JP5658953B2 - Method for producing hair cosmetics - Google Patents

Description

  The present invention relates to a method for producing hair cosmetics.

Branched polyglycerol-modified silicone is known to have good blending stability, give a high conditioning effect to hair after washing and drying, and is useful as a cosmetic ingredient for hair (Patent Document 1).
On the other hand, (A) General formula (1)
R ¹ O— (AO) _n —R ² (1)
(In the formula, R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 10 carbon atoms, AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and n represents the number of alkyleneoxy groups, which is an average. And a number of 0.5 to 3.5, and R ² represents a hydrogen atom or a methyl group.)
0.2 to 20% by weight of a compound represented by
(B) Surfactant other than component (A) 5 to 60% by weight, and (C) one or more selected from the group consisting of silicones and C15-28 monohydric alcohols 0.1 to 10% by weight It is disclosed that the detergent composition for skin or hair containing the fragrance has excellent foaming property and good usability from washing to after drying (Patent Document 2).

Japanese Patent Laying-Open No. 2005-097150 JP 2008-063294 A

However, when polyglycerol-modified silicone is blended in the hair cleaning composition of Patent Document 2, the viscosity is high and it is difficult to disperse the silicone in the hair cosmetic.
Accordingly, an object of the present invention is to stably mix silicone with a component that imparts a good feeling of use to hair represented by the above-mentioned compounds, and to easily disperse polyglycerol-modified silicone in hair cosmetics. An object of the present invention is to provide a method for producing a hair cosmetic, a hair cosmetic obtained by the production method, and a silicone composition for hair cosmetic that is easy to handle and exhibits excellent effects in the hair cosmetic.

  As a result of intensive studies, the inventor mixed the following specific component (A) with a component (B) at a specific ratio, and then mixed a surfactant other than the component (A) and / or water, The present invention was completed by finding that the component (B) can be easily blended into the hair cosmetic, and that the obtained hair cosmetic has a high conditioning effect. This is presumably because the specific component (A) can finely disperse the component (B) in the cosmetic for hair if this production method is used.

That is, this invention provides the manufacturing method of the cosmetics for hair which has the following process 1 and 2. FIG.
Step 1: The following components (A) and (B) are mixed at a weight ratio of (A) / (B) = 1/10 to 10/1 to obtain a silicone composition (A) General formula ( I)
^{R 1 O- (PO) n /} (EO) m-R 2 (I)
(In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 3 to 10 carbon atoms, PO represents a propyleneoxy group, EO represents an ethyleneoxy group, and the average added mole number n is 1. A compound having a number of 0.5 to 5.0, an average added mole number m of 0 to 1.0, and R ² represents a hydrogen atom or a methyl group. Silicone Step 2: A step of obtaining a hair cosmetic by mixing the silicone composition obtained in Step 1 with a surfactant other than the component (A) and / or water.

  Moreover, this invention provides the cosmetics for hair obtained by the said manufacturing method.

  Furthermore, the present invention contains the components (A) and (B) in a weight ratio of (A) / (B) = 1/10 to 10/1, and the components (A) and (B) The present invention provides a silicone composition for cosmetics for hair having a total content of 90 to 100% by weight.

  According to the present invention, high-viscosity polyglycerol-modified silicone can be easily and stably blended into hair cosmetics, and the resulting hair cosmetics have a high conditioning effect.

It is an optical microscope photograph (450 times) of the hair conditioning agent of Example 15. It is an optical microscope photograph (450 times) of the hair conditioning agent of Comparative Example 13.

Ingredient (A)
In the general formula (I) of the component (A), R ¹ is from the viewpoint of dispersing the component (B) in the cosmetic for hair and from the viewpoint of improving hair unity, moisturizing feeling, gloss, and slipping feeling of the hair. The carbon number is a linear or branched alkyl group or alkenyl group having 3 or more carbon atoms, preferably 6 or more carbon atoms, and more preferably 8 or more carbon atoms. From the viewpoint of dispersing the component (B) in the cosmetic for hair, improving the moisturizing feeling, and suppressing stickiness, it is a linear or branched alkyl group or alkenyl group having 10 or less carbon atoms. . Summing up these viewpoints, R ¹ represents a linear or branched alkyl group having 3 to 10 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 8 to 10 carbon atoms, and still more preferably 8 carbon atoms. An alkenyl group. Further, from the viewpoint of low bromide, a linear or branched alkyl group is preferable. From the viewpoint of low bromide, and the feel as a cosmetic for hair (stickiness, moisturizing feeling, gloss, hair cohesion, hair slipping feeling), R ¹ is preferably one having 8 carbon atoms. Those having 8 carbon atoms are preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 98 mol% or more.

In the general formula (I) of the component (A), PO and EO may be block or random, but the block is preferable, and (PO) n / (EO) m is based on R ¹ O from the viewpoint of low bromide. More preferably, (PO) n and (EO) m are arranged in the order of (addition) in the order of (PO) n and (EO) m.

In the compound of the general formula (I) of the component (A), the average added mole numbers n and m are the viewpoints of dispersing the component (B) in the hair cosmetic and reducing the odor, as a hair cosmetic. It is limited from the viewpoint of touch (stickiness, moisturizing feeling, gloss, hair unity, hair slipping). That is, when the average number of added moles n and m is small, the content of raw material alcohol is increased, the odor is increased, the dispersibility of the component (B) in the cosmetic for hair is lowered, and the moisturizing feeling and the unity of the hair are reduced. , Gloss and slipperiness of the hair are reduced. On the other hand, when the average added mole numbers n and m are large, the elongation at the time of application and the cohesion of the hair are good, but the dispersibility of the component (B) in the cosmetic for hair is lowered, and the sticky feeling is increased. Absent.
The average added mole number n is 1.5 from the viewpoint of dispersing the component (B) in the cosmetic for hair, from the viewpoint of reducing odor, improving the unity and gloss of the hair, the moisturizing feeling, and the slipping feeling of the hair. It is above, 2.0 or more are preferred, 2.3 or more are still more preferred, and 2.5 or more are still more preferred. Further, from the viewpoint of dispersing the component (B) in the cosmetic for hair, reducing the stickiness, and improving the moisturizing feeling, it is 5.0 or less, preferably 3.0 or less, and preferably 2.9 or less. Is more preferable. Taking these viewpoints together, the average added mole number n is 1.5 to 5.0, preferably 1.5 to 3.0, more preferably 2.0 to 3.0, and 2.3 to 2 .9 is more preferable, and 2.5 to 2.9 is still more preferable.
The average added mole number m is 0 or more from the viewpoint of reducing odor, and is 1.0 or less and 0.5 or less from the viewpoint of improving the unity and gloss of the hair, the moisturizing feeling, and the slipperiness of the hair. 0.2 or less is more preferable. Taking these viewpoints together, the average added mole number m is 0 to 1.0, preferably 0 to 0.5, and more preferably 0 to 0.2.
Further, n + m is 1.5 or more from the viewpoint of dispersing the component (B) in the cosmetic for hair, reducing the odor, improving the unity and gloss of the hair, the moisturizing feeling, and the slipping feeling of the hair. Preferably, 2.0 or more is more preferable, and 2.3 or more is more preferable. Further, from the viewpoint of dispersing the component (B) in the cosmetic for hair, reducing the stickiness, and improving the moisturizing feeling, 5.0 or less is preferable, 4.0 or less is more preferable, 3.0 The following is more preferable, and 2.9 or less is more preferable. From these viewpoints, n + m is preferably 1.5 to 5.0, more preferably 1.5 to 4.0, further preferably 1.5 to 3.0, and 2.0 to 3.0. More preferably, 2.3 to 2.9 is even more preferable.

