JP2930810B2 - Hairdressing base - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hairdressing base.
More specifically, the present invention relates to a hairdressing base having excellent adhesion to hair, imparting excellent gloss and smooth feel to hair, and having good set holding power.

[0002]

2. Description of the Related Art Hitherto, low-polymerization degree polysiloxanes having a degree of polymerization of about 1 to 50, such as volatile cyclic siloxane and dimethylpolysiloxane, have been used for hair styling agents because of their good compatibility with other raw materials. However, recently, it has been recognized that the higher the degree of polymerization of the silicone oil, the better the combability exhibited by the silicone oil. Therefore, expectations for a silicone oil having a high degree of polymerization are increasing.

[0003] However, silicone oil has the disadvantage that its compatibility with other raw materials such as alcohol becomes poor when the degree of polymerization exceeds about 50, and it is easy to separate.

[0004] Therefore, various types of silicone oils have been improved, and attempts have been made to improve water solubility and adhesion to hair by modifying the functional groups thereof. Such techniques include, for example, polyether-modified silicones (JP-A-60-126209 and JP-A-61-6) and amino-modified silicones (JP-A-1-203314,
2-111712) is known.

[0005] However, these silicones are all based on silicone oil, and have various characteristics when used as a hair styling agent while having characteristics unique to silicone. For example, if the film is modified to increase its hardness, impart water solubility, or improve its adhesion to hair, it tends to be expensive, and blended with low molecular weight silicone oil. When used for long periods of time, some of them elute after use on the hair, so there are drawbacks such as increased squeaky feeling and greasyness when used in large quantities or when used for a long time. .

Further, in order to impart smoothness to hair, cationic surfactants have been conventionally used in hair styling agents. Among such cationic surfactants, cationic polymers, which are particularly high molecular compounds, are widely used because they are water-soluble and have excellent fixing and setting power for hair. However, cationic surfactants impart a stiff feel and do not impart the desired gloss or sufficient smoothness to the hair.

[0007]

SUMMARY OF THE INVENTION Accordingly, the present inventors
In view of the above prior art, it dissolves or disperses stably in a very wide range of solvents such as water and hydrophilic solvents, has a large fixing setting force on hair, and has excellent gloss, smoothness, and comb, which are characteristics of silicone oil. As a result of intensive studies to develop a hairdressing base capable of imparting passability and antistatic properties to hair, a hairstyling base that simultaneously satisfied these properties was finally found, and the present invention was completed. It was just.

[0008]

That is, the present invention provides a compound represented by the general formula (I):

[0009]

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(Wherein R ¹ is a hydrogen atom or a methyl group,
R ² represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 23), 20 to 80% by weight of a monomer (A) represented by the following general formula (II):

[0011]

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Wherein ¹ to 20% by weight of a monomer (B) represented by the formula (wherein R ¹ is as defined above) and a general formula (III):

[0013]

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(Wherein R ¹ is the same as above, and R ³ is an alkoxyl group or an amide group having 1 to 4 carbon atoms) A monomer component containing 5 to 60% by weight of a monomer (C) represented by the following formula: The present invention relates to a hairdressing base comprising:

[0015]

Action and Examples As described above, the base for hair styling of the present invention has the general formula (I):

[0016]

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(Wherein R ¹ is a hydrogen atom or a methyl group,
R ² represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 23), 20 to 80% by weight of a monomer (A) represented by the following general formula (II):

[0018]

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Wherein ¹ to 20% by weight of the monomer (B) represented by the formula (R ¹ is as defined above) and the general formula (III):

[0020]

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(Wherein R ¹ is the same as above, and R ³ is an alkoxyl group or an amide group having 1 to 4 carbon atoms). It was done.

The monomer (A) used in the present invention is, as described above, a monoester (meth) acrylate of polyethylene glycol represented by the general formula (I).

In the present invention, one of the major features is that the monomer (A) is used. When the monomer (A) is used in combination with a monomer having a siloxy group, excellent compatibility with water or a hydrophilic solvent is obtained. While showing, it also has excellent adhesion to hair.

