JPH02172906A - Hair cosmetic - Google Patents

Abstract

PURPOSE:To obtain a hair cosmetic, containing a partially crosslinked type organopolysiloxane polymer, a specific liquid oil and volatile oiling agent, excellent in hair conditioning and hairdressing effects and having high persistence with good feeling of use. CONSTITUTION:The objective substance obtained by containing a partially crosslinked type organopolysiloxane polymer in an amount of 0.5-30.0wt.% based on the total composition, a low-viscosity silicone oil and/or liquid ester oil in an amount of 1.0-20.0wt.% based on the total composition and a volatile oiling agent of a volatile hydrocarbon oil and/or fluorocarbons in an amount of 5.0-98.5wt.% based on the total composition as essential components and suitably blending perfumes, preservatives, ultraviolet ray absorbers, surfactants, antioxidants, alcohols, etc., as other ingredients therewith. The cosmetic can be applied as a hair liquid, hair cream, hair spray, hair conditioner, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to hair cosmetics, and more particularly, the present invention relates to hair cosmetics that have good adhesion to hair, have excellent conditioning and hair styling effects, and are long-lasting. This invention relates to a hair cosmetic that is expensive and feels good when used.

[Conventional technology]

In recent years, it has become important for hair cosmetics to have a conditioning effect from the so-called hair care T aspect, which prevents hair damage and damage and protects the hair. To obtain such effects, cationic cellulose derivatives, polyvinylpyrrolidone derivatives, cationic surfactants, silicone derivatives, ester oils, proteins, polypeptides, amino acids, moisturizing ingredients, etc. are used as conditioning agents. They are selected and blended appropriately to take advantage of their respective properties.

Furthermore, when applied to hair, hair cosmetics are desired to have a silky feel without oiliness or stickiness, and to have a smooth and light finish. In order to obtain these effects, silicone derivatives such as silicone oil and silicone rubber among the conditioning agents have to have a non-sticky feel and are water repellent, so they can impart water resistance to the hair and provide a natural bond. It is widely used because it can give

[Problem to be solved by the invention]

However, low-viscosity silicone oils cannot be expected to provide a moisturizing feeling or hair set-holding ability, and when used in large amounts, they can feel oily or sticky, and they also have the drawbacks of being easy to wash off when hair is washed and not lasting. Ta.

In addition, high molecular weight silicone rubbers and resins have a set-holding power on hair and can give shine and smoothness, but it is difficult to apply them as is to hair, so volatile silicone oil, It is used by dissolving it in a volatile solvent such as volatile hydrocarbon oil. However, when high molecular weight silicone is used by simply dissolving it in a volatile solvent, there are problems such as squeaks and poor spreadability due to the solvent, and the applied high molecular weight silicone may be damaged by physical causes such as brushing. It had the disadvantage that it easily peeled off. In addition, the setting power was not sufficiently satisfactory, and the conditioning effect could not be expected much.

Therefore, it has been desired to develop hair cosmetics that feel good when used, have conditioning and hair styling effects, and are highly durable.

[Means to solve the problem]

Under these circumstances, the present inventors conducted intensive research and found that a hair cosmetic containing a partially cross-linked organopolysiloxane polymer, a specific liquid oil, and a volatile oil agent solves the above problems and improves hair care. The present invention has been completed based on the discovery that it has an excellent conditioning effect and can also impart a hair styling effect.

That is, the present invention comprises the following components (A) to (C) (A) partially crosslinked organopolysiloxane polymers.
0.5 to 30.0% by weight (II) One or more liquid oils selected from low viscosity silicone oil and/or liquid ester oil 1.0 to 20
．． 0% by weight (C) One or more volatile oil agents selected from volatile hydrocarbon oils and/or fluorocarbons
The present invention provides a hair cosmetic characterized by containing 5.0 to 98.5% by weight.

The partially crosslinked organopolysiloxane polymer, which is component (A) of the present invention, is, for example, an organopolysiloxane polymer that is insoluble in benzene and has a three-dimensional crosslinked structure that can contain benzene in an amount equal to or more than its own weight. It is a polymer obtained by crosslinking polysiloxane, has a three-dimensional crosslinked structure in part, and has Ra5iO units and R3+O
R55iQ(1,
It may include a % unit and/or a Si unit.

Examples of R in each of the above-mentioned structural units include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, and a propyl group, an aryl group such as a phenyl group and a tolyl group, and an aliphatic unsaturated group such as a vinyl group. They may be of the same type or different types.