Since the average addition moles n and m in the general formula (I) are averages, the addition moles of individual molecules are distributed. Regarding the distribution of the number of moles of PO added among the number of moles added, the viewpoint of dispersing the component (B) in the cosmetic for hair and the feel as a hair cosmetic (stickiness, moisturizing, gloss, hair From the viewpoint of smoothness and smoothness of hair), the total proportion of the compounds having 2 and 3 PO addition moles in the compound having 1 to 5 PO addition moles contained in the component (A) is: 58-80 mol% is preferable and 60-70 mol% is more preferable.
Furthermore, from the viewpoint of dispersing the component (B) in the cosmetic for hair, and the touch as a hair cosmetic (sticky feeling, moisturizing feeling, cohesion of hair, gloss, slipping feeling of hair), component (A) From the viewpoint of production, the ratio of the compound having 1 addition mole of PO to the compound having 1 to 5 addition moles of PO contained in the component (A) is preferably 9 to 25 mol%, and the addition of PO The proportion of the compound having 2 moles is preferably 30 to 40 mol%, the proportion of the compound having 3 moles of PO added is preferably 20 to 30 mol%, and the proportion of the compound having 4 moles of PO added is 9 to 18 moles. %, And the proportion of the compound having 5 addition moles of PO is preferably 3 to 9 mol%.
The average added mole numbers n and m can be determined by ¹ H-NMR. The distribution of the number of moles of PO added can be determined by gas chromatography, which will be described later. The above value is determined by paying attention to the compound to which only PO is added even when EO is added.

R ² in the general formula (I) is a hydrogen atom or a methyl group from the viewpoint of improving the productivity of the component (A), reducing the stickiness, and improving the hair uniting and hair slipping feeling. As shown, a hydrogen atom is preferred.

In the general formula (I), R ¹ OH wherein n = m = 0, R ² is a hydrogen atom, and R ¹ is a linear or branched alkyl or alkenyl group having 3 to 10 carbon atoms. A compound represented by R ¹ OH wherein R ¹ is a linear or branched alkyl group or alkenyl group having 6 to 10 carbon atoms, more preferably R ¹ is 8 to 10 carbon atoms. The compound represented by R ¹ OH, which is a linear or branched alkyl group or alkenyl group, is preferably not more than 3000 ppm in the component (A) from the viewpoint of low bromide, moisturizing feeling and hair unity. 2000 ppm or less, further 1500 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 ppm or less. The amount of R ¹ OH can be reduced by distillation or the like as described later.

Component (A) used in the present invention uses a basic catalyst and R ¹ OH (wherein R ¹ has 3 to 10 carbon atoms, preferably 6 to 10 carbon atoms, more preferably 8 to 10 carbon atoms). It can be obtained by reacting propylene oxide or propylene oxide and ethylene oxide with a raw material alcohol represented by a linear or branched alkyl group or alkenyl group), and distilling off the raw material alcohol. The average added mole number of propylene oxide or ethylene oxide to be added during the reaction is preferably the above-mentioned values of n, m, and n + m.
Therefore, R ¹ OH contained in the component (A) is derived from the raw material alcohol, and in the general formula (I) of the component (A), R ¹ has 3 to 10 carbon atoms (preferably 6 to 10 carbon atoms). , More preferably 8 to 10 carbon atoms, the carbon number of R ¹ of R ¹ OH contained in the component (A) is also 3 to 10 (preferably 6 to 10 carbon atoms, more preferably 8 carbon atoms). To 10).
As a basic catalyst used for manufacture of a component (A), potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium alkoxide etc. are used, 0.1-5 mol% of the raw material alcohol represented by R < ¹ > OH is used. Preferably, 0.1 to 2 mol% is more preferable. The reaction temperature is preferably 80 to 200 ° C, more preferably 110 to 160 ° C, and the reaction pressure is preferably 0.1 to 0.8 MPa, more preferably 0.1 to 0.6 MPa.

The reaction product can be subjected to distillation as it is, but the basic catalyst can also be removed by distillation after removing the basic catalyst with a neutralizing agent or an adsorbent. Distillation distillation of raw material alcohol means distilling off raw material alcohol by distillation or steam treatment, or combining distillation and steam treatment. The steam treatment means that steam is blown into the reaction composition, and raw alcohol is distilled out of the system together with the steam. Preferred distillation conditions are as follows.
Temperature: 80-200 ° C, preferably 80-150 ° C.
Pressure: 27 kPa (200 torr) or less, preferably 6 kPa (45 torr) or less.
Water vapor amount: 0 to 50 parts by weight with respect to 100 parts by weight of the reaction composition.

Ingredient (B)
The polyglycerol-modified silicone of component (B) is one in which a polyglycerol chain is bonded to the silicone main chain.
As the component (B), glycerol groups or glycidol groups represented by the following structural formulas (1), (2), (3), (4) or (5) are the same or different, and an average of 4 or more bonds. In addition, a branched polyglycerol-modified silicone (hereinafter referred to as “a branched polyglycerol-modified silicone”) in which at least one branched polyglycerol chain containing at least one group represented by the structural formula (1) or (5) is bonded to the silicon atom of the silicone via a linking group. Component (b)).

  The two oxygen atoms in the structural formula (1) may be the same or different from each other and may be a glycerol group or glycidol represented by the structural formula (1), (2), (3), (4) or (5). A glycerol group or a glycidol group represented by the structural formula (1), (2), (3), (4) or (5) is bonded to the oxygen atom of the structural formula (2). The glycerol group or glycidol group represented by the structural formula (1), (2), (3), (4) or (5) is bonded to the oxygen atom of the structural formula (3), and the structural formula ( A glycerol group or a glycidol group represented by the structural formula (1), (2), (3), (4) or (5) is bonded to the two oxygen atoms of 5), which are the same or different.

  This branched polyglycerol chain has a branched glycerol group represented by a structural formula (1) (hereinafter referred to as group (1)) and a glycidol group represented by b structural formula (2) (hereinafter referred to as group). (Referred to as (2)), c glycerol groups represented by structural formula (3) (hereinafter referred to as group (3)), glycerol groups represented as d structural formula (4) (hereinafter referred to as group (4) )), And e branched branched glycerol groups (hereinafter referred to as groups (5)) represented by the structural formula (5). In the branched polyglycerol chain, the groups (1), (2), (3) and (5) may be bonded to each other in any sequence. As the number of groups (1) and / or groups (5) increases, the branched structure develops, and the group (4) is present at the end of each branched chain.

