DE9318715U1 - Hair care products - Google Patents

Description

P 92-1348 U Hair care products

The present invention relates to hair care products that are applied in the form of hair sprays, in particular those that do not cause a bad smell when applied and have an improved fixing effect on the hairstyle with a reduced drying time.

Hairsprays are widely used to hold hair and give the hairstyle a certain hold. These hairsprays usually contain film-forming resins as the main ingredients to hold the hair and also an oil to improve the grip, lower alcohols such as ethanol or isopropyl alcohol as a solvent, a propellant gas, etc.

Solvents such as ethanol and propellant gas evaporate and disperse in the air when the hairspray is sprayed. This can cause unpleasant sensations due to the bad and irritating smell that is perceived by the consumer. However, since hairsprays are excellent for holding hair in place and maintaining the hairstyle, they are widely used by consumers. At present, masking fragrances etc. are used to reduce the smell in order to suppress the unpleasant smell, but their effectiveness has so far been inadequate. In recent years, unscented hairsprays have also been brought onto the market, but they have not been able to effectively reduce the inherent smell of the raw materials and the lower alcohols.

JP-A 61-161214 describes a hairspray that contains a certain organic silicone resin, a volatile silicone oil and a propellant gas; the purpose of this hairspray, however, is to achieve a firm hold of the hairstyle, an excellent shine and smooth hair; there is no indication that this can be used to suppress the inherent odor of the raw materials, in particular the lower alcohols.

It is therefore the object of the present invention to create a hair care product that allows satisfactory fixing of the hair without causing an irritating or unpleasant smell to the consumer during use.

The problem is solved by the combined use of a special volatile substance, a special film-forming resin for hair fixation and a liquefied gas or propellant to create a composition that not only has no unpleasant odor when used, but also significantly shortens the drying time after spraying, which plays an important role in hair sprays, so that the hairstyle is fixed immediately and lasts for a long time, and the handle of the treated hair is increased.

In particular, the present invention relates to a hair care product, which is characterized in that it

(A) at least one or more volatile silicone oils of the general formula (I)

CHr

CH2O-Si-O-

_CH3

CHo

Si-O -I

_CH3

CH-CH,

- Itself.

CH-CH,

where m is a number from 0 to 5, and/or the general formula (II)

CH-CH,

-Si-O

CH-CH,

where η is a number from 3 to 7, and/or a volatile hydrocarbon having a boiling point of 0 to 40 ⁰ C,

(B) at least one water-soluble high molecular weight compound,

and

(C) contains at least one propellant gas.

The component (A) of the present invention, a volatile silicone oil represented by the above-mentioned general formula (I), is preferably hexamethyldisiloxane (m = O) or octamethyltrisiloxane (m = I)/ the volatile silicone oil represented by the above-mentioned general formula (II) is preferably hexamethylcyclotrisiloxane (n = 3) or octamethylcyclotetrasiloxane (n = 4).

P92-1348 4

The other possible constituent of component (A), the volatile hydrocarbon, is a hydrocarbon having a boiling point of 0 to 40 ⁰ C (preferably 5 to 40 ⁰ C), and/or a linear or branched hydrocarbon having 4 to 6 carbon atoms; examples are neopentane (boiling point 9.5 ⁰ C), isopentane (boiling point 27.9 ⁰ C) and n-pentane (boiling point 36.1 ⁰ C).

At least one of the possible compounds listed is used as component (A) of the present invention; but several of the volatile silicone oils and/or volatile hydrocarbons mentioned can also be used.

The amount of the above-mentioned component (A) in the hair care product is preferably 0.01 or 0.1, especially 1 to 50 wt.%, in particular 5, especially 10 to 40 wt.%, calculated on the total composition.

A natural or synthetic polymer can be used as the water-soluble high molecular compound which represents component (B) according to the invention.

Examples of natural water-soluble high molecular weight compounds are high molecular weight plant compounds such as gum arabic, gum tragacanth, galactan, guar gum, locust bean gum, karaya gum, carrageenan, pectin, agar-agar, quince seeds (quince), glycyrrhetinic acid; xanthan gum, dextran, succinic glucan, pullulan; as well as high molecular weight protein hydrolysates such as keratin hydrolysates.