In the general formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrogen atom, a methyl group,
Ethyl group, propyl group, n-butyl group, i-butyl group,
Among them, an s-butyl group, a t-butyl group and a phenyl group, among which a hydrogen atom and a methyl group are preferred because of their excellent dispersibility in water or an aqueous solvent. Further, n is an integer of 2 to 23, preferably 4 to 9. When n is smaller than the above range, dispersibility of the obtained hairdressing preparation base in water or an aqueous solvent decreases. ,
In the case of an aqueous solution, agglomeration occurs. When n is too large, the hardness of the film formed by the obtained hairdressing base decreases, and the setting force decreases. Will begin to fall.

Specific examples of the monomer (A) include, for example, methoxytetraethylene glycol (meth) acrylate, methoxynonaethylene glycol (meth) acrylate, phenoxynonaethylene glycol (meth) acrylate, tetraethylene glycol mono (meth) acrylate And nonaethylene glycol mono (meth) acrylate and methoxytricosaethylene glycol (meth) acrylate. These monomers may be used alone or as a mixture of two or more.

The amount of the monomer (A) used is desirably adjusted so as to be 20 to 80% by weight, preferably 30 to 70% by weight, based on the monomer component to be subjected to polymerization.
When the amount of the monomer (A) used is less than 20% by weight, the water solubility of the obtained hairdressing preparation base decreases, and when it is used as an aqueous solution, the dispersibility decreases and aggregation occurs. In addition, it is difficult to wash and remove the obtained hairdressing base, and if it exceeds 80% by weight, the moisture resistance of the film formed by the obtained hairdressing base may be reduced.

As described above, the monomer (B) used in the present invention is a siloxy group-containing (meth) acrylic acid derivative represented by the general formula (II). In the present invention, there is another great feature in using the monomer (B). The monomer (B) has the property of improving the smoothness and the fixing setting force while giving the obtained base for a hairdressing agent excellent gloss, which is the characteristic of silicone oil. In addition, unlike a commonly used silicone oil blend, a siloxy group is fixed as a single polymer chain in a hairdressing preparation base, so that a portion of the silicone oil is not eluted, Even if used for a long time, the hair will not feel squeaky or greasy.

Specific examples of the monomer (B) include acryloxypropyltris (trimethylsiloxy) silane and methacryloxypropyltris (trimethylsiloxy) silane.

The monomers (B) may be used alone or as a mixture of two kinds.

The amount of the monomer (B) used is desirably adjusted so as to be 1 to 20% by weight, preferably 2 to 15% by weight, based on a monomer component to be subjected to polymerization.
When the amount of the monomer (B) is less than 1% by weight, smoothness such as silicone oil is not provided, glossiness is not recognized, and when the amount exceeds 20% by weight, Since the hardness of the film formed using the obtained hairdressing preparation base decreases, silicone rubber-like properties begin to appear, and the hair may become white when applied to the hair by means such as spraying.

The monomer (C) used in the present invention is, as described above, a (meth) acrylic ester or (meth) acrylamide represented by the general formula (III):
It is a monomer used to improve physical properties such as blocking resistance and smoothness of a film formed by the obtained hair dressing base.

In the general formula (III), R ¹ is a hydrogen atom or a methyl group, and R ³ is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or an amide group.
Among these, butoxy groups are particularly preferred because they have excellent compatibility or dispersibility with aqueous solvents and non-aqueous solvents.

Specific examples of the monomer (C) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Butyl methacrylate, Nt-butylacrylamide, Nt-butylmethacrylamide and the like,
These monomers are used alone or in combination of two or more.

The amount of the monomer (C) used is desirably adjusted so as to be 5 to 60% by weight, preferably 10 to 50% by weight, based on the monomer component used for the polymerization.
When the amount of the monomer (C) used is less than 5% by weight, the film formed by the obtained hair styling preparation base will have reduced blocking resistance and smoothness, and if it exceeds 60% by weight. In some cases, the removability of the film formed by the obtained hair dressing base may be reduced.

The ethylenically unsaturated monomer (D) used in the present invention is used as necessary to impart flexibility and appropriate hardness to the film formed by the obtained hairdressing base and to change the tactile sensation. It is a component to be performed.