Although organopolysiloxane is insoluble in benzene,
In order to obtain an organopolysiloxane polymer structure having a three-dimensional crosslinked structure that can contain benzene in an amount equal to or more than its own weight, R51O,, s units and/or SiO* units and R
, SiO units and/or RiS+ (1°, , units) must be in an appropriate range, and if the ratio of R51Ot, s units and/or 5t02 units is not sufficiently large, the organopolysiloxane will not be sufficient. It does not form a three-dimensional crosslinked structure and becomes soluble in benzene, which is undesirable.
RzSi port unit and/or R5Si port. , S units, if there are too many R310, s units and/or 5iOz units, the organopolysiloxane will take on a strong crosslinked structure, and although it is insoluble in benzene, it will contain only less than its own weight of benzene. First, if it is mixed with a low-viscosity silicone oil of component (B) or a volatile oil agent of component (C), which will be described later, separation and discharge will occur, making it difficult to use.

The ratio of R5Si units to R31O+, s units in the organopolysiloxane polymer used here, which is insoluble in benzene and can contain benzene in an amount equal to or more than its own weight, is highly influenced by the molecular weight of the entire organopolysiloxane polymer. Although it is difficult to specify, a ratio of 1 to 3021 is desirable.

R11+0+, when the number of s units exceeds this ratio, it becomes a hard organopolysiloxane polymer and can only contain benzene in an amount equal to or less than its own weight. ) When the component (2) is mixed with a volatile oil agent, the organopolysiloxane polymer does not swell sufficiently, and the silicone oil separates and is discharged, making it impossible to maintain stability. On the other hand, if the R5Si unit exceeds the above range, the structural viscosity becomes poor, which is not preferable for use.

The organopolysiloxane polymer described above, which is insoluble in benzene but has a three-dimensional crosslinked structure that can contain benzene in an amount equal to or more than its own weight, can be synthesized by various methods such as those shown below.

(2) A catalytic amount of an alcoholic aqueous solution of an alkali metal hydroxide is added to an organohydrodiene polysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule and heated to carry out a dehydrogenation reaction and a condensation reaction.

■ An organohydrodiene polysiloxane having at least two silicon-bonded hydrogen atoms in one molecule and an organopolysiloxane having at least two silicon-bonded hydroxyl groups in the other molecule in a catalytic amount of alkali metal water. Heating in the presence of oxides, platinum compounds, etc.
Perform a dehydrogenation condensation reaction.

(2) An organopolysiloxane having at least two hydroxyl groups directly bonded to silicon atoms in one molecule is heated in the presence of a catalytic amount of an alkali metal hydroxide or an organotin compound to carry out a hydrophilic condensation reaction.

■An organopolysiloxane having at least two hydroxyl groups directly bonded to silicon atoms in one molecule and an organopolysiloxane having at least two alkoxy groups bonded to silicon atoms in the other molecule are oxidized with a catalytic amount of alkali metal hydration. The dealcoholization reaction is carried out by heating in the presence of organic compounds or organometallic tin compounds.

Although it is insoluble in benzene by any of these methods,
An organopolysiloxane polymer having a three-dimensional crosslinked structure that can contain benzene in an amount equal to or less than its own weight can be easily obtained.

In addition, the partially crosslinked organopolysiloxane polymer of component (A) is an organopolysiloxane polymer that is insoluble in silicone oil but swells sufficiently, including (a) organohydrodiene polysiloxane and (b) aliphatic It is a polymer obtained by addition polymerizing an unsaturated group-containing organopolysiloxane, and examples thereof include those in which -g has a three-dimensional crosslinked structure.

The organohydrodiene polysiloxane (a) used here has H5iO+, s unit, R8i port 1. , unit, R) ISiO unit, R*SiO unit, R2H5iO
0,, unit, R5Si mouth. , units, etc., and the molecular structure of this substance may be linear, branched, or cyclic, and each molecule contains at least two hydrogen atoms bonded to silicon atoms. . Moreover, it is more preferable that the organohydrodiene polysiloxane is straight-shaped in order to control the organopolysiloxane polymer synthesis reaction.

In addition, the hydrogen atoms bonded to the silicon atoms (=SiH bonds) in this organohydrodiene polysiloxane are generally considered to be included in the molecular chain, but may also be at the end of the molecular chain. The amount of these Mi-SiH bonds is usually 1 to 20 mol% when the molecular structure is linear or branched, and preferably 1 to 50 mol% when the molecular structure is cyclic. There are 50 organic groups
Preferably, at least mol% is methyl group.