The average total number of bonds (a + b + c + d + e) of the groups (1), (2), (3), (4) and (5) in the branched polyglycerol chain is determined by NMR analysis or molecular weight comparison with the precursor silicone, The number is preferably 4 or more, more preferably 4 to 201, still more preferably 4 to 101, still more preferably 4 to 51, and still more preferably 4 to 21. The branching ratio [(a + e) / (a + b + c + d + e)] in the branched polyglycerol chain is preferably 1/20 or more, more preferably 1/10 or more, further preferably 1/6 or more, and preferably less than 1/2.
In the branched polyglycerol chain, the groups (1), (2), (3), (4) and (5) may be arbitrarily bonded.

  The number of groups (1) (that is, a) is preferably 0 to 100, more preferably 1 to 100, and even more preferably 2 to 100 in the branched polyglycerol chain. 2 to 50 are more preferable, 2 to 25 are more preferable, and 2 to 10 are more preferable.

  The number of groups (4) (that is, d) is preferably 1 to 101, more preferably 2 to 101, still more preferably 3 to 101, and 3 to 51. More preferably, 3 to 26 are present, more preferably 3 to 11 are present.

  The number of groups (2) (ie, b) and the number of groups (3) (ie, c) are the same or different and are preferably 0 to 199, more preferably 0 to 198. 0 to 196 are more preferable, 0 to 96 are more preferable, 0 to 46 are more preferable, and 0 to 16 are more preferable.

  The number of groups (5) (ie, e) is preferably 1 when a is 0, and is preferably 0 or 1 when a is 1 or more. A branched polyglycerol chain containing at least one branched glycerol group represented by the following structural formula (1) via a linking group to a silicon silicon atom, wherein a is 1 or more and e is 0, One bonded, branched polyglycerol-modified silicone is more preferred.

(In the formula, a glycerol group or a glycidol group represented by the above structural formula (1), the following structural formula (2), (3) or (4) is bonded to the two oxygen atoms, which are the same or different.

In this case, the glycerol group or glycidol group represented by the structural formula (1), (2), (3) or (4) is bonded to the two oxygen atoms of the structural formula (1), which are the same or different. A glycerol group or a glycidol group represented by the structural formula (1), (2), (3) or (4) is bonded to the oxygen atom of the structural formula (2), and the oxygen of the structural formula (3) A glycerol group or glycidol group represented by the structural formula (1), (2), (3) or (4) is bonded to the atom. )
The branched polyglycerol-modified silicone preferably has a divalent group having an ether group or an ester group as the linking group that binds the silicon atom of the silicone and the branched polyglycerol chain. From the viewpoint of chemical stability and the like, it is preferably a divalent group having an ether group.

The divalent group having an ether group is preferably a group represented by the general formula (7) (hereinafter referred to as a linking group (7)). In the linking group (7), the (R ⁹ ) _p side is bonded to the silicon atom of the silicone chain, and the (AO) _q side is bonded to the branched polyglycerol chain.

_{^{- (R 9) p -O- (}} AO) q - (7)
(Wherein R ⁹ may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms, an alkenylene group or an arylene group having 6 to 28 carbon atoms, preferably 1 carbon atom) -22 linear or branched alkylene group or alkenylene group, AO is an alkyleneoxy group having 1 to 4 carbon atoms (also referred to as an oxyalkylene group) or an aryleneoxy group having 6 to 10 carbon atoms (also referred to as an oxyarylene group). Preferably an alkyleneoxy group having 1 to 4 carbon atoms, p is a number of 0 or 1, q is a number of 0 to 30, and q AOs may be the same or different.)
The divalent group having an ester group is preferably a group represented by the general formula (8) (hereinafter referred to as a linking group (8)). In the linking group (8), the R ¹⁰ side is bonded to the silicon atom of the silicone chain, and the (AO) _r side is bonded to the branched polyglycerol chain.

—R ¹⁰ —COO— (AO) _r − (8)
(In the formula, R ¹⁰ may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms, an alkenylene group, or an arylene group having 6 to 28 carbon atoms, preferably 1 carbon atom. -22 linear or branched alkylene group or alkenylene group, r is a number from 0 to 30, AO is as defined above, and r AOs may be the same or different.
In the linking groups (7) and (8), bonded to the branched polyglycerol group on the oxygen side of the alkyleneoxy group or aryleneoxy group of AO, and the linking group contains on the alkylene or arylene side of the alkyleneoxy group or aryleneoxy group To an ether group or an ester group.

As substituents in R ⁹ and R ¹⁰ , a hydroxy group, an amino group (1 to 22 carbon atoms), an imino group (1 to 22 carbon atoms), a carboxy group, an alkoxy group (1 to 22 carbon atoms), an acyl group ( C1-C22) etc. are mentioned.

  The most preferred linking group is a linking group represented by the following general formula (9) (hereinafter referred to as linking group (9)). In the linking group (9), the trimethylene side is bonded to the silicon atom of the silicone chain, and the oxygen atom side is bonded to the branched polyglycerol chain.

—CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ O— (9)
Another preferred linking group is a linking group containing an oxyphenylene group. Among such linking groups, a group represented by the following general formula (10) (hereinafter referred to as linking group (10)) or a group represented by the general formula (11) (hereinafter referred to as linking group (11)). ) Is preferred. In the linking group (10), the (R ¹¹ ) _u side is bonded to the silicon atom of the silicone chain, and the (AO) _v side is bonded to the branched polyglycerol chain. In the linking group (11), the (R ¹² ) _z side is bonded to the silicon atom of the silicone chain, and the (AO) _x and (AO) _y sides are bonded to the branched polyglycerol chain.

(In the formula, R ¹¹ is an optionally substituted linear or branched alkylene group or alkenylene group having 1 to 22 carbon atoms, u is 0 or 1, and v is 0 to 30. Number, AO indicates the above meaning, and v AOs may be the same or different.)

(In the formula, R ¹² is an optionally substituted linear or branched alkylene group or alkenylene group having 1 to 22 carbon atoms, z is a number of 0 or 1, and x is 0 to 30. Number, y is a number from 0 to 30, AO is as defined above, and x and y AOs may be the same or different.)
In the linking group (10) and the linking group (11), (R ¹¹ ) _u and (R ¹² ) _z are groups linking the silicon atom of the silicone chain and the phenylene group of the oxyphenylene group contained in the linking group. R ¹¹ and R ¹² are preferably an alkylene group or alkenylene group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene. , Octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene group and the like. Among these, an ethylene, propylene or trimethylene group is more preferable, and an ethylene or trimethylene group is more preferable.