The keratin hydrolysates mentioned are obtained by splitting them either by oxidation or reduction and subsequent modification of the thiol group. Keratin starting products are, for example, fur, hair, feathers, nails, horn, hooves, scales and the like, but wool, hair and feathers are particularly preferred. The derivatives in the thiol group include those represented by formulas 3 and 4 below, in particular those of formula 4 are preferred.

Formula 3:

-SCH ₂ COOH, -SCHCOOH,

CH2COOH

-SCH ₂ CHCOOH, CH ₃

-SCH ₂ CH ₂ SO ₃ H,

-SCH ₂ CH ₂

-SCH ₂ CH ₂ COOH, -SCHCHoCOOH,

_CH3
-SO ₃ H, -SSO ₃ H,

_SO3H ,

_CH3

I -SCH ₂ CH ₂ CONHCCH ₂ So ₃ H,

CH ₃ -SCH ₂ CH ₂ So ₂ CH ₂ COOH .

P92-1348

Formula 4:

-SCH ₂ COOH, -SCHCOOH

_CH2COOH

The above-mentioned chemical modification of the thiol group is carried out by known methods, such as those described in "Textile Progress" (N. H. Leon, Volume 7, page 1, 1975), in "Organic Sulfur Compounds" (Shigeru Daikyo, Kagaku Dojin Publication, 1968), or in "Polymer Experimentology Course" (Masami Oku, Volume 12, published by Kyoritsu Shuppan, 1957).

Examples of water-soluble high molecular weight compounds are also high molecular weight starch products such as carboxymethyl starch and methylhydroxypropyl starch; high molecular weight cellulose compounds such as methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, carboxymethylcellulose sodium (CMC), crystalline cellulose and cellulose powder; as well as high molecular weight alginate compounds such as sodium alginate and propylene glycol alginate.

Synthetic water-soluble high molecular weight compounds are

also the following: · \

III .·

II

(1) High molecular weight polyvinylpyrrolidone compounds: These include, for example, polyvinylpyrrolidone and vinylpyrrolidone copolymers with vinyl acetate, an alkylaminoalkyl (meth)acrylate, etc. such as commercially available products, including Luviskol K (a BASF product), PVP K (a GAF product), etc.; Luviskol VA (a BASF product), PVP/VA (a GAF product) etc. as vinylpyrrolidone/vinyl acetate copolymers; Luviskol VAP (a BASF product), etc. as a copolymer of vinylpyrrolidone, vinyl acetate and vinyl propionate; Copolymer 845 (a GAF product) as a copolymer of vinylpyrrolidone and an alkylaminoalkyl acrylate; Copolymer VC-713 (a GAF product) as a ternary copolymer of vinylpyrrolidone, an alkylaminoalkyl acrylate and vinylcaprolactam; and Vem (a product of Ban-Stalfort) as a copolymer of vinylpyrrolidone and acrylic acid/methacrylic acid.

(2) High molecular weight vinyl ether compounds: These include, for example, lower alkyl half esters of copolymers of methyl vinyl ether and maleic anhydride; commercially available products are Gantrez ES-225, ES-335, ES-425 and SP-215 (GAF products).

(3) Acidic high molecular weight polyvinyl acetate compounds: These contain, for example, copolymers of vinyl acetate and crotonic acid; commercially available products are Resin 28-1310 (a National Starch product) and Rubiset CA (a BASF product) as copolymers of vinyl acetate and crotonic acid; Resin 28-2930 (a National Starch product) as a ternary copolymer of vinyl acetate, crotonic acid and vinyl neodecanate; Rubiset CAP (a BASF product) as a ternary copolymer of vinyl acetate, crotonic acid and vinyl propionate; and Dewlex as a copolymer of vinyl acetate and N-vinyl-5-methyl-2-oxazoline.

(4) Acidic high molecular weight acrylic compounds: These include, for example, copolymers of acrylic acid and/or methacrylic acid with an alkyl acrylate and/or alkyl methacrylate, and copolymers of acrylic acid, an alkyl acrylate and an N-alkylacrylamide; commercially available products are Plasize L-53P (a product of Gao Kagaku Co.) and Ultrahold 8 (a product of BASF).