The aliphatic unsaturated group-containing organopolysiloxane (b) used at the same time contains at least two aliphatic unsaturated groups bonded to a silicon atom in one molecule. Examples of the organopolysiloxane include a vinyl group and an aryl group, but a vinyl group-containing sulganovinylpolysiloxane is generally exemplified.
in1. s unit, R51O+, s unit, R(CH=
C) It) SiO unit, R*SxO unit, Ra (CH=
C) Iz) SIOo, s unit, R55iOo, s unit, etc., and the molecular structure of this product may be straight, branched, or cyclic, and each molecule contains an aliphatic compound bonded to a silicon atom. It contains at least two unsaturated groups, such as vinyl groups. The aliphatic unsaturated group-containing organopolysiloxane used here is preferably linear in order to control the organopolysiloxane polymer synthesis reaction.

Furthermore, this organovinylpolysiloxane is usually considered to have a linear structure in which both ends of the molecular chain are blocked with dimethylvinylsilyl groups, but this vinyl group may be included in the chain, and this vinyl group is is 1 to 20 mol% when the molecular structure is linear or branched, and 1 to 5 mol% when the molecular structure is cyclic.
The content is preferably 0 mol %, and it is preferable that 50 mol % or more of the organic groups other than vinyl groups are methyl groups.

A hydrogen atom bonded to a silicon atom that is a reactive group in each molecule of (a) Suruganohydrogenpolysiloxane and (b) aliphatic unsaturated group-containing organopolysiloxane, such as organovinylpolysiloxane. Alternatively, the inclusion of at least two vinyl groups in one molecule is essential for the addition polymer of the two to partially form a three-dimensional structure. In addition, the content of each of these reactive groups in the organopolysiloxane is from 20 mol% when the molecular structure is linear or branched.
In addition, in the case of a cyclic material, if it exceeds 50 mol%, it becomes a hard polymer, and the low viscosity silicone oil of the component (B) described later and the volatile oil agent equivalent to (C) tL are included in the three-dimensional crosslinked structure. It has been recognized that this tends to make it difficult to maintain stable storage due to separation and discharge. Conversely, if the content is less than 1 mol%, the structural viscosity tends to be poor. Therefore, although not limited to this, the content of the reactive group is 1 to 20 mol% when the molecular structure is linear or branched, and 1 to 50 mol% when the molecular structure is cyclic.

In addition, the organic group R of the organohydrodiene polysiloxane (a) may be an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an aryl group such as a phenyl group or a tolyl group, a cyclohexyl group, or a cyclohexyl group thereof. Unsubstituted or substituted-valent hydrocarbon groups, excluding aliphatic unsaturated groups such as vinyl groups, selected from groups in which some or all of the hydrogen atoms bonded to the carbon atoms of the group are substituted with halogen atoms, cyano groups, etc. Examples are given below.

A typical example of this is (C1l=)ss+low -, child (CHs) 2siO→
-7, + CHsHSi03-T%5i(CHs)s
(However, p=10-500% Q=2-50) A suitable material is methylhydrodiene polysiloxane.

Further, the organic group R of the organovinylpolysiloxane which is the aliphatic unsaturated group-containing organopolysiloxane (b) is the same as R of the organohydrodiene polysiloxane.

A typical example of this is (CH2=C)l) (CH3) 2siO-1÷(
CHs)aSiO→-rl-3i(CHs)i(CH=
CL), (however, r = 10 to 100), or (CH3)3Slrho+ (CH-)zsiOtoT1
Volume (C)l=CHt)CHsSiOH.

-3i(C)I-)s (However, m=10~500
, n=2 to 50), which may be a mixture and are suitable materials.

The addition reaction between the organohydrodiene polysiloxane (a) and the aliphatic unsaturated group-containing organopolysiloxane (b) may be carried out by a conventionally known general method. For example, after blending the appropriate organohydrodiene polysiloxane and organovinyl polysiloxane in a molar ratio of the silicon-bonded hydrogen group and the vinyl group, which are each reactive group, in the range of 1/3 to 3/1, By adding an addition polymerization catalyst such as platinum or palladium and stirring while heating, the desired organopolysiloxane polymer insoluble in silicone oil can be easily obtained. In particular, as the addition polymerization catalyst, it is preferable to use chloroplatinic acid described in Japanese Patent Publication No. 33-9969.

