding molecule having one or two types of bonding groups selected from any one selected from an ether bond, an ester bond and a urethane bond.

  The copolymer (1) can be generally produced by reacting substances containing molecules (X, R and B) constituting the copolymer as main elements with each other in the presence of an alkali catalyst. The copolymer (1) can be produced with reference to, for example, descriptions in JP-A-52-25840, JP-A-9-71766, JP-A-9-71767, and the like.

Examples of the substance having X as a main element include the aforementioned polyalkylene oxides. Moreover, as a substance having R as a main element, hydrocarbons having 6 or more carbon atoms, fluorocarbons having 4 or more carbon atoms, alcohol ethoxylates (R ¹ —O— (CH ₂ CH ₂ O) _p- H: R ¹ and p are the same as described above).

  In addition, as a substance having B as a main element, a substance that gives an ester bond as a linking group, for example, an aliphatic dicarboxylic acid, a substance that gives an ether bond as a linking group, for example, an aliphatic dihydric alcohol, etc. Examples of the substance that gives a urethane bond as a linking group include aliphatic diisocyanate, alicyclic diisocyanate, biphenyl diisocyanate, and phenylmethane diisocyanate.

  Examples of the aliphatic diisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, Octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, paraxylylene Range isocyanate, Examples include tetramethylxylylene diisocyanate. Examples of the aromatic diisocyanate include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4- Naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate and the like can be mentioned.

  Examples of the alicyclic diisocyanate include hydrogenated xylylene diisocyanate and isophorone diisocyanate.

  Examples of biphenyl diisocyanate include biphenyl diisocyanate, 3,3′-dimethylbiphenyl diisocyanate, 3,3′-dimethoxybiphenyl diisocyanate, and the like.

  Examples of the diisocyanate of phenylmethane include diphenylmethane-4,4′-diisocyanate, 2,2′-dimethyldiphenylmethane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, 2,5,2 ′. , 5′-tetramethyldiphenylmethane-4,4′-diisocyanate, cyclohexylbis (4-isothiontphenyl) methane, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4′-dimethoxydiphenylmethane 3,3′-diisocyanate, 4,4′-diethoxydiphenylmethane-3,3′-diisocyanate, 2,2′-dimethyl-5,5′-dimethoxydiphenylmethane-4,4′-diisocyanate, 3,3′- Dichlorodiphenyldimethylmethane-4,4'-diisocyanate, benzophenone -3,3'-diisocyanate and the like.

In the present invention, as an example of the most preferable copolymer (1), the hydrophilic molecule X is polyethylene oxide having an average degree of polymerization of ethylene oxide units of 240, and the hydrophobic molecule R (two identical molecules) is represented by the formula ( 2) is an alcohol ethoxylate group [R ¹ is a 2-dodecyl-dodecyl group [CH ₃ (CH ₂ ) ₉ CH (C ₁₂ H ₂₅ ) CH ₂ —], and the average degree of polymerization p is 20. And a polyether polyol-based urethane polymer in which the divalent linking molecule B (two molecules are the same) is a hexamethylene diisocyanate molecule bonded by a divalent urethane bond. The copolymer (1) is also referred to as “specific copolymer (1)”. Examples of commercially available products of the specific copolymer (1) include Adecanol GT-700 ((PEG-240 / decyltetradeceth-20 / hexamethyldiisocyanate) copolymer: manufactured by Asahi Denka Co.).

  It is suitable for this hair cosmetic to mix | blend copolymer (1) 0.1-10.0 mass% with respect to hair cosmetics. When the blending amount is less than 0.1% by mass of the hair cosmetic, the effect of improving the spinnability may not be sufficiently observed. When it exceeds 10.0% by mass, the viscosity is high. This may cause inconvenience in handling during manufacturing, resulting in reduced work efficiency, inconvenience in removal from the container during actual use, and poor elongation when applied to hair and skin. In some cases.

[ (B) component ]
The dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymer (B) is generally called a pendant type silicone surfactant and is typically represented by the following chemical formula (3). Dimethicone copolyol.

[In formula, m, n, and a which show an average degree of polymerization respectively show the number of m being 5-13, n being 4-8, and a being 6-13.]

  Moreover, said dimethicone copolyol (3) can be manufactured by performing reaction of following formula (4) etc., for example.

[Wherein m and n are the same as those in the above formula (3)]

  The polyoxyethylene modification rate in the dimethicone copolyol (3) is preferably 60% by mass or more based on the copolymer, and the HLB of the dimethicone copolyol (3) is approximately 12 or more. And having a hydrophilic property (the HLB of the dimethicone polyol (3) is preferably 12 or more).