Specific examples of the monomer (D) include, for example, (meth) acrylic acid, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate. ) Acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, N −
t-octyl (meth) acrylamide, acrylonitrile, styrene, methylstyrene, chlorostyrene, vinyltoluene, vinyl acetate and the like. In general, when these monomers are blended, compatibility with a propellant when used in the form of an aerosol, for example, Can be improved. These monomers are used singly or in a mixture of two or more kinds, and the amount of use can be selected according to the physical properties of the desired hairdressing base. If it is used in an amount exceeding 30% by weight, the smoothness and transparency of the film formed using the obtained hairdressing preparation base may be impaired.
It is preferably in the range of 3030% by weight, especially 2-20% by weight.

The base for a hairdressing composition of the present invention is obtained by adjusting the desired amount of the monomers (A) to (D) and copolymerizing the same in a hydrophilic solvent.

Here, the hydrophilic solvent is an organic solvent having a solubility in water of 10 g / 100 g of water (25 ° C.) or more.
Specific examples of such a hydrophilic solvent include, for example, aliphatic mono- to tetra-hydric alcohols having 1 to 4 carbon atoms, ethyl cellosolve, butyl cellosolve, dioxane, methyl acetate, dimethylformamide and the like. Dihydric alcohols are particularly preferred for handling as cosmetic ingredients.

Specific examples of the monohydric alcohol include, for example, methanol, ethanol, isopropanol and the like. Specific examples of the dihydric alcohol include:
For example, propylene glycol and the like can be mentioned.

In addition, the base for a hairdressing composition of the present invention may adhere to the skin of the human body.
Among the hydrophilic solvents, ethanol and isopropanol are particularly preferred.

In the copolymerization, a monomer mixture comprising the monomers (A) to (D) is dissolved in the hydrophilic solvent, a polymerization initiator is added, and the mixture is heated under a stream of an inert gas such as nitrogen gas. It is performed by stirring while stirring.

The polymerization initiator is not particularly limited as long as it is generally used in a solution polymerization method. Specific examples thereof include peroxides such as benzoyl peroxide and lauroyl peroxide, azobis Examples include azo compounds such as isobutyronitrile. When an acrylate-based monomer is selected from monomers to be subjected to polymerization, an azo-based compound may be used because a cross-linking gelation may occur when a peroxide is used as a polymerization initiator. preferable.

In the polymerization, the hydrophilic solvent is preferably used by adjusting the concentration of the monomer mixture to about 20 to 70% by weight. When the concentration of the monomer mixture is more than 50% by weight, the polymerization is carried out by dividing the monomer mixture and gradually adding the monomer mixture to avoid rapid generation of polymerization heat and to carry out the polymerization safely. Is preferred.

The polymerization temperature cannot be unconditionally determined because it varies depending on the type of polymerization initiator used, but it is usually preferable to set the 10-hour half-life temperature of the polymerization initiator, especially the hydrophilic solvent used. It is preferable that the temperature is close to the reflux temperature because polymerization with higher reproducibility can be performed.

If the polymerization time is shorter than 8 hours, the polymerization may be incomplete and unreacted monomers may remain. Therefore, the polymerization time should be 8 hours or more, preferably 12 to 36 hours. Is desirable.

The presence or absence of the residual monomer is determined by
It can be performed by confirming whether or not a double bond exists by a general method, for example, the PSDB method.

The hairdressing base of the present invention thus obtained has a copolymer having a weight-average molecular weight of about 10,000 to 150,000, and can be used as it is or without solvent. However, in order to further impart water solubility, for example, when (meth) acrylic acid is used as the monomer (D), neutralization is performed by adding, for example, a water-soluble basic substance to the base for a hairdressing agent. Is preferred. In this case, the neutralization ratio is preferably 50 to 90 mol%. When the neutralization ratio is less than 50 mol%, the water solubility tends to decrease, and the dispersibility in water tends to decrease. When the neutralization ratio exceeds 90 mol%, the obtained hair styling agent There is a tendency that the water resistance of the film formed using the base for use is reduced.

Examples of the water-soluble basic substance include ammonia water, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, morpholine, aminomethylpropanol, aminomethylpropanediol, aminomethyl Ethyl propanediol and the like are mentioned, and these compounds are usually used alone or in combination of two or more.

When the hair styling base of the present invention is used as an aerosol, the hair styling base is dissolved in, for example, the hydrophilic solvent used as the polymerization solvent, and a propellant or other additive is used. The aerosol container may be pressurized and filled together with an auxiliary agent and sealed. In this case, it is generally desirable that the mixing ratio of the various components to be filled in the aerosol container is appropriately adjusted depending on the intended use or the like.