These partially crosslinked organopolysiloxane polymers are blended in an amount of 0.5 to 30.0% by weight (hereinafter simply expressed as %) in the total composition, and when less than 0.5%, sufficient conditioning and hair styling effects are obtained. If it exceeds 30.0%, it will spread on the hair too hard or feel sticky, which is not preferable in terms of feeling of use.

As the liquid oil which is component (B) of the present invention, a low viscosity silicone oil or liquid ester oil which is liquid at room temperature is used. As a low viscosity silicone oil, the viscosity is approximately 100cs
Examples of liquid ester oils include isopropyl myristate, isopropyl palmitate, cetyl isooctanoate, isotridecyl isononanoate, and decyl oleate. Examples include. One or more of these liquid oils can be selected and used as required, and are blended in an amount of 1.0 to 20.0% in the total composition. 1.0%
If it is less than 20.0%, it is difficult to obtain the desired effect, and if it exceeds 20.0%, it is difficult to spread onto the hair, the drying speed is slow, and the hair feels sticky, which is not preferable.

In the present invention, when the liquid oil of the component (8) is used, it is possible to prevent the hair from becoming squeaky, to obtain a smooth feeling of use, and to improve the spreadability on the hair. It prevents the polymer from easily falling off from the hair after use, maintains conditioning effects such as moisturizing and smoothness, luster, and hair styling effects, and further improves the combination with (C) a volatile oil agent described later. Depending on the situation, the drying speed after use can be controlled.

In addition, as the volatile oil agent which is component (C) of the present invention,
Volatile hydrocarbon oils or fluorocarbons are used. Examples of volatile hydrocarbon oils include low-boiling liquid isoparaffins with a boiling point of 260°C or less, such as IP Solvent (all manufactured by Idemitsu Oil Co., Ltd.), Isopar (manufactured by Esso Chemical Co., Ltd.), and Scherzl (manufactured by Shell Chemical Co., Ltd.); n-octane, n-octane; Examples include low-boiling point liquid paraffins such as -decane, and examples of fluorocarbons include trichlorotrifluoroethane (Freon 113) and 70 linat, which are liquid at room temperature. One or more of these volatile oils can be selected and used as required, and are blended in an amount of 50 to 98.5% in the total composition. If it is less than 5.0%, it is difficult to obtain the desired effect, which is not preferable.

In the present invention, when these volatile oils are used, (A)
The partially cross-linked organopolysiloxane polymer component can be uniformly adhered to the hair to improve the finish, and since it does not volatilize and remain after use, it does not adversely affect the feeling after use.

In addition to the above-mentioned essential ingredients, the hair cosmetic of the present invention may also contain fragrances, preservatives, ultraviolet absorbers, surfactants, antioxidants, polymer compounds, polyhydric alcohols, lower alcohols, water, and colorants, as required. Pigments, cosmetic ingredients, and the like can be blended within a range that does not interfere with the effects of the present invention.

To produce the hair cosmetic of the present invention, first, the partially crosslinked organopolysiloxane as the component (A) is appropriately selected from the low viscosity silicone oil of the component (B) or the volatile oil agent as the component (C). Knead with other ingredients to swell. In this case, the mixing ratio of the partially crosslinked organopolysiloxane and the low viscosity silicone oil or volatile oil agent is 5:
The range of 95 to 30 Nia is preferable, and in this range, a composition with a soft gel-like structure can be obtained, so it is preferable for use. Next, the gel composition of the partially crosslinked organopolysiloxane polymer thus obtained is appropriately mixed with other essential ingredients and optional ingredients to obtain the hair cosmetic of the present invention.

The hair cosmetic composition of the present invention can be prepared from a liquid to a soft solid by changing the blending ratio of the above-mentioned essential ingredients, and can also be made into an emulsion or aerosol if necessary.

And it can be applied as hair liquid, hair cream, hair conditioner, hair spray, etc.

〔Example〕

Next, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Hair conditioner: A hair conditioner having the composition shown in Table 1 was prepared, and when used, the moist feeling, smoothness, shine, hair styling ability,
The non-stickiness and adhesion were evaluated. Results first
Shown in the table.

Production method> Components (2) to (6) were added to component (1), kneaded and swollen, and then components (7) and (8) were mixed to obtain a hair conditioner.

Evaluation criteria> ○: Good or present △: Fairly bad or absent ×: Bad or absent 14.5 mol%) and 710 g of dimethylvinylsilyl end-capped dimethylpolysiloxane (average molecular weight 9301 vinyl group 7.7 mol%>710 g) were added and mixed with stirring.To the same mixed solution, 2% chloroplatinic acid was added. 0.5 g of propatool solution was added, the temperature was raised to 70-80°C, and stirring was continued for 2 hours.Then, the pressure inside the system was reduced to 5-10 maHg, and stripping was performed for 30 minutes. Polymerized organopolysiloxane powder with soft white color.

As is clear from Table 1, the hair conditioner of the present invention is not sticky to the hands, can impart a moist feeling when applied to the hair, has a setting power, has excellent conditioning and hair styling effects, and has excellent drying properties on the hair. It adhered well, was long-lasting, had a smooth and silky feel without stickiness, was glossy, and was useful for hair protection. On the other hand, Comparative Product 1 could not impart a moisturized or smooth feeling to the hair.
It was squeaky and easily peeled off, and Comparative Product 2 was unsatisfactory as it spread hard on the hair, was sticky, and dried slowly.

Example 2 Hair cream (type 0/11): (ingredients)
(%) (1) Partially crosslinked organopoly 2,0 siloxane polymer *2 (2) Methylphenyl polysilo 7. Roxane (3) n-decane 6.0 (4) Stearin 1 2.0 (5) Lipophilic monostearic acid 0.5 Glycerin [6) Stearyl alcohol 2.0 (7) Monooleic acid 2 parts 8 parts 0 .5bitan (20B
(8) Sodium monooleate 0.5 (9) Sodium hydroxide 0.05α11.3-Butylene glyco 5.0-L OD carboxyvinyl polymer 0.20 purified water Remaining amount *2 Nitrimethylsilyl terminal Blocked dithyl methylhydrodiene polysiloxane, molecular weight 2300, CHsH3iO to (CHs) asl port = 1 to 41% potassium hydroxide solution (ethanol to water = 2 to 1) was added in an appropriate amount, and the mixture was heated and refluxed to initiate a polymerization reaction. A reaction product was obtained. Next, this reaction product is washed with water to remove the alkali agent, and then air-dried to obtain an organopolysiloxane polymer which is insoluble in benzene and can contain 180% of its own weight in benzene.

(Manufacturing method) Components (1) and (3) are added to component (1), and after kneading and swelling, components (4) to (8) are added thereto and mixed with heating.

Next, the components (9) to 9, which had been heated and mixed in advance, were added to this while stirring to emulsify the mixture, and after cooling, the mixture was filled into a container to obtain a hair cream.

Example 3 Hair cream (w10 type) (ingredients)
(%) (1) Dimethylsiloxane/methyl 3.0l (polyoxyethylene) Siloxane copolymer (2) Partially cross-linked organopolymer 3.0-l xane polymer (same as Example 1) (3) Dimethyl Polysiloxane 10.0 (20
cs) [Xun IP Solvent 1620 7.0 (5
) Sorbitol 12.0 (8N, 3
-Butylene glycol 8,0(7) glycerin
5.0(8) Purified water
Remaining amount (manufacturing method) Components (3) and (4) are added to component (2), kneaded and swollen, and then component (1) is added and mixed. Next, premixed components (5) to (8) were added to this while stirring and emulsified, and the mixture was filled into a container to obtain a hair cream.

Example 4 Hairspray: (Ingredients) (%) (1) Partially crosslinked organopolymer 0.50 xane polymer (
Same as Example 1) (2) Dimethylpolysiloxane 1.0 (50c
s) (3) Freon 113 98.5 (manufacturing method) Component (2) is added to component (1) and after kneading and swelling, the component (
3) was added and mixed, and then filled into an aerosol dispenser to obtain a hair spray.

〔Effect of the invention〕

As detailed above, the hair cosmetic of the present invention has an excellent conditioning effect and a hair styling effect on hair. That is, the hair cosmetic of the present invention has good adhesion and leaves a moist feeling and a moist feeling on the hair. It can give a good shine, the finish is smooth and does not feel sticky, it has a light texture and has a good texture, it has an excellent setting effect, it does not peel off from the hair, it is long-lasting, and it has a smooth finish that does not feel sticky. It prevents damage and has a protective effect.

that's all

Claims (1)

[Claims] 1. Components (A) to (C) (A) Partially crosslinked organopolysiloxane polymer 0.5
~30.0% by weight (B) 1.0 to 20.0% by weight of one or more liquid oils selected from low viscosity silicone oil and/or liquid ester oil (C) Volatile hydrocarbon oil and/or A hair cosmetic comprising 5.0 to 98.5% by weight of one or more volatile oils selected from chlorofluorocarbons.