  Examples of commercially available dimethicone copolyol (3) satisfying such suitable conditions include, for example, silicone SC1014M, silicone SC1014M (BF) (both manufactured by Shin-Etsu Chemical Co., Ltd.), SILWET-10E, and SILWET-10P (manufactured by Nihon Unicar). Etc.

  The hair cosmetic composition preferably contains 0.1 to 10.0% by mass, more preferably 0, of the dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymer (B) with respect to the hair cosmetic composition. .1 to 5.0% by mass. When the blending amount is less than 0.1% by mass with respect to the hair cosmetic, sufficient spinnability cannot be imparted, and when it exceeds 10.0% by mass, the base viscosity becomes low. There are concerns about the problem of dropping off and usability.

  As described above, by blending the components (A) and (B) in the hair cosmetic composition in the manner described above, it is possible to impart excellent spinnability to the hair cosmetic composition. It can be carried out. Furthermore, the present hair cosmetics with more excellent temperature stability can be produced by blending the carboxyvinyl polymer as the following component (C) and the polyacrylate as the component (D). .

[ Ingredient (C) ]
By mix | blending a carboxy vinyl polymer with this hair cosmetics, the viscosity fall at the high temperature of this hair cosmetics can be suppressed. Carboxyvinyl polymer is a component that is widely used as a cosmetic ingredient. Examples of commercially available products of carboxyvinyl polymer include Sinterene K and Sinterene L (both manufactured by Sigma).

  When the carboxyvinyl polymer (C) is blended with the present hair cosmetic, the blending amount is preferably 0.01 to 3.0% by mass, more preferably 0.05 to 1.%. 0% by mass. If the blending amount is less than 0.01% by mass, sufficient viscosity stability at high temperature cannot be imparted, and if the blending amount exceeds 3.0% by mass, the base viscosity becomes too high. There are concerns about usability problems such as loss of yarn properties.

[ Ingredient (D) ]
By mix | blending polyacrylate with this hair cosmetics, the fall of the stringiness in low temperature conditions can be suppressed. Specific examples of the polyacrylate include sodium polyacrylate, potassium polyacrylate, and ammonium polyacrylate. These are components that are widely used as cosmetic ingredients. Examples of commercially available products of polyacrylate include Aronbis S ′ (manufactured by Nippon Pure Chemicals Co., Ltd.), Aron A (Toagosei Co., Ltd.), and the like.

  The blending amount when the polyacrylate (D) is blended with the present hair cosmetic is preferably 0.001 to 1.0 mass%, more preferably 0.005 to 0 with respect to the hair cosmetic. 0.5% by mass. If the blending amount is less than 0.001% by mass, sufficient spinnability cannot be imparted at a low temperature, and if it exceeds 1.0% by mass, the spinnability becomes excessive and dripping or There are concerns about usability problems such as stickiness.

  The present hair cosmetic is mainly used as a cosmetic for hair, but can also be used as a cosmetic for eyelashes. Further, the hair cosmetic is not particularly limited as long as it is a dosage form premised on having a certain degree of viscosity, such as a gel-like agent or a cream-like agent.

  In the present hair cosmetic, other additive components other than the above components (A) to (D) can be arbitrarily blended within a range not impairing the effects of the present invention. Examples of such components include powder components, liquid fats and oils, solid fats and oils, waxes, hydrocarbons, ester oils, silicone oils, surfactants, humectants, water-soluble polymers, thickeners, UV absorbers, metals Use sequestering agents, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, water, etc. as necessary. Can do.

  Hereinafter, the present invention will be described more specifically by way of examples. The description of this example is not intended to limit the scope of the invention. Unless otherwise specified, the blending amount in the description of the examples is mass% with respect to the blending target.

[Test Example 1] Examination of spinnability in examples having the basic composition of the present hair cosmetics Test products (Example 1, Comparative Examples 1 and 2) having the formulations shown in Table 1 below were prepared, and wrinkles about these The yarn properties were evaluated, and the results are also shown in the table.

Manufacturing method of test product Each test product was prepared by stirring and dissolving each component in water and filling the container. This preparation method is the same in Examples 2 to 6 described later.