As a substituent which may be present in R ¹¹ and R ¹² , a hydroxy group, an amino group (C1 to C22), an imino group (C1 to C22), a carboxy group, an alkoxy group (C1 to C1). 22), an acyl group (C1-C22), etc. are mentioned.
u and z are 0 or 1, but 1 is more preferable.

  In the linking group (10) and the linking group (11), AO is an oxyalkylene group or an oxyarylene group that connects the branched polyglycerol chain and the oxygen atom of the oxyphenylene group contained in the linking group, Bonded to the branched polyglycerol chain on the oxygen side of the oxyarylene group, and bonded to the oxygen atom of the oxyphenylene group on the alkylene or arylene side of the oxyalkylene group or oxyarylene group. As AO, an oxyethylene group, an oxypropylene group or an oxyphenylene group is preferable, and among these, an oxyethylene group is more preferable.

  v, x and y are each a number of 0 to 30, preferably 0 to 15, more preferably 0 to 5, and most preferably 0. When v, x, and y are non-zero numbers, v AOs, x AOs, and y AOs may be the same or different. It may be an alternating type, a block type, a periodic arrangement other than these, or a random type.

In the linking group (10), the bonding mode of the oxygen atom and the (R ¹¹ ) _u group (the silicon atom on the silicone chain when u is 0) bonded to the phenylene group of the oxyphenylene group is the ortho position, the meta Either the position or the para position may be used, or a mixture thereof may be used. Further, in the linking group (11), any two of the two oxygen atoms bonded to the phenylene group of the oxyphenylene group and the (R ¹² ) _z group (a silicon atom on the silicone chain when z is 0) In addition, the bonding mode may be any of the ortho position, the meta position, and the para position, or a mixture thereof.

  Among the oxyphenylene group-containing linking groups, the most preferable one is a linking group represented by the following general formula (12) (hereinafter referred to as linking group (12)). In the linking group (12), the trimethylene side is bonded to the silicon atom of the silicone chain, and the oxygen atom side is bonded to the branched polyglycerol chain.

  In the linking group (12), the bonding mode of the oxygen atom and trimethylene group bonded to the phenylene group of the oxyphenylene group may be any of ortho, meta, and para positions, and a mixture thereof. However, the ortho position, the para position, or a mixture thereof is more preferable.

  The silicone forming the component (b) is derived from a polysiloxane having two or more silicon atoms, and the shape of the polysiloxane may be linear, branched or cyclic. Moreover, the number average molecular weight of polysiloxane becomes like this. Preferably it is 300-700,000, More preferably, it is 300-200,000, More preferably, it is 1000-20,000. The number average molecular weight can be determined by gel permeation chromatography (hereinafter, GPC) method or the like.

  As the component (b), a linear silicone represented by the general formula (6) (hereinafter referred to as silicone (6)) is preferable.

Wherein R ¹ , R ² , R ³ , t R ⁴ , t R ⁵ , R ⁶ , R ⁷ , R ⁸ are the same or different and are a linking group to which a branched polyglycerol chain is bonded, A linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms, or an aryl group having 6 to 22 carbon atoms, which may have a substituent and may be substituted with a fluorine atom Wherein at ^{least one} of R ¹ , R ² , R ³ , t R ⁴ , t R ⁵ , R ⁶ , R ⁷ , R ⁸ is a linking group to which a branched polyglycerol chain is bonded. t represents a number from 0 to 10,000.)
In silicone (6), R ¹ , R ² , R ³ , t R ⁴ , t R ⁵ , R ⁶ , R ⁷ , R ⁸ other than the linking group to which the branched polyglycerol chain is bonded are A linear or branched alkyl group, alkenyl group or alkoxy group having 1 to 22 carbon atoms which may have a substituent and may be substituted with a fluorine atom, or the number of carbon atoms Examples of the alkyl group having 6 to 22 carbon atoms and having 1 to 22 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, trifluoropropyl and the like. Examples of the alkenyl group having 1 to 22 carbon atoms include a vinyl group and an allyl group. Examples of the alkoxy group having 1 to 22 carbon atoms include methoxy, ethoxy, propoxy, Butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and a phenoxy group. In these, a C1-C12 linear or branched alkyl group, a vinyl group, an allyl group, or a C6-C12 aryl group is preferable, and a C1-C3 alkyl group or a phenyl group is preferable. More preferably, a methyl group, a propyl group or a phenyl group is more preferable, and a methyl group or a phenyl group is still more preferable.

In the silicone (6), the substituents that R ^{1 to} R ⁸ may have include a phenyl group, a hydroxyphenyl group, a hydroxy group, a carboxy group, an amino group (0 to 14 carbon atoms), an imino group, (amino And ethyl) amino group, (dimethylaminoethyl) amino group, polyoxyalkylene group, mercapto group, and epoxy group. When these substituents are present, a propyl group is more preferable as R ^{1 to} R ⁸ .

In the silicone (6), at ^{least one} of R ¹ , R ² , R ³ , t R ⁴ , t R ⁵ , R ⁶ , R ⁷ , R ⁸ , preferably 1 to 10, more preferably Are 1-5, more preferably 1-2 are linking groups to which branched polyglycerol chains are bonded. This linking group may be located at any of the side chain, one end and / or both ends of the silicone (6), or may be a mixture thereof.

Of the silicone (6), one selected from the group consisting of R ^{1 to} R ³ and one selected from the group consisting of R ^{6 to} R ⁸ represent a linking group to which a branched polyglycerol chain is bonded, and the remainder R ^{1 to} R ³ and R ^{6 to} R ⁸ , t R ⁴ , and t R ⁵ are preferably methyl groups.

Further, when the linking group to which the branched polyglycerol chain is bonded is present in three or more selected from t R ⁴ and t R ⁵ , it is preferable to be a side-chain multi-substituted branched polyglycerol-modified silicone. .

  T in silicone (6) shows the number of 0-10,000, Preferably it shows the number of 1-3000, More preferably, it shows the number of 5-500, More preferably, it shows the number of 10-150. .

  The number average molecular weight of the component (b) is preferably 500 to 500,000, more preferably 750 to 200,000, still more preferably 1000 to 100,000. The number average molecular weight is measured by GPC method (standard polystyrene or polyethylene glycol conversion).

  Component (b) is a total number of silicon atoms (Si) in silicone and groups (1), (2), (3), (4) and (5) in the branched polyglycerol chain (hereinafter referred to as glycerol group number). The ratio (G / Si) of (G) is preferably 0.001 to 50, more preferably 0.05 to 10, still more preferably 0.1 to 3, and still more preferably 0.15 to 1.

  In the component (b), a small amount of ethyleneoxy group and / or propyleneoxy group may be present in the branched polyglycerol chain as long as the effect of the present invention is not significantly inhibited. Ethyleneoxy groups and / or propyleneoxy groups may be present randomly in the branched polyglycerol chain, or a plurality of ethyleneoxy groups and / or propyleneoxy groups form a chain and block in the branched polyglycerol chain May be present. In this case, the block composed of a plurality of ethyleneoxy groups and / or propyleneoxy groups may be present in the vicinity of the linking group of the branched polyglycerol chain, may be present at the terminal, or may be present in the middle. You may do it. The ethyleneoxy group and / or propyleneoxy group is preferably present in an amount of 0.001 to 0.5 molar equivalent, more preferably 0.02 to 0.2 molar equivalent.

