JPH02188519A - Hairdressing - Google Patents

Abstract

PURPOSE:To obtain a hairdressing, containing two specific kinds of hydrocarbon oils and an organosilicone resin in a specified proportion, having excellent set holding power without causing decomposition and oxidation and emitting irritant smell in preservation for a long period and capable of improving gloss of hair. CONSTITUTION:A hairdressing containing (A) 0.1-50wt.% organosilicone resin consisting of units expressed by the average formula RnSiO(4-n)/2 (R is 1-6C hydrocarbon group or phenyl; n is preferably 1.0<=n<=2.0), (B) 0.1-95wt.% hydrogenated 4C oligomer consisting of a hydrocarbon fraction consisting essentially of an ingredient having the boiling point within the range of 80-260 deg.C expressed in terms of ordinary pressure and (C) 0.1-50wt.% hydrogenated 4C oligomer consisting of a hydrocarbon fraction consisting essentially of an ingredient having the boiling point within the range of 270-360 deg.C expressed in terms of ordinary pressure as active ingredients. An aqueous ingredient and suitable surfactant can be further blended therewith to provide an emulsified composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a hair styling product as a cosmetic for use on hair. More specifically, the present invention relates to a hair styling product comprising a hydrogenated product of 04 oligomer and an organic silicone resin. The hair styling product of the present invention uses two types of hydrogenated C4 oligomers with different boiling point ranges to supplement moisture and oil to the hair, prevent hair breakage and hair loss, and add shine to the hair. It is a cosmetic product that has many hair styling functions in a well-balanced manner as a hair styling agent, including the effect of giving hair a smooth and refreshing look, as well as shaping and maintaining the hair set.

[Prior Art and Problems to be Solved by the Invention] Hair styling products for styling hair and making it last longer include pomades, hair dyes, hair liquids, setting lotions, and hair sprays.

By the way, recently, hair setting products that are not highly oily and sticky like pomades, nor moisturizing like hair creams, and have a dry, saran-like finish have been preferred.

These hair styling products contain gum and resinous polymer compounds that play a role in fixing (setting) the hairstyle. That is, the following polymer compound is used as the setting agent.

Natural gums include gum tragacanth, and synthetic polymer resins include polyvinylpyrrolidone, vinyl acetate copolymer, carboxyvinyl polymer, acrylic resin 5-alkanolamine liquid, methoxyethylene maleic anhydride copolymer, polydimethyl chloride. Methylene piperidium, vinylpyrrolidone/N,N-dimethylaminoethyl methacrylic acid copolymer sulfate (cationic resin), polymethacrylate ester ethanol solution (amphibiic resin)
etc.

Furthermore, ethoxylated cholesterol, silicone derivatives, and the like are added to improve the affinity of the setting agent for hair and the state of film formation on the hair.

In addition, silicone oil,
Oils such as higher alcohols, liquid paraffin, and ester oils, and various surfactants are used.

However, the above-mentioned ethoxylated cholesterol, silicone derivatives, and oils added for the purpose of imparting shine and moisture act as factors that inhibit hair set retention.

As a solution to these drawbacks, Japanese Patent Application Laid-Open No. 61-1
Japanese Patent No. 58914 proposes a hair styling product consisting of 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 technique, it is said that it is possible to impart excellent gloss and smoothness to hair while having high set retention power. However, the hair styling product manufactured according to the description in the above-mentioned publication has the disadvantage that it generates a pungent odor when stored for a long period of time.

Although this pungent odor can be masked to some extent with fragrances, it can be a fatal drawback in the cosmetics field. Furthermore, cosmetics may be used for a long period of time, in which case there is a concern that they may generate a pungent odor. Therefore, it has been desired to improve these drawbacks.

Furthermore, the hair styling products described in the publication cannot necessarily exhibit various hair styling functions in a well-balanced manner.

However, the present inventors have discovered that by actively allowing the hydrogenated product of heavy 04 oligomer to remain in the hair, the various hair styling functions of the hair styling agent can be exhibited in a well-balanced manner. Volatile hydrocarbon oils evaporate when hair styling products are used. Therefore, in the hair styling preparation described in the same publication, the hydrocarbon oil does not remain on the hair, and it is unlikely that the hydrocarbon oil contributes to the hair styling effect on the hair.