(5) Amphoteric high molecular weight acrylic compounds: These include, for example, substances obtained by copolymerizing a dialkylaminoethyl methacrylate, dialkylaminoethyl acrylate or diacetoneacrylamide, etc. with acrylic acid,

P92-1348 9

methacrylic acid, an alkyl acrylate or alkyl methacrylate, etc., and then amphotericized with halogenated acetic acid; commercially available products are Yukaphomer AM75/R205 and AM75S/SM (products of Mitsubishi Yuka Inc.) · In addition, ternary copolymers of hydroxypropyl acrylate, butylaminoethyl methacrylate and octylamidoacrylate, etc., commercially available e.g. under the trade name of Amphomer 28-4910 and LV-71 (products of National Starch), are suitable.

(6) Basic high molecular weight acrylic compounds: These include, for example, copolymers of alkylacrylamides, acrylates, alkylaminoalkylacrylamides and polyethylene glycol methacrylate (e.g. the water-soluble polymeric compound described in JP-A 2-180911).

Among the above-mentioned water-soluble high molecular compounds, it is preferable to partially or completely neutralize those containing an acid group from the standpoint of improving hair washing performance and feel. The alkalis to be used for neutralization are not specifically limited; the acid group in the high molecular compound may contain an alkali metal salt of sodium, potassium, etc., an ammonium salt or an organic basic salt of ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, aminomercaptopropanediol, triisopropanolamine, glycine, histidine, alginine, etc.

P92-1348 10

The salts of 2-amino-2-methylpropanol and 2-amino-2-methyl-1,3-propanediol are particularly preferable.

In addition, it is also preferable to partially or completely neutralize the basic groups of those high molecular weight compounds that are basic. The acid to be used for neutralization is not particularly limited, but for example, hydrochloric acid, sulfuric acid, phosphoric acid, etc. are preferred among inorganic acids, and acetic acid, lactic acid, glycolic acid, dimethylolpropionic acid, tartaric acid, citric acid, maleic acid, malic acid, etc. are preferred among organic acids.

The proportion of the above-defined component (B) in the hair care product according to the invention is preferably 0.1 to 20% by weight, in particular 1, especially 5 to 10% by weight, calculated on the total composition.

As the propellant gas referred to as component (C) in the composition of the invention, there may be mentioned hydrocarbons such as liquefied alkanes, etc., mainly propane, η-butane, isobutane, etc.; liquefied gases are ethers such as dimethyl ether, methyl ethyl ether, diethyl ether, etc.; and compressed gases such as CO ₂ , N ₂ , N ₂ O, etc. These propellants may be used alone or in combination with one another;

P92-1348 11

their proportion in the composition according to the invention is preferably 30 to 70 wt.%, in particular 40 to 60 wt.% in the case of liquefied propellants, and preferably 0.1 to 10 wt.%, in particular 0.3 to 5 wt.% in the case of a compressed gas.

In the hair cosmetic composition according to the invention, a solvent can also be used to improve the compatibility of the above-mentioned components (A) to (C); solvents suitable for this purpose are in particular linear or branched alcohols with 1 to 4 carbon atoms (preferably ethanol) and/or water. The proportion of said solvent in the hair care product according to the invention is preferably 1 to 55% by weight, in particular 3 to 50% by weight, calculated on the total composition.

Depending on the intended use and as long as the effect of the present invention is not impaired, all other ingredients usually used in hair cosmetic products can also be added to the composition according to the invention. These include, for example, flavorings, surfactants (anionic, non-ionic, cationic), foaming agents, stabilizers, preservatives, pigments, colorants, thickeners, emulsifiers, higher alcohols, waxes, substances

P92-1348 12

to regulate dandruff formation, bactericides, reducing agents, UV absorbers, plant extracts, dyes, suspending agents, liquid paraffin, squalane, lanolin derivatives, oils in the form of ester oils, other silicone oils, polyalkylene glycols, polyethers and their oligocarboxylate compounds, pearlescent agents and terpene hydrocarbons.

The invention is illustrated in the following examples. Example 1

Hair cosmetic compositions Nos. 1 to 6 according to the invention are prepared as shown in Table 1 below using the following method.

Compositions Nos. 1 - 3 are then evaluated in comparison with a commercially available spray (A) for odor, setting power and drying time according to the procedure described below.

The results are summarized in Table 2.

P92-1348 13

Production method:

First, the components, excluding the propellant gas, are mixed or dissolved together to prepare a stock solution, which is placed in a pressure vessel into which the propellant gas is poured, thus resulting in the finished hair cosmetic composition.