Test Method The contents of each test product were taken from the container to the finger, and the stringiness at that time was determined in a room at a temperature of 30 ° C. Evaluation was performed as follows.
◎: Thoroughly thread from the contents on the finger to the base in the jar.
○: A thread is drawn from the content on the finger to the base in the jar, but breaks when the distance is 10 cm or more.
Δ: The yarn is combed but can be cut at a short distance.
X: The yarn is not twisted at all.

result

(*): Adecanol GT-700 (manufactured by Asahi Denka Co., Ltd.), which is the same in the following examples.
(**): Yodosol PUD (manufactured by Nippon NC), the same as in the following examples.
(***): SILWET10-E (manufactured by Nippon Unicar Co., Ltd.), dimethicone copolyol (3), each average degree of polymerization, m is 6 to 13, n is 4 to 8, and a is 10 (The same applies in the following examples).
(***): POLYSILICONE-13 (CAS No.:158451-77-5)

  From the results shown in Table 1, it became clear that the spinnability was recognized only when the specific copolymer (1) and the dimethicone copolyol (3) were combined. When a linear silicone surfactant was blended in place of dimethicone copolyol (3) (Comparative Example 2), almost no spinnability was observed.

[Test Example 2] Examination of effect on high-temperature stability when carboxyvinyl polymer is added In this test example, the present invention product (Example 2) not containing carboxyvinyl polymer and the present invention product (Examples) blended The viscosity stability at a high temperature of 3-4) was evaluated by the following method. Table 2 shows the prescriptions and test results of each test product.

Viscosity and temperature stability test method Viscosity was measured using a single cylindrical rotational viscometer bismetron VS-H1 (manufactured by Shibaura System Co., Ltd.) under the conditions of 50 ° C., 37 ° C. and 30 ° C. The reduction rate of the viscosity at 50 ° C. and 37 ° C. with respect to the viscosity at 30 ° C. was calculated according to <1> and formula <2>.

Formula <1> 1- (50 ° C. measured viscosity) / (30 ° C. measured viscosity)
Formula <2> 1- (Measurement viscosity at 37 ° C.) / (Measurement viscosity at 30 ° C.)

result

  From the results shown in Table 2, it was found that by adding an appropriate amount of carboxyvinyl polymer, the viscosity was increased as a whole, and at the same time, the rate of decrease in viscosity at 50 ° C. and 37 ° C. was decreased.

[Test Example 3] Examination of influence on low-temperature stability when polyacrylate is added In this test example, the present invention product not containing sodium polyacrylate (Example 4: already shown in Table 2) and blending The spinnability at low temperatures of the inventive products (Examples 5 to 6) was evaluated by the following method. Table 2 shows the prescriptions and test results of each test product.

Low temperature spinnability test method Each test article was allowed to stand overnight at a low temperature (5 ° C.), and the spinnability of the next day was judged. The method for determining the spinnability is the same as the method performed in Test Example 1. For comparison, Table 3 shows the results of leaving each test product at 30 ° C. overnight together with the prescription of each test product.

result

From the results shown in Table 3, it has been clarified that a decrease in spinnability at low temperatures can be clearly suppressed by blending an appropriate amount of polyacrylate.

Claims (4)

Hair cosmetics containing the following components (A) and (B).
(A) 0.1-10.0 mass% of the copolymer represented by following formula (1) with respect to hair cosmetics :
R—B—X—B—R (1)
[ Wherein X is polyethylene oxide having an average degree of polymerization of ethylene oxide units in the range of 30 to 6000 , and R is an alcohol ethoxylate group having 10 or more carbon atoms which may be the same or different from each other. B is a divalent linking molecule having a urethane bond that may be the same or different from each other, and the mass ratio of X and R is X: R = 5: 1 to 1000: 1. Yes ]
(B) Dimethylsiloxane methyl (polyoxyethylene) siloxane represented by the following formula (3), wherein the polyoxyethylene modification rate is 60% by mass or more with respect to the copolymer and the HLB is 12 or more. 0.1-10.0% by mass of the copolymer with respect to the hair cosmetic:
[In formula, m, n, and a which show an average degree of polymerization respectively show the number of m being 5-13, n being 4-8, and a being 6-13.] The hair cosmetic composition according to claim 1, wherein the copolymer represented by the formula (1) is a PEG-240 / decyltetradeceth-20 / hexamethyldiisocyanate) copolymer. Furthermore , 0.01-3.0 mass% of carboxy vinyl polymers were mix | blended with respect to hair cosmetics , The hair cosmetics of Claim 1 or 2 characterized by the above-mentioned. Furthermore , 0.001-1.0 mass% of polyacrylic acid salt was mix | blended with respect to hair cosmetics , The hair cosmetics in any one of Claims 1-3 characterized by the above-mentioned.