  Component (b) is a hydrosilylation reaction between a branched polyglycerol having a reactive unsaturated group and a so-called organohydrogen silicone in which a hydrogen atom is bonded to a part of a silicon atom in a silicone chain in the presence of a platinum-based catalyst. It can obtain by the method of making it. A branched polyglycerol having a reactive unsaturated group is obtained by adding glycidol (2,3-epoxy) to a compound having a reactive unsaturated group and a functional group (preferably a hydroxy group or a carboxy group) in the presence of an acidic catalyst or a basic catalyst. -1-propanol) can be obtained by adding and reacting while controlling the addition rate. A branched polyglycerol having a reactive unsaturated group having a high degree of branching can be produced by slowing the addition rate.

In addition, presence of a basic catalyst such as acidic or potassium in silicone having one or more functional groups selected from the group consisting of a hydroxy group, a carboxy group, an amino group, an imino group, a mercapto group and an epoxy group as a reactive group The component (b) can also be produced by a method of adding glycidol and graft polymerization.
Polyglycerol-modified silicones can also be produced by the methods described in JP-A-2005-97150 and JP-A-2004-339244.

(Method for producing hair cosmetics)
The cosmetic for hair of the present invention has the following steps 1 and 2.
Step 1: The above components (A) and (B) are mixed at a weight ratio ((A) / (B)) of 1/10 to 10/1 to obtain a silicone composition Step 2: In Step 1 A step of obtaining a hair cosmetic by mixing the obtained silicone composition with a surfactant other than the component (A) and / or water.

In step 1, components (A) and (B) are mixed to obtain a silicone composition. Here, the component (B) may be added to the component (A), or vice versa. From the viewpoint of improving productivity, it is preferable to add and mix the component (A) into the reaction vessel containing the component (B) after the production of the component (B).
In light of uniformly mixing the components (A) and (B), the mixing temperature is preferably 10 ° C. or higher, and more preferably 15 ° C. or higher. Moreover, 100 degreeC or less is preferable from a viewpoint of suppressing coloring of a silicone composition, and 80 degreeC or less is more preferable. When these viewpoints are put together, the mixing temperature is preferably 10 to 100 ° C, more preferably 10 to 80 ° C, and further preferably 15 to 80 ° C. By mixing, the components (A) and (B) become a substantially uniform solution, and the component (B) is reduced in viscosity, so that handling becomes easy.
The mixing weight ratio [(A) / (B)] of the components (A) and (B) is the viewpoint that the component (B) is uniformly dispersed in the cosmetic for hair, and the productivity in step 2 (handling property). And 1/10 or more, preferably 1/5 or more, from the viewpoint of improving the feel of hair cosmetics (feeling of stickiness, moisturizing, gloss, hair cohesion, hair slipping) 1/4 or more is more preferable. In addition, from the viewpoint of improving the feel as a hair cosmetic (stickiness, hair mass, gloss, moisturizing feeling, hair slipping feeling), it is 10/1 or less, preferably 5/1 or less, and 1/1. The following is more preferable, and 2/3 or less is more preferable. Taking these viewpoints together, the mixing weight ratio [(A) / (B)] of the components (A) and (B) is 1/10 to 10/1, preferably 1/10 to 5/1. 1/5 to 5/1 is more preferable, 1/5 to 1/1 is more preferable, 1/4 to 1/1 is still more preferable, and 1/4 to 2/3 is still more preferable.
In the silicone composition, the total content of the components (A) and (B) is preferably 90 to 100% by weight, more preferably 95 to 95%, from the viewpoint of improving the feel and the degree of freedom of blending as a cosmetic for hair. 100% by weight, more preferably 99-100% by weight.

  In the silicone composition, components other than components (A) and (B) include water, alcohols such as ethanol and isopropanol, organic solvents such as glycols such as propylene glycol and dipropylene glycol, and a low degree of polymerization (low viscosity). Examples include dimethicone, preservatives, and antioxidants.

The viscosity at 30 ° C. of the obtained silicone composition is preferably 20000 mPa · s or less, more preferably 5000 mPa · s or less, and further preferably 2000 mPa · s or less, from the viewpoint of improving the productivity in Step 2. Further, from the viewpoint of improving the productivity (meterability) in Step 2 and the storage stability of the cosmetic for hair, 10 mPa · s or more is preferable, 50 mPa · s or more is more preferable, 100 mPa · s or more is more preferable, and 500 mPa -More than s is still more preferable. Taking these viewpoints together, the viscosity at 30 ° C. of the silicone composition is preferably 10 to 20000 mPa · s, more preferably 50 to 5000 mPa · s, further preferably 100 to 2000 mPa · s, and more preferably 500 to 2000 mPa · s. Further preferred. The viscosity at 30 ° C. of the silicone composition is measured by the method described in the examples below.
The adjustment of the viscosity of the silicone composition is carried out by selecting the mixing weight ratio of the component (A) and the component (B), selecting the R ¹ and n number (PO chain length) of the component (A), the molecular weight of the component (B), This can be done by adjusting the number of moles of glycidol added in the component (B).

  The resulting silicone composition has a low viscosity, can be easily mixed with a surfactant and / or water, and the component (B) can be uniformly dispersed in the surfactant and / or water. Since component (A) as well as component (B) has a high hair conditioning effect, component (A) as well as component (B) can be made into a cosmetic for hair.

In step 2, the silicone composition obtained in step 1 is mixed with a surfactant other than component (A) and / or water to obtain a cosmetic for hair. The silicone composition containing the component (A) and the component (B) can be easily mixed with water and / or a surfactant other than the component (A). can do.
For example, in the case of a hair shampoo, etc., a surfactant other than the component (A), other oil agents, preservatives and the like and water are heated and mixed at 70 to 80 ° C., stirred, and then cooled to 30 to 40 ° C. A silicone composition can be added to obtain a shampoo.
In addition, for example, in the case of a hair conditioning agent, a hair perm agent, a hair color agent, etc., a higher alcohol, a water phase obtained by heating and mixing a surfactant other than the component (A), a preservative and the like at 70 to 80 ° C. An oil phase, which is a mixture of an oil agent, is added and emulsified, and then cooled and a silicone composition is added at 40 to 50 ° C. and cooled to room temperature to obtain a hair conditioning agent.