Next, the base for a hairdressing composition of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 A 500 ml five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, a dropping funnel and a stirrer was charged with 55 parts of methoxynonaethylene glycol methacrylate (parts by weight, the same applies hereinafter). 5 parts of roxypropyltris (trimethylsiloxy) silane, 40 parts of t-butyl methacrylate and 150 parts of ethanol were added thereto.
-0.2 parts of azobisisobutyronitrile was added, and the mixture was heated and refluxed at 80 ° C under a nitrogen stream while stirring. Six hours after the start of the polymerization, 0.2 part of α, α'-azobisisobutyronitrile was added, and the reaction was completed for another 6 hours to complete the reaction.

When the resin solid content of the obtained hairdressing preparation base was 40% by weight, the weight average molecular weight of the resin composition was measured.
72000.

The appearance and water solubility of the obtained hair dressing base were examined according to the following methods. Table 2 shows the results.

(Appearance) The appearance of the obtained hairdressing preparation base was visually observed.

(Water-soluble) 45 g of water was added to 5 g of a 40% ethanol solution of the resin composition, and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: Completely dissolved within 5 minutes. B: Dissolve completely within 15 minutes. C: Turbidity occurs.

Examples 2 to 10 and Comparative Examples 1 and 2 A hairdressing preparation base was obtained in the same manner as in Example 1 except that the respective monomer components were changed as shown in Table 1.

However, in Example 5 and Comparative Example 2, the obtained resin composition was cooled to 50 ° C. or less, a 40% ethanol solution of aminomethylpropanol was added, and the acid neutralization rate was reduced to 80 mol%. And

The weight average molecular weight and physical properties of the obtained hairdressing preparation base were examined in the same manner as in Example 1. The results are shown in Tables 1 and 2, respectively.

The abbreviations in the table mean the following.

MNEM: methoxynonaethylene glycol methacrylate MNEA: methoxynonaethylene glycol acrylate MTCEM: methoxytricosaethylene glycol methacrylate MPTMS: methacryloxypropyl tris (trimethylsiloxy) silane TBM: t-butyl methacrylate TBA: t-butyl acrylate EM: Ethyl methacrylate IBM: i-butyl methacrylate IPM: i-propyl methacrylate MAA: methacrylic acid LM: lauryl methacrylate SM: stearyl methacrylate HPM: hydroxypropyl methacrylate DAAM: diacetone acrylamide MAAM: methacrylamide NVP: N-vinylpyrrolidone VA

[0062]

[Table 1]

[0063]

[Table 2]

From the results shown in Table 2, the first embodiment of the present invention was obtained.
It can be seen that the hair styling preparations obtained in Nos. To 10 were all excellent in appearance and water solubility.

Formulation Examples 1 to 10 and Comparative Formulation Examples 1 to 3 7.5 g of an ethanol solution containing 15% of the resin component of the hairdressing preparation base obtained in Examples 1 to 10 and Comparative Examples 1 to 2 and purification An aerosol container (full amount: 80 ml) was charged with 2.5 g of water and 5 g of dimethyl ether as a propellant, and a valve was attached thereto to produce an aqueous hairdressing aerosol product.

Further, methylpolysiloxane (n = 10) (L-45, manufactured by Nippon Unicar Co., Ltd.) was used based on the solid content of the hairdressing preparation base (solid content: 40% by weight) obtained in Comparative Example 2. 5 parts were added, and an aqueous hair styling aerosol product was prepared in the same manner as above except for using 10 g of an ethanol solution adjusted to a solid content of 10% with ethanol (Comparative Prescription Example 3).

Using the obtained aerosol product, the setting power of the hair styling agent and the physical properties of the formed film were examined according to the following methods. Table 3 shows the results.

(Setting power) A hair styling agent was sprayed on 2 g of hair having a length of 25 cm from a distance of 20 cm for 10 seconds, and the hair was wound around a curler having an outer diameter of 1.2 cm, and heated with 40 ° C. warm air for 60 minutes. After drying, remove the hair from the curler, temperature 30 ℃,
Length immediately after hanging vertically in an atmosphere with a relative temperature of 80% (L
₁ ) and the length (L ₂ ) after standing for 1 hour were measured, and the curl retention was calculated from the following equation.

[0069]

(Equation 1)

In addition, those having a curl retention of 60% or more were regarded as passing (indicated by A in the table), and those having less than 60% were rejected (indicated by B in the table).

(Physical Properties of Film) (a) Detergency The hair styling agent was sprayed onto a glass plate 2.5 cm long and 7.5 cm wide from a distance of 20 cm for 5 seconds, and then air-dried at 20 ° C. for 3 hours to form a film. did. This glass plate was immersed in warm water containing 0.2% shampoo at 40 ° C., and the time-dependent change in the dissolved state of the film was examined. The evaluation was performed according to the following evaluation criteria.

(Evaluation Criteria) A: Completely dissolved within 30 minutes. B: Dissolve completely within 40 minutes. C: The film remains after 40 minutes.

(B) Blocking resistance 3 g of a hair dressing agent was uniformly applied to 2 g of hair having a length of 25 cm by spraying. The hair was dried with warm air at 40 ° C. for 60 minutes, and the state of the comb was evaluated using a commercially available comb based on the following evaluation criteria.

(Evaluation Criteria) A: There is no snagging, and the comb passes smoothly. B: Although it is caught, it can pass through the comb. C: It is hard to catch and it is hard to pass through the comb. D: Comb does not pass.

(C) Smoothness The hair styling agent was sprayed onto a glass plate of 2.5 cm × 7.5 cm from a distance of 20 cm for 5 seconds, and then air-dried at 20 ° C. for 3 hours to form a film. Next, the tactile sensation of the formed film surface was examined with a finger, and the smoothness was evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: Completely smooth. B: There is some roughness. C: There is considerable roughness.

(D) Transparency The above hair styling agent was placed on a glass plate 2.5 cm long and 7.5 cm wide by 20 cm.
And spray-dried at 20 ° C. for 3 hours to form a film. Next, the state of the formed film was visually observed and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: Completely transparent. B: Partially whitened. C: The entire surface is whitened.

(E) Gloss 3 g of a hairdressing agent was uniformly applied to 2 g of hair having a length of 25 cm by spraying.

The hair was dried with warm air at 40 ° C. for 60 minutes, and the gloss was visually observed.

(Evaluation Criteria) A: Very glossy. B: There is some gloss. C: No gloss.

(F) Sensation over time A hair styling agent (3 g) was uniformly applied to 2 g of hair having a length of 25 cm by spraying.

The hair was dried with warm air at 40 ° C. for 60 minutes, and the difference in feel between immediately after drying and after 12 hours was observed by applying pressure with a finger.

(Evaluation Criteria) A: No change after 12 hours. B: There is some stickiness after 12 hours. C: Sticky after 12 hours.

[0085]

[Table 3]

From the results shown in Table 3, it can be seen from Example 1 of the present invention.
Each of the hair styling preparations obtained in ~ 10 has the necessary properties as a hair styling preparation, and also has a gloss characteristic of silicone oil that was not present in conventional hair styling preparations as a polymer-based setting agent. You can see that there is.

[0087]

The base for a hairdressing composition of the present invention is soluble in water or a hydrophilic organic solvent, has a large fixing force on hair, and can be easily removed by a hair wash. Moreover, it has excellent blocking resistance.

Furthermore, the base for a hairdressing composition of the present invention has excellent affinity for hair, has properties peculiar to silicone oil, and has the properties of a conventional cosmetic blended with a low-molecular silicone oil. It has no such oily exudation at all times and has excellent gloss.

Claims (2)

(57) [Claims] [Claim 1] General formula (I): Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms, and n is an integer of 2 to 23.
80% by weight, general formula (II): (Wherein R ¹ is as defined above) and 1 to 20% by weight of a monomer (B) represented by the following general formula (III): (Wherein R ¹ is the same as above, and R ³ represents an alkoxyl group or an amide group having 1 to 4 carbon atoms). A monomer component containing 5 to 60% by weight of a monomer (C) represented by the following formula: Base for hair styling. 2. The hairdressing composition according to claim 1, wherein the monomer component contains a copolymerizable ethylenically unsaturated monomer (D) in an amount of 30% by weight or less.