JP2715131B2 - Hairdressing fee - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a hairdressing product as a cosmetic used for hair. More particularly, it relates to hair dressing consisting of C ₄ oligomers of hydrogenated product with an organic silicone resin. The hair styling composition of the present invention uses two types of hydrogenated C ₄ oligomers having different boiling points to supplement the hair with moisture and oil, prevent cut hair, loose hair, etc., and provide gloss and moisture to the hair. It is a cosmetic product that has an effect of giving hair a refreshing effect, and has a good balance of many hair styling functions as a hair styling agent, such as styling a hairstyle and holding a set.

[Problems to be Solved by Conventional Techniques and Inventions] Hair styling products that prepare hair styles and make the set last longer include pomade, tics, hair liquids, set lotions, and hair sprays.

By the way, recently, a hair styling product for setting which has strong oiliness and is not tacky like pomade and is not wettable like hair cream and has a dry and smooth finish feeling has been favorably used.

These hair styling materials contain a gum or resinous high molecular compound that has a role of fixing (setting) the hairstyle. That is, the following high molecular compounds are used as the setting agent.

Natural gums include tragacanth gum and the like, and synthetic polymer resins include polyvinylpyrrolidone, vinyl acetate copolymer, carboxyvinyl polymer, acrylic resin, alkanone amine liquid, methoxyethylene maleic anhydride copolymer, polychlorinated Dimethylmethylenepiperidium, vinylpyrrolidone / N, N-dimethylaminoethylmethacrylic acid copolymer sulfate (cationic resin), polymethacrylic acid ester ethanol solution (zwitterionic resin)
And so on.

Further, ethoxylated cholesterol, a silicon derivative, and the like are added to improve the affinity of the setting agent for hair and the state of film formation on hair.

In addition, oils such as silicone oils, higher alcohols, liquid paraffin, and ester oils, various surfactants, and the like are used to give gloss and moisture to hair.

However, the above-mentioned ethoxylated cholesterol, silicon derivatives, and oils added for the purpose of giving gloss and moistness act as an inhibitory factor on the set holding power of hair.

To solve such disadvantages, Japanese Patent Application Laid-Open No.
No. 8914 proposes a hairdressing composition comprising a combination of an organic silicone resin and a volatile hydrocarbon oil having a boiling point in the range of 60 to 260 ° C. at normal pressure.

According to this technology, while having a high set holding power,
It is said that it is possible to impart excellent gloss and smoothness to hair. However, the hair styling manufactured according to the description of the above publication has a drawback that it generates an irritating odor when it is held for a long time.

This irritating odor can be masked to some extent by a fragrance or the like, but can be a fatal drawback in the cosmetics field. Further, cosmetics may be used for a long period of time, in which case there is a concern that a pungent odor may be generated. Therefore, it has been desired to improve such disadvantages.

Furthermore, the hair styling materials described in the publication do not necessarily exhibit various hair styling functions in a well-balanced manner.

However, the present inventors have found that by leaving the C ₄ hydrogenated product of the oligomer of heavy positively to the hair, found that can balance was good exhibit various styling features hair fixatives. Volatile hydrocarbon oils volatilize when the hairdressing agent is used. Therefore, in the hair styling described in the publication, the hydrocarbon oil does not remain in the hair, and the hydrocarbon oil cannot contribute to the hair styling effect on the hair.

The present inventors have conducted intensive studies to solve the above-mentioned drawbacks, and as a result, while having excellent set holding power, can exhibit many hair styling functions such as gloss and smoothness in a well-balanced manner, and A hairdressing composition having good long-term stability has been completed.

[Means for Solving the Problems] That is, the present invention provides (a) an average formula R _n SiO _{(4-n) / 2} (R is a hydrocarbon group having 1 to 6 carbon atoms or a phenyl group, and n is 1.0 ≦ n ≦ 2.0)
0.1 to 50% by weight of an organosilicone resin consisting of: (b) a hydrogenated product of a C ₄ oligomer, which is a hydrocarbon fraction mainly containing a component having a boiling point in the range of 80 to 260 ° C. in terms of normal pressure 0.1 to 95%, a hydrogenated product of Ayobi (c) C ₄ oligomers, consisting of a hydrocarbon fraction from 0.1 to 50 wt% consisting mainly of certain components in the range of the boiling point two hundred seventy to three hundred and sixty ° C. under normal pressure in terms The present invention relates to a hairdressing composition characterized by the following.

 Hereinafter, the present invention will be further described.

The above-mentioned organic silicone resin can be manufactured by various methods. As an example, the general formulas R ₃ SiX, R ₂ SiX ₂ , RSiX ₃ and SiX ₄ (X is a hydrolyzable group such as chlorine, bromine,
A compound represented by fluorine, an alkoxy group, for example, a methoxy group, an ethoxy group, or an acyloxy group) to an appropriate solvent such as benzene, toluene, xylene, etc. This solution is then added to a sufficient amount of water to effect the desired hydrolysis and co-condensation in a suitable acidic solvent.
The aqueous layer is removed from the two-layer system thus obtained, the remaining resinous material is neutralized with a sufficient amount of sodium bicarbonate or an alkaline substance, and the desired organic silicone resin is obtained by distilling off the solvent. Can be The average molecular weight of the organosilicone resin is desirably about 1500 to 10,000.
When the molecular weight is lower than this, the set holding power is insufficient, and when the molecular weight is higher than this, it is difficult to impart smoothness and the like to the hair, so that neither is preferable.

The organic silicone resin of the present invention contains 0.1% of the total amount of the hairdressing composition.
~ 50% by weight. If the amount of the organic silicone resin is smaller than this, the effect of adding the organic silicone resin cannot be obtained. On the other hand, it is not preferable to add a larger amount than this range because the organic silicone resin is a polymer and the set holding power becomes rather high.

Hydrocarbon oils to be added to hair dressing of the present invention is a hydrogenated product of a C ₄ oligomers. The C ₄ oligomers, mainly of isobutylene alone or isobutylene, a portion of butene-1, is obtained by copolymerizing the butene-2.

For example, the C ₄ oligomers, petroleum, naphtha, butane and the like from the C ₄ fraction in produced by thermal decomposition, a B-B fraction including the remainder of isobutylene and butene excluding butadiene as a raw material, It is produced by polymerizing in the presence of a Friedel-Crafts catalyst such as phosphoric acid or aluminum chloride.

The C ₄ oligomer terminated has a double bond, which is also because it can cause irritating odor, and hydrocarbon saturation by performing hydrogenation treatment. The hydrogenation treatment can be carried out according to a conventional method. For example, the hydrogenation treatment can be easily carried out by reacting with hydrogen in the presence of a hydrogenation metal catalyst such as palladium or nickel. Distillation may be performed before or after the hydrogenation treatment to separate the oligomer having the desired boiling point range.

In the present invention, 0.1 to 95% by weight of a hydrocarbon fraction, which is a hydrogenated C ₄ oligomer and has a boiling point of 80 to 260 ° C. in terms of normal pressure, is blended. Also, a hydrogenated product of a C ₄ oligomer, which is a hydrocarbon fraction mainly composed of components having a boiling point in the range of 270 to 360 ° C. in normal pressure.
0.1 to 50% by weight is blended. These amounts are all percentages in the total hairdressing composition.

By blending the sparingly volatile hydrocarbon oil with volatile hydrocarbon oils, it has become possible to combine the effect on hair hydrogenated C ₄ oligomers. That is, since the hydrocarbon fraction mainly composed of components having a boiling point in the range of 80 to 260 ° C. in terms of normal pressure can be used as a solvent for the organic silicone resin, its compounding amount is 0.1 to 95% by weight. Commercially available such hydrocarbon oils are available from Nippon Petrochemical Co., Ltd. under the trade name "Isolzol" (registered trademark) 200 (boiling point range of 80 to 145 ° C in normal pressure), 300 (both in normal pressure). Boiling range 170-200
° C) and 400 (boiling point range from 200 to 270 ° C in terms of normal pressure).

Further, the hydrocarbon fraction mainly composed of components having a boiling point in the range of 270 to 360 ° C. in normal pressure can be a solvent for the organic silicone resin. Therefore, the compounding amount is 0.1 to 50% by weight. This weight fraction can also be a solvent for the organosilicone resin, but its solubility is inferior to the light fraction.
Further, the viscosity is relatively high. Therefore, it is important to use it together with the above light components.

The hydrocarbon oils described in the above-mentioned patent publications, that is, the trade names “Isopar” (registered trademark), “Saltrol”
(Registered trademark) and the like contain a considerable amount of propylene as polymerized units, and thus have a so-called tertiary carbon in the carbon skeleton. This is unstable to energy such as heat and ultraviolet light, and decomposition and oxidation are likely to occur from this carbon atom. However, C ₄ oligomers comprising C ₄ monoolefin present invention, since such energetically unstable carbon has no little, even if the long-term storage less likely to cause degradation and oxidation, as a result stimulation Low odor.

In addition to the organosilicone resin and hydrogenated C ₄ oligomer, and emulsified composition of the aqueous component and the water-in-oil or oil-in-water within a range which does not impair the water repellency by blending emulsifying appropriate surfactant You can also.

In the hair styling composition of the present invention, in addition to the above essential components, as long as the effects of the present invention are not impaired, other components of an appropriate type or in an appropriate amount, for example, liquid paraffin, squalane, a lanolin derivative, a higher alcohol, Various ester oils, silicone oils, polyalkylene glycol polyethers or their carboxylic acid oligoester compounds, oils such as terpene-based hydrocarbon oils, cationic, anionic or nonionic surfactants, drugs and fragrances may be further compounded. it can. Even if an appropriate amount of these other components is blended, the hairdressing composition of the present invention hardly impairs the hair holding power and long-term stability.

[Effect of the Invention] The hydrocarbon oil used in the hairdressing composition of the present invention is stable because it hardly contains a tertiary carbon atom that is unstable to energy such as heat or ultraviolet light in its skeleton. Therefore, even when stored for a long period of time, it is less likely to be decomposed or oxidized, and therefore less irritating odor is generated.

Odors can also be generated with the production of difficult-to-analyze compounds. Moreover, the problem of odor is important in the field of cosmetics such as hair styling. Therefore, it can be said that the industrial value of the hairdressing composition of the present invention which has solved the problem of odor generation is extremely large.

In addition, since two types of hydrocarbon oils are blended, it has an excellent set holding power, and can exhibit well-balanced hair styling functions such as gloss and feel given to hair. Therefore, it is optimal for a hairdressing agent.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples. In addition, below, all% show weight%.

Reference Production Example A so-called Spent BB fraction (mainly isobutylene) from which butadiene was removed from a C ₄ fraction generated by thermal decomposition of petroleum was polymerized with a phosphoric acid catalyst to produce a C ₄ oligomer. Next, the oligomer was subjected to a hydrogenation treatment with a nickel catalyst according to a conventional method. The bromine value was measured, and it was confirmed that hydrogen was added to the double bond. By distillation the hydrogenation C ₄ oligomers to obtain two kinds of prototypes below.

Kind Atmospheric pressure conversion boiling point (° C) Prototype P 272-318 Prototype S 282-350 Example 1 Hair spray (1) Nisseki Isosol 200 75.0% (2) Prototype P 5.0% (3) About 8000 molecular weight And an organic silicone represented by the average formula (CH ₃ ) _0.30 (C ₆ H ₅ ) _0.85 SiO _1.43 which has (C ₆ H ₅ ) SiO _3/2 units: (CH ₃ ) ₂ SiO units = 5.67: 1 Resin 18.5% (4) Methylphenyl polysiloxane 1.0% (5) POE (4 mol) stearyl ether 0.5% The above components (1) to (5) are stirred and dissolved at 70 to 80 ° C to obtain a stock solution. Injection gas (CFC 1
(1: Freon 12 = 40: 60) 70 parts by weight were added and filled into an aerosol can to obtain a hair spray.

Example 2 Set lotion (1) Nisseki Isosol 300 8.0% (2) Prototype P 2.0% (3) It has a molecular weight of about 3000 and (CH ₃ ) ₃ SiO _1/2 unit: SiO ₂ unit = 0.8 1: 1 Organic silicone resin represented by the average formula (CH ₃ ) _1.33 SiO _1.34 7.0% (4) Cetyl-2-ethylhexanoate 1.0% (5) Stearyl trimethylammonium chloride 0.2% (6) Ethyl alcohol 70.0% (7) Purified water residue The above (1) to (4) were stirred and dissolved at 70 to 80 ° C., and separately dissolved (5) to (7) were added to obtain a set lotion.

Example 3 Hair Liquid (1) Nisseki Isosol 200 35.0% (2) Nisseki Isosol 400 20.0% (3) Prototype S 10.0% (4) It has a molecular weight of about 2000 and (CH ₃ ) ₃ SiO _{1 / 2} unit: (C ₆ H ₅ ) ₂ SiO unit: (C ₆ H ₅ ) SiO _3/2 unit: SiO ₂ = 0.9: 0.1: 0.2: 1 Average formula (CH ₃ ) _1.23 (C ₆ H ₅ 3) Organic silicone resin represented by _0.18 SiO _1.30 30.0% (5) Cetyl-2-ethylhexanoate 5.0% The above (1) to (5) were dissolved at 50 to 60 ° C. to obtain a hair liquid.

Comparative Example 1 Hair spray (1) Nisseki Isosol 200 80.0% (2) having a molecular weight of about 8000 and (C ₆ H ₅ ) SiO _3/2 units: (CH ₃ ) ₂ SiO units = 5.67: 1 Average formula (CH ₃ ) _0.30 (C ₆ H ₅ ) _0.85 Organic silicone resin represented by SiO _1.43 18.5% (3) Methylphenyl polysiloxane 1.0% (4) POE (4 mol) stearyl ether 0.5% The above (1) ) To (4) are stirred and dissolved at 70 to 80 ° C to make a stock solution. 70 parts by weight of a propellant gas (CFC 11: CFC 12 = 40: 60) was added to 30 parts by weight of the stock solution, and the mixture was filled in an aerosol can to obtain a hair spray.

The following experiments were performed for the above Examples and Comparative Examples, and the performance as a hairdressing agent was evaluated.

Commercial hair strands (weight 3g, width 2cm, length 20cm)
Was sprayed with a hair spray for 5 seconds. On the other hand, 0.5 g of set lotion and hair liquid were applied. The hair of these samples was curled and dried thoroughly before being tested.

That is, four types of curled hair strands are used for 30
Leave for 24 hours under constant temperature and humidity of 90 ° C and humidity of 90%. Original hair strand length (L), initial curl diameter (L
e) The curl diameter (Lt) after standing for 24 hours was measured, and the curl retention calculated based on the following equation was used as the set force. The larger the value, the stronger the setting force.

Further, gloss and feel were evaluated by a sensory test according to the following evaluation criteria. The results are summarized below.

Comparative Example 2 Hair Liquid (1) Isopar (registered trademark) A 30.0% (2) Saltrol (registered trademark) A 35.0% (3) having a molecular weight of about 2000 and (CH ₃ ) ₃ SiO _1/2 units : (C ₆ H ₅ ) ₂ SiO unit: (C ₆ H ₅ ) SiO _3/2 : SiO ₂ = 0.9: 0.1: 0.2: 1 Average formula (CH ₃ ) _1.23 (C ₆ H ₅ ) _0.18 SiO _1.30 30.0% (4) Cetyl-2-ethylhexanoate 5.0% The above (1) to (4) were stirred and dissolved to obtain a hair liquid. Comparative Example 2 was the same as the hair liquid composition described in Example 4 of JP-A-61-158914. However, a fragrance was not added because it was prepared for comparing odors.

(Exposure Test) An exposure test was performed on the hair liquids of Example 3 and Comparative Example 2.

In the test method, the sample was sealed and placed in opaque glass (frosted glass) and exposed outdoors for 15 days and 30 days, and the change in odor during that time was measured.

In the measurement of the odor, the irritating odor of the sample was evaluated by the following three levels from 0 to 2 and indicated by the average value of 10 sensory test measurers.

As is clear from the results of the above-mentioned exposure tests, the composition described in the above publication showed generation of an irritating odor, but the composition of the present invention showed almost no generation of irritating odor. Even after a day, the degree was practically acceptable.

Claims (1)

(57) [Claims] (1) An average formula R _n SiO _{(4-n) / 2} (R is a hydrocarbon group having 1 to 6 carbon atoms or a phenyl group, and n is 1.
An organic silicone resin having a unit of 0 ≦ n ≦ 2.0) 0.1 to 5
0% by weight, (b) a hydrogenated product of a C ₄ oligomer, 0.1 to 95% by weight of a hydrocarbon fraction mainly composed of components having a boiling point in the range of 80 to 260 ° C. in terms of normal pressure; C ₄ a hydrogenated product of the oligomer, hair dressing, characterized in that it consists of a hydrocarbon fraction from 0.1 to 50 wt% consisting mainly of certain components in the range of the boiling point two hundred seventy to three hundred and sixty ° C. at normal pressure terms.