  The mixing weight ratio of the silicone composition and the surfactant other than component (A) and / or water, that is, the silicone composition / [surfactant other than component (A) + water] varies depending on the product to be obtained. From the viewpoint of improving the unity and gloss of the hair, the moisturizing feeling, and the slipperiness of the hair, preferably 1/10000 or more, more preferably 5/10000 or more, further preferably 1/1000 or more, and further more preferably 2/1000 or more. preferable. Moreover, 2/10 or less is preferable from a viewpoint of suppressing a sticky feeling and improving a moisturizing feeling, 1/10 or less is more preferable, 5/100 or less is further more preferable, and 3/100 or less is more preferable. From these viewpoints, the silicone composition / [surfactant other than component (A) + water] is preferably 1/10000 to 2/10, more preferably 5/10000 to 1/10, and 1/1000. ~ 5/100 is more preferable, and 2/1000 to 3/100 is further more preferable.

Known surfactants can be used as the surfactant other than the component (A).
For example, as the anionic surfactant, those of sulfuric acid type, sulfonic acid type, carboxylic acid type, phosphoric acid type and amino acid type are preferable, for example, alkyl sulfate, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether. Sulfate, sulfosuccinic acid alkyl ester salt, polyoxyalkylene sulfosuccinic acid alkyl ester salt, polyoxyalkylene alkyl phenyl ether sulfate, alkane sulfonate, acyl isethionate, acyl methyl taurate, higher fatty acid salt, polyoxyalkylene alkyl Examples thereof include ether acetates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, acyl glutamates, alanine derivatives, glycine derivatives, and arginine derivatives.

  Examples of amphoteric surfactants include betaine surfactants and amine oxide surfactants. Of these, betaine surfactants such as imidazoline betaines, alkyldimethylaminoacetic acid betaines, fatty acid amidopropyl betaines, and sulfobetaines, and amine oxide surfactants such as alkyldimethylamine oxides are more preferred, and alkylcarboxymethylhydroxyethylimidazo More preferred are sulfobetaines such as lithium betaine, fatty acid amidopropyl betaine, alkylhydroxysulfobetaine, alkylsulfobetaine, fatty acid amidopropylhydroxysulfobetaine and fatty acid amidopropylsulfobetaine, and alkyldimethylamine oxide.

  Among the cationic surfactants, mono long chain alkyl (carbon number 12 to 28) quaternary ammonium salts include stearyl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, aralkyl trimethyl ammonium chloride, and behenyl trimethyl ammonium. Examples thereof include chloride, lauryltrimethylammonium chloride, N-stearyl-N, N, N-tri (polyoxyethylene) ammonium chloride (total 3 mol addition), and the like. Examples of the di long-chain alkyl or alkenyl (C12-28) quaternary ammonium salt include distearyldimethylammonium chloride, dioleyldimethylammonium chloride, dipalmitylmethylhydroxyethylammonium methosulfate, diisostearyldimethylammonium methosulfate, Examples include di [(2-dodecanoylamino) ethyl] dimethylammonium chloride, di [(2-stearoylamino) propyl] dimethylammonium etosulphate, and the like. Examples of the alkylamide (carbon number 12 to 28) alkyl (carbon number 1 to 5) quaternary ammonium salt include stearamide propyl quaternary ammonium salt. Examples of the N-hydrocarbon (C12-28) carbamoylalkyl (C1-5) quaternary ammonium salt include N-stearylcarbamoylpropyl quaternary ammonium salt. Examples of acyl (C12-28) oxyalkyl (C1-5) quaternary ammonium salts include stearoylpropyl quaternary ammonium salts. Examples of the hydrocarbon (C12-28) oxyalkyl (C1-5) quaternary ammonium salt include octadecyloxypropyltrimethylammonium chloride.

Nonionic surfactants include polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbit fatty acid esters, polyoxyalkylene glycerin fatty acid esters, polyoxyalkylene fatty acid esters, and polyoxyalkylene alkyl ethers other than component (A). , Polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene (cured) castor oils, sucrose fatty acid esters, polyglycerin alkyl ethers, polyglycerin fatty acid esters, alkyl glycosides and the like. Of these, alkyl glycosides, polyoxyethylene (C ₈ -C ₂₀₎ alkyl ether - ether (preferably having an average addition mole number of EO 3 to 50), polyoxyethylene sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, fatty acid alkanol Amides are preferred.
Examples of hair cosmetics that can be suitably used in the present invention include hair shampoos, hair conditioning agents, hair perm agents, hair color agents and the like.

  The content of the silicone composition in the cosmetic for hair obtained by the production method of the present invention is preferably 0.05% by weight or more from the viewpoint of improving the unity and gloss of the hair, the moisturizing feeling, and the slipperiness of the hair, 0.1 wt% or more is more preferable, and 0.2 wt% or more is more preferable. On the other hand, from the viewpoint of improving the storage stability of hair cosmetics and suppressing stickiness, it is preferably 10% by weight or less, more preferably 5% by weight or less, and even more preferably 3% by weight or less. Taking these viewpoints together, the content of the silicone composition is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, and 0.2 to 3% by weight in the cosmetic for hair. Further preferred.

  In addition, in the cosmetic for hair obtained by the production method of the present invention, the content of component (A) is such that component (B) is uniformly dispersed, improving moisturizing feeling, hair cohesion, gloss, and slipperiness of hair. From the viewpoint of making it preferable, 0.05% by weight or more is preferable, and 0.1% by weight or more is more preferable. Preferably, it is 3% by weight or less. Summing up these viewpoints, the content of the component (A) in the cosmetic for hair is preferably 0.05 to 10% by weight, more preferably 0.1 to 7% by weight, and still more preferably 0.1 to 3% by weight. .

In the general formula (1), the hair cosmetic obtained by the production method of the present invention has n = m = 0, R ² is a hydrogen atom, and R ¹ is a straight chain having 3 to 10 carbon atoms. the compound represented by an alkyl or alkenyl group branched R ¹ OH, preferably represented by R ¹ OH R ¹ is an alkyl or alkenyl group of a straight-chain or branched-chain having 6 to 10 carbon atoms The compound, more preferably a compound represented by R ¹ OH, wherein R ¹ is a linear or branched alkyl group or alkenyl group having 8 to 10 carbon atoms, is from the viewpoint of low bromide, moisturizing feeling and hair unity. In hair cosmetics, 300 ppm or less is preferable, 150 ppm or less is more preferable, 80 ppm or less is more preferable, 50 ppm or less is more preferable, and 30 ppm or less is more preferable. Although there is no particular lower limit, 1 ppm or more is preferable from the viewpoint of ease of production.
R ¹ OH contained in the cosmetic for hair is derived from R ¹ OH contained in the component (A). In the general formula (1) of the component (A), R ¹ has 3 to 10 carbon atoms ( In the case of preferably 6 to 10 carbon atoms, more preferably 8 to 10 carbon atoms, R ¹ OH of R ¹ OH contained in the cosmetic for hair also has 3 to 10 carbon atoms (preferably 6 to 6 carbon atoms). 10, more preferably 8 to 10 carbon atoms. Therefore, in order to make the R ¹ OH content 300 ppm or less in the cosmetic for hair obtained in the present invention, the raw alcohol in the component (A) is distilled off, and the raw alcohol is used as described above. It is preferable to reduce the content of.
In order to make the content of R ¹ OH in the above range, the component (A) having a low content of R ¹ OH may be used as described above, and the raw alcohol of R ¹ OH is added after the component (A) is blended. Can be removed, but the former can be reduced more efficiently.