Odour assessment procedure:

The intensity of the odor at the time of spraying, the unpleasant odor at the time of spraying, and the intensity of the remaining odor after spraying are assessed based on the following rating:

K)J = very weak

■

O ~ Δ -

/\ = moderate
X = strong

weak

normal

P92-1348 14

Procedure for assessing the
Strength (degree of strength):

A lock of hair 18 cm long and weighing 1.5 g is moistened with water, then wrapped around a rod 2 cm in diameter and left to air dry. After drying, the rod is removed from the curled hair and the hair product is sprayed from a distance of 15 cm. After drying, the hair is hung in a thermohygrostatic device (at 20 ⁰ C and 98% humidity) for 30 minutes, observing the lengthening of the curls to determine the degree of fixation (in %). The degree of fixation is 35% in the case where no hair product is sprayed onto the hair (untreated).

Method for assessing drying time:

Hair, which is placed on a replica of the human head (wig), is placed and sprayed with hair care product from a distance of 15 cm/ immediately afterwards an organoleptic examination of the degree of drying is carried out at specified intervals.

P92-1348 15

Scale for assessing drying time:

(Qj = fast iy = fairly fast

= normal

/ \ = quite slow S\ = slow

■ · • *

■ ·· • *

16

Table 1

composition Dimeric *■'■ oil ** LPC 1 Inventive
Products 3 4 5 6 Trimeres *^ Propellant DMEA 20 2 - - - - Fleeting Cycl.Silicon* ³ Total (weight percent) - - - - - - Silicone or n-pentane - 30 25 - - - fleeting Amphomer LV-71* ⁴
Yukaphomer AM75* ⁵ - - - 30 20 22 Hydrocarbon SP-215* ⁶ - - - - 5 - Water-soluble
high molecular
Connection Polymer M*' - 10 8th - - - Ethanol 8th - - 5 - 3 Water 16 - 11 34 34 32 solvent - 4 - - - 22 1 - 1 1 1 1 55 1 15 - 40 - - - 40 30 - 30 10
0 55 10
0 10
0 10
0 10
0 10
0

•♦ « · · a

17

In the table above, *1 to *8 mean:

*1 Hexamethyldisiloxane

*2 Octamethyltrisiloxane

*3 Octamethylcyclotetrasiloxane

*4 amphoteric polymeric acrylic compound, represented by the

formula below (a National Starch product) *5 amphoteric polymeric acrylic compound represented by the

formula below (a Mitsubishi Yuka product) *6 Vinyl acetate/ether polymer, represented by the

formula below (a GAF product) *7 water-soluble high molecular compound as in the

JP-A 2-180911 described
*8 ot-monoisostearylglyceryl ether

Formula 5:

■f CH ₂ CH Y ₅

CONHC ₈ H ₂₇

CO ₂ Et

CO ₂ CH ₂ CH ₂ NHBu

COOH

Formula 6:

CH-

-(- _CH2C )

CO ₂ R

CH-CH,

CH:

CO ₂ CH ₂ CH ₂ ^ NCH ₂ CO ₂

CH-

Formula 7

OCH-

(CHCH) ₁₅

_CO2H

CO ₂ R

Table 2:

Inventive examples 12 3

Commercially available spray A

Odor

Odor during spraying

Unpleasant smell during spraying

Extent of remaining fragrance after spraying

OOOOOO

OO

Δ Δ

Strength (degree of durability in %)

90 82

Drying time:

Co) (&dgr;) (o>

Ω~ΔΩ

As can be seen from the results in Table 2, all samples according to the invention show no characteristic unpleasant and bad smell during application, and the setting properties and drying times are superior to the reference product.

Claims (2)

P 92-1348 U Claims 1. Hair care products containing (A) at least one or more volatile silicones according to the general formula I . CH, CHO - Si - O CHo CH- SiO CH- Itself: CHr where m is a number from 0 to 5, and/or according to the general formula (II) where η is a number from 3 to 7, and/or a volatile hydrocarbon having a boiling point of 0 to 40 ⁰ C, (B) at least one water-soluble high molecular weight compound, and (C) at least one propellant gas. 2. Hair care product according to claim 1, characterized in that it contains, in each case calculated on the total composition, 0.1 to 50 wt.% of component (A), and 0.1 to 10 wt.% of component (B).