The inventors of the present invention have conducted intensive research to solve the above-mentioned drawbacks, and as a result, the present inventors have found that they have excellent hair set holding power, and are able to exhibit many hair styling functions such as gloss and smoothness in a well-balanced manner. We have completed a hair styling product that has good stability over a long period of time.

[Means for Solving the Problems] That is, the present invention has (a) an average formula Rn5tO+a-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) organic silicone resin 0.
1 to 50% by weight, (b) 0.1 to 95% by weight of a hydrocarbon fraction, which is a hydrogenated product of C4 oligomer and mainly contains components with a boiling point in the range of 80 to 260°C in terms of normal pressure, and (c) A hydrogenated product of C4 oligomer, which has a boiling point of 270 to 3 when converted to normal pressure.
Hydrocarbon fraction with mainly components in the range of 60℃ 0.1
The present invention relates to a hair styling product characterized by comprising 50% by weight.

The present invention will be further explained below.

The above organic silicone resins can be manufactured by various methods.

- Examples include Celt, - Formula R35iX, R25iX2.
1' (SiX* and 5IX4 (X represents a hydrolyzable group, such as chlorine, bromine, fluorine, an alkoxy group, such as a methoxy group, an ethoxy group, or an acyloxy group), as the target. Depending on the resin to be used, the solution is added to a suitable solvent such as benzene, toluene, xylene, etc., and the solution is then dissolved in 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 substance is neutralized with a sufficient amount of sodium bicarbonate or an alkaline substance, and the solvent is distilled off to obtain the desired organic silicone resin. The average molecular weight of this organic silicone resin is approximately 1500 to 1.
Preferably up to 0000. If the molecular weight is lower than this, the setting holding power will be insufficient, and if the molecular weight is higher than this, it will be difficult to impart smoothness to the hair, so both are not preferred.

The organic silicone resin of the present invention is 0.1% of the total amount of hair styling product.
~50% by weight. If the amount of organic silicone resin is less than this, the effect of adding organic silicone resin cannot be obtained. On the other hand, if it is added in an amount larger than this range, since the organic silicone resin is a polymer, the set retention force will become too high, which is not preferable.

The hydrocarbon oil to be added to the hair styling product of the present invention is a hydrogenated product of C4 oligomers. This C4 oligomer is composed of isobutylene alone or mainly isobutylene partially copolymerized with butene-1, butene-2, etc.

For example, this C4 oligomer is extracted from the C1 fraction produced by thermally decomposing petroleum, naphtha, butane, etc.
It is produced by polymerizing the B-B fraction containing isobutylene, butene, etc. remaining after removing butadiene as a raw material in the presence of a Friedel-Krach catalyst such as phosphoric acid or aluminum chloride.

This 04 oligomer has a double bond at the end, which can also cause a pungent odor, so it is hydrogenated to become a saturated hydrocarbon. The hydrogenation treatment can be carried out according to a conventional method, and can be easily carried out, for example, 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 oligomers having the desired boiling point range.

In the present invention, 0.1 to 95% by weight of a hydrocarbon fraction, which is a hydrogenated product of C4 oligomer and whose main component is a component having a boiling point in the range of 80 to 260°C calculated at normal pressure, is blended.

Further, 0.1 to 50% by weight of a hydrocarbon fraction, which is a hydrogenated product of the same <C4 oligomer and whose main component is a component having a boiling point in the range of 270 to 360°C in terms of normal pressure, is blended. All of these blending amounts are proportions in the total hair styling product.

By blending a hardly volatile hydrocarbon oil with a volatile hydrocarbon oil, it has become possible to combine the effects of the hydrogenated C4 oligomer on hair. That is, since the hydrocarbon fraction containing mainly components having a boiling point in the range of 80 to 260° C. in terms of normal pressure can serve as a solvent for the organic silicone resin, the blending amount thereof is 0.1 to 95% by weight. Commercially available hydrocarbon oils such as these are manufactured by Nippon Petrochemical under the trade name "Isosol" (registered trademark) 200 (boiling point range of 80 to 145°C when converted to normal pressure) and 300 (boiling point range when converted to normal pressure). 170 to 200°C) and 400 (boiling point range of 200 to 270°C in terms of normal pressure).

In addition, hydrocarbon fractions mainly containing components with boiling points in the range of 270 to 360°C converted to normal pressure can also be used as solvents for organic silicone resins, but 8I should remain in the hair to exert its effect on the hair. Therefore, the mixture t is 01~
It is 50%.

This heavy duty fraction can also be used as a solvent for organic silicone resins, but its solubility is inferior to the above-mentioned light fractions.

It also has a relatively high viscosity. Therefore, it is important to use it together with the above-mentioned light substances.

The hydrocarbon oils described in the above patent publication, namely the product names “Isopar” (registered trademark) and “Tsurtrol”
(registered trademark) and the like contain a considerable amount of propylene as a polymerized unit, and therefore have so-called tertiary carbon in their carbon skeleton. It is unstable to energy such as heat and ultraviolet rays, and decomposition and oxidation easily occur from this carbon atom.

However, C
Since the 4 oligomer has almost no such energetically unstable carbon, it is less likely to undergo decomposition or oxidation even when stored for a long period of time, and as a result, less irritating odor is generated.

In addition to the above organic silicone resin and hydrogenated 04 oligomer, an aqueous component and an appropriate surfactant are blended and emulsified to form a water-in-oil or oil-in-water emulsion composition within a range that does not lose water repellency. You can also do it.

In addition to the above-mentioned essential ingredients, the hair styling product of the present invention may include other ingredients of appropriate types or amounts insofar as they do not impair the effects of the present invention, such as liquid paraffin, squalane, lanolin derivatives, higher alcohols, Various ester oils,
Oils such as silicone oil, polyalkylene gellicol polyether or its carboxylic acid oligoester compound, terpene hydrocarbon oil, cationic, anionic or nonionic surfactants, drugs, and fragrances can be further blended. Even if appropriate amounts of these other ingredients are blended, the hair styling composition of the present invention will hardly impede the set-holding ability and long-term stability of the hair.

[Effects of the Invention] The hydrocarbon oil used in the hair styling product of the present invention is stable because it contains almost no tertiary carbon atoms, which are unstable to energy such as heat and ultraviolet rays, in its skeleton.

Therefore, even if stored for a long period of time, it is less likely to be decomposed or oxidized, so it is less likely to generate a pungent odor.

Odors can also be produced by the production of compounds in quantities that are difficult to analyze. Moreover, the problem of odor is important in the field of cosmetics such as hair conditioners. Therefore, it can be said that the industrial value of the hair styling product of the present invention that solves the problem of odor generation is extremely large.

In addition, since it contains two types of hydrocarbon oils, it has excellent set-holding power and can perform hair styling functions such as gloss and texture in a well-balanced manner.

Therefore, it is most suitable for hair styling products.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples. In addition, in the following, all percentages indicate weight percentages.

Reference Production Example A so-called spent B-B fraction (mainly composed of isobutylene) obtained by removing butadiene from the C4 fraction produced by thermal decomposition of petroleum was polymerized using a phosphoric acid catalyst to produce a C4 oligomer. Next, this oligomer was subjected to hydrogenation treatment using a nickel catalyst according to a conventional method. The bromine number was measured and it was confirmed that hydrogen was added to the double bond.

The following two types of prototype products were obtained by distilling this hydrogenated 04 oligomer.

Type Normal pressure equivalent boiling point ('C) Prototype 2 272-318 Prototype S 282-350 Example 1 Hairspray (1) Nisseki Isosol 200 75.0% (2
) Prototype P 5.0% (3)
has a molecular weight of about 8000, and (GeHs)SiO
+/z unit: (C:H+)zsiO = 5.67:
Organic silicone resin represented by the average formula % formula % consisting of 1 18.5% (4) Methylphenyl polysiloxane 1.0% (5) P, O
, E, (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. To 30 parts by weight of the stock solution, 70 parts by weight of a propellant gas (Freon 11:Freon 12=40:60) was 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) Has a molecular weight of approximately 3000 and (CH+) ss io
+/□ unit: SiO, average formula (C) consisting of unit = 0.8:1 13) +,:++Organosilicone resin represented by SiO+, i, + 7.0% (4) Cetyl-2
- Ethylhexanoate 1.0% (5) Stearyltrimethylammonium chloride 0.2% (6) Ethyl alcohol 70.0% (7) Purified water
The remaining components 1) to (4) above were stirred and dissolved at 70 to 80° C., and separately dissolved components (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 5 10.0% (4) Approx. 20
00, and ((:H3)3Si01/2
Unit: (C614g)2s10 Threat: (CgHs)S
j037□Unit: SiO, =0.9: 0.1:
Average formula (CH3) consisting of 0.2 : 1 r , 2,
1 (C6H5). , l6SiO1,3° Organosilicone resin 30.0% (5) Cetyl-2-ethylhexanoate S, 0% Hair liquid is obtained by melting (1) to (5) above at 50-60°C. I got it.

Comparative Example 1 Hairspray (1) 8 Stone Isosol 200 80.0% (2
) has a molecular weight of about 8000, and ((:,H,)Si
037□Unit: ((:H3)2sio unit=5.67
: Organic silicone resin represented by the average formula % formula % consisting of 1, 18.5% (3) Methylphenylpolysiloxane 1.0% (4) P, ○,
E, (4 mol) stearyl ether 0.5% The above (1) to (4) are dissolved with stirring at 70 to 80°C to obtain a stock solution. For 30 parts by weight of stock solution, injection gas (11:12
=40: 70 parts by weight of 60) was added and filled into an aerosol can to obtain a hair spray.

The following experiments were conducted for the above examples and comparative examples,
The performance as a hair conditioner was evaluated.

Commercially available hair strands (weight 3 g, width 2 cm, length 20
01Il) was sprayed with hairspray for 5 seconds.

0.5 g of hair setting lotion and hair liquid was applied. After curling the hair of these samples and thoroughly drying them, the hair for the test was prepared, i.e., the four types of curled hair strands were heated at 30°C.
, and left for 24 hours under constant temperature and humidity conditions of 90% humidity. Original hair strand length (L), initial curl diameter (L)
e) Measure the curl diameter (LL) after standing for 24 hours,
The curl sotension calculated based on the following formula was taken as the setting force.

The larger the value, the stronger the setting force is.

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

O: excellent Δ: average And (CH3)+S
iO+7□Si037□6HB)2SiO unit: (C:
J@) Si037□: 5iO2=0.9: 0.1
: 0.2 : Average formula consisting of 130.0% 35.0% (CH3) 1.23(CsHs) o
, +aSiO+, 3° Organosilicone resin 30.0% (4) Cetyl-2 = Ethylhexanoate 5.0% was stirred and dissolved in (1) to (4) below to obtain a hair liquid. . Note that this comparative example 2 is based on the above-mentioned Japanese Patent Application Laid-Open No. 61-1589.
It is the same as the hair liquid composition described in Example 4 of Publication No. 14. However, since this was prepared for odor comparison, no fragrance was added.

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

The test method was to place a sample in a sealed opaque glass (frosted glass) and expose it outdoors for 15 and 30 days, and measure the change in odor during that time.

When measuring odor, the following 0
The average value of 10 sensory testers was evaluated on a 3-grade scale of 2 to 2.

Table 2 Evaluation of exposure test results 0: No irritating odor 1: Slightly irritating odor 2: Clearly irritating odor As is clear from the results of the above-mentioned exposure test, the composition described in the above publication does not have an irritating odor. Although the occurrence of
In the composition of the present invention, almost no irritating odor was observed, and even after 30 days of exposure, the level of irritating odor was acceptable for practical use.

Patent applicant: Japan Petrochemical Co., Ltd.

Claims (1)

[Claims] (1) (a) Average formula R_nSiO_(_4_-_n_)
0.1 to 50% by weight of an organic silicone resin consisting of units of _/_2 (R is a hydrocarbon group or phenyl group having 1 to 6 carbon atoms, n is 1.0≦n≦2.0), (b) A hydrogenated product of C_4 oligomer, 0.1 to 95% by weight of a hydrocarbon fraction mainly containing components having a boiling point in the range of 80 to 260°C in terms of normal pressure, and (iii) a hydrogenated product of C_4 oligomer. and the boiling point converted to normal pressure is 270
0 hydrocarbon fractions mainly containing components in the range of ~360℃
．． A hair styling product characterized by comprising 1 to 50% by weight.