  In the cosmetic for hair obtained by the production method of the present invention, the content of the component (B) is 0.05% by weight or more from the viewpoint of improving the moist feeling of the hair, the gloss, the cohesion of the hair, and the slipperiness of the hair. Preferably 0.1% by weight or more, more preferably 0.3% by weight or more, from the viewpoint of suppressing stickiness, preferably 10% by weight or less, more preferably 7% by weight or less, and 3% by weight or less. Is more preferable. Taking these viewpoints together, the content of the component (B) in the hair cosmetic is preferably 0.05 to 10% by weight, more preferably 0.1 to 7% by weight, and still more preferably 0.3 to 3% by weight. . In the cosmetic for hair, the weight ratio of the components (A) and (B) is the same as the mixing ratio described above.

The dispersed particle size of the component (B) in the hair cosmetic obtained by the production method of the present invention, particularly a hair conditioning agent, a hair perm agent, and a hair color agent, is preferably 50 μm or less from the viewpoint of uniformly adhering to the hair, 30 μm or less is more preferable, and 10 μm or less is more preferable. Moreover, from a viewpoint of improving the adsorption amount to hair, 0.1 micrometer or more is preferable, 0.5 micrometer or more is more preferable, and 1 micrometer or more is further more preferable. Taking these viewpoints together, the dispersed particle size of the component (B) in the cosmetic for hair is preferably 0.1 to 50 μm, more preferably 0.5 to 30 μm, and even more preferably 1 to 10 μm. The dispersed particle diameter of the component (B) in the cosmetic for hair is measured by the method described in Examples below. In order to adjust the dispersed particle diameter of the component (B) to the above range, the mixing weight ratio of the component (A) and the component (B), and the R ¹ and n number (PO chain length) of the component (A) are selected. It is preferable to adjust the molecular weight of component (B), the number of moles of glycidol added in component (B), the production conditions (stirring power, mixing temperature, mixing time) of hair cosmetics, and the like.

In the case of a hair shampoo, the surfactant other than the component (A) is preferably an anionic surfactant, and the content of the surfactant other than the component (A) in the cosmetic for hair is from the viewpoint of improving foaming. It is preferably 1% by weight or more, more preferably 3% by weight or more, and preferably 15% by weight or less, more preferably 10% by weight or less from the viewpoint of improving the blending stability. If these viewpoints are put together, 1-15 weight% is preferable and, as for content in surfactant for hair of surfactant other than a component (A), 3-10 weight% is more preferable. The content of water is preferably 50 to 90% by weight, and more preferably 60 to 85% by weight.
The weight ratio of the component (A) to the surfactant other than the component (A) [surfactant other than the component (A) / component (A)] provides a cohesive, glossy, moisturizing feeling and slipperiness of the hair. From the viewpoint of improvement, 5/1000 or more is preferable, 1/100 or more is more preferable, and 2/100 or more is more preferable. Moreover, from a viewpoint of improving quick-foaming property, 1/5 or less is preferable, 1/10 or less is more preferable, and 1/20 or less is further more preferable. Summing up these viewpoints, [component (A) / surfactant other than component (A)] is preferably 5/1000 to 1/5, more preferably 1/100 to 1/10, and 2/100 to 1/20 is more preferable.

In the case of a hair conditioning agent, hair perm agent or hair color agent, the surfactant is preferably a cationic surfactant or a nonionic surfactant, and the content of the surfactant other than the component (A) in the cosmetic for hair is From the viewpoint of improving the slipperiness of hair, 0.05% by weight or more is preferable, 0.1% by weight or more is more preferable, and 0.3% by weight or more is more preferable. Moreover, from a viewpoint of improving mixing | blending stability, 10 weight% or less is preferable, 5 weight% or less is more preferable, and 2.5 weight% or less is further more preferable. Summing up these viewpoints, the content of the surfactant other than the component (A) in the cosmetic for hair is preferably 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, and 3 to 5 weight% is further more preferable, and 0.3 to 2.5 weight% is still more preferable. The water content is preferably 50 to 98% by weight, more preferably 60 to 97% by weight.
The weight ratio of the component (A) to the surfactant other than the component (A) [component (A) / surfactant other than the component (A)] is a sticky feeling, hair cohesion, gloss, moisturizing feeling, From the viewpoint of improving the feeling of slip, 1/100 or more is preferable, 5/100 or more is more preferable, and 1/10 is more preferable. Further, from the viewpoint of suppressing the sticky feeling and improving the slipperiness of the hair, 5/1 or less is preferable, 3/1 or less is more preferable, and 1/1 or less is more preferable. Taking these viewpoints together, [component (A) / surfactant other than component (A)] is preferably 1/100 to 5/1, more preferably 5/100 to 3/1, and 1/10 to 1 / 1 is more preferable.

The hair cosmetic obtained by the production method of the present invention may further contain an oily component as long as the present invention is not impaired.
Examples of the oil component include silicones other than the component (B), ester oils, hydrocarbons, glycerides, vegetable oils, animal oils, lanolin derivatives, higher fatty acid esters, and the like, and silicone is preferable.

  Examples of silicones other than component (B) include (a) dimethylpolysiloxane, (b) methylphenylpolysiloxane, and (c) amino-modified silicone described in JP-A-6-48916. SM8704C (made by Toray Dow Corning Silicone), DC939 (made by Toray Dow Corning Silicone), etc.], (d) Fatty acid-modified polysiloxane, (e) Alcohol-modified silicone, (f) Aliphatic alcohol-modified Polysiloxane, (g) polyether-modified silicone, (h) epoxy-modified silicone, (i) fluorine-modified silicone, (j) cyclic silicone, (k) alkyl-modified silicone, (l) amino-modified siloxane-polyoxyalkylene block copolymer A polymer etc. are mentioned.

The ester oil is preferably a monoester oil or a mixture of two or more ester oils having two or more ester bonds in the molecule.
The monoester oil is a monoester oil having 8 to 40 carbon atoms in total, preferably 2 to 22 carbon atoms, more preferably a monovalent fatty acid having 8 to 20 carbon atoms and a monovalent or polyhydric alcohol having 1 to 20 carbon atoms. These may be linear or branched, and may be saturated or unsaturated. Specifically, isopropyl palmitate, isopropyl myristate, isononyl isononanoate, triisodecyl isononanoate, stearyl stearate, and diglyceryl monoisostearate are preferable.
The polyvalent ester oil having two or more ester bonds in the molecule is a polyvalent ester oil having a total carbon number of 8 to 120, preferably one or two monovalent or polyvalent fatty acids having 2 to 22 carbon atoms. Examples thereof include polyvalent esters of the above mixture and a monovalent or polyhydric alcohol having 2 to 20 carbon atoms, and these may be linear or branched, and may be saturated or unsaturated. It may also contain an aromatic ring. Specifically, an ester of neopentyl glycol dicaprate, diglyceryl diisostearate, dipentaerythritol and a mixed fatty acid such as hydroxystearic acid, stearic acid, or rosin is preferable.

Moreover, a polymeric thickener can be mix | blended with the cosmetics for hair obtained by the manufacturing method of this invention. Examples of the polymer thickener include hydroxyethyl cellulose, guar gum, xanthan gum, and polyacrylic acid polymer. The content of the polymer thickener is preferably 0.01 to 20% by weight, more preferably 0.05 to 15% by weight in the hair cosmetic.
Moreover, the hydrolyzate represented by the water-soluble collagen and collagen derivative which are well-known components can also be mix | blended with the cosmetics for hair obtained by the manufacturing method of this invention. Further, chelating agents, coloring agents, preservatives, pH adjusting agents, viscosity adjusting agents, fragrances, pearlescent agents, wetting agents, styling polymers, and the like may be blended.

The cosmetics for hair obtained by the production method of the present invention include the following components (A ′) to (C) from the viewpoints of hair stickiness, gloss, moisturizing feeling, hair cohesion, and hair softness. The thing containing is preferable.
(A ′) General formula (1 ′)
^{R 1 O- (PO) n /} (EO) m-R 2 (1 ')
(In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 8 to 10 carbon atoms, PO represents a propyleneoxy group, EO represents an ethyleneoxy group, and the average added mole number n is 1. A compound having a number of 0.5 to 5.0, an average added mole number m of 0 to 1.0, and R ² represents a hydrogen atom or a methyl group. Surfactant and / or water other than silicone (C) (A ')

  In the case of a hair shampoo, the cosmetic for hair produced in the present invention is preferably 2 to 7 and more preferably 5 to 7 in the case of a hair shampoo. Moreover, in the case of a hair conditioning agent, pH (20 degreeC) has preferable 2-7, and 2.5-5.5 are more preferable. In the case of a hair perm agent and a hair color agent, the pH (20 ° C.) of the first agent containing a basic compound is preferably 8 to 11, more preferably 9 to 10.5, and the pH (20 ° C.) of the second agent is 2-7 are preferable and 2.5-6 are more preferable.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

Production Example 1
161-5.0 g (12.35 mol) of 1-octanol (Calcoal 0898, manufactured by Kao Corporation) and 6.9 g (0.12 mol) of potassium hydroxide were charged into an autoclave, dehydrated at 110 ° C. and 13.3 kPa, and then 120 ° C. Then, 1434 g (24.69 mol) of propylene oxide was added at 0.3 MPa to carry out the addition reaction.
After completion of the reaction, the mixture was aged at the same reaction temperature for 6 hours and then cooled to 80 ° C.
As a post-treatment, 55 g of a synthetic adsorbent (KYOWARD 600S, Kyowa Chemical Industry Co., Ltd.) was added to the obtained reaction composition and treated at 4.0 kPa for 1 hour, and then the catalyst was removed by filtration. The 1-octanol content of the obtained filtrate was 9000 ppm as determined by gas chromatography.
Subsequently, about 1000 g of the obtained filtrate, 1-octanol was distilled off by distillation under the conditions of 130 ° C. and 1.3 kPa. Further, steam treatment was performed by blowing 100 g of steam under the conditions of 145 ° C., 6.0 kPa, and 5 hours.
The 1-octanol content in the obtained component (A) (alkylene glycol ether 1 shown in Table 1) was quantified by gas chromatography.

Gas chromatography conditions Gas chromatograph: Agilent HP6890N
Column: Frontier LAB Ultara-Alloy-1
Temperature condition: Initial temperature 100 ° C (0 min)
Temperature increase rate 10 ° C / min (up to 350 ° C)
Final temperature 350 ℃ (20min)
Sample volume: 1 μL
Inlet condition: Injection mode Split method
Inlet temperature 300 ° C
Carrier gas: helium flow rate 60mL / min
Detector: FID

  The distribution of the number of moles of PO added as the component (A) before distillation, after distillation, and after steam treatment was determined by gas chromatography.

Distribution (molar ratio) of PO1-5 of alkylene glycol ether 1 before distillation
PO addition mole number 1: 35.6
PO addition mole number 2: 34.9
PO addition mole number 3: 18.7
PO addition mole number 4: 7.8
PO addition mole number 5: 3.0

Distribution (molar ratio) of PO1 to alkylene glycol ether 1 of component (A) after distillation and steam treatment
PO addition mole number 1: 24.6
PO addition mole number 2: 39.8
PO addition mole number 3: 22.4
Number of moles of PO added 4: 9.5
PO addition mole number 5: 3.7

The average addition mole number n of PO of the obtained alkylene glycol 1 and the average addition mole number m of EO were determined by ¹ H-NMR. The results are shown in Table 1.

Production Example 2: An alkylene glycol ether 2 was obtained in the same manner as in Production Example 1 except that hexyl alcohol was used and the average number of moles of polypropylene oxide added was 3.0 moles.

Production Example 3: An alkylene glycol ether 3 was obtained in the same manner as in Production Example 1 except that n-propyl alcohol was used and the average number of moles of polypropylene oxide added was 3.1 moles.

Production Example 4: An alkylene glycol ether 4 was obtained in the same manner as in Production Example 1 except that the average number of added moles of polypropylene oxide was 2.9 mol.

Production Example 5 An alkylene glycol ether 5 was obtained in the same manner as in Production Example 2 except that 2-ethylhexyl alcohol was used.

Production Example 6: An alkylene glycol ether 6 was obtained in the same manner as in Production Example 2 except that 1-decanol was used.

Production Example 7: An alkylene glycol ether 7 was obtained in the same manner as in Production Example 5 except that the average added mole number of polypropylene oxide was 2.0 mol.

Production Example 8: An alkylene glycol ether 8 was obtained in the same manner as in Production Example 5 except that the average added mole number of polypropylene oxide was 4.0 mol.

Production Example 9: An alkylene glycol ether 9 was obtained in the same manner as in Production Example 1 except that the average added mole number of polypropylene oxide was 2.0 mol.

Production Example 10: An alkylene glycol ether 10 was obtained in the same manner as in Production Example 2 except that lauryl alcohol was used.

Production Example 11: An alkylene glycol ether 11 was obtained in the same manner as in Production Example 3 except that the average number of moles added of polypropylene oxide was 6.9 mol.

Production Example 12: An alkylene glycol ether 12 was obtained in the same manner as in Production Example 1 except that the average addition mole of polypropylene oxide was several 7.2 moles.

Production Example 13: An alkylene glycol ether 13 was obtained in the same manner as in Production Example 6 except that the average added mole number of polypropylene oxide was 6.7 mol.
The alkylene glycol ethers obtained in Production Examples 2 to 13 are shown in Table 1.

Production Example 14: Synthesis of branched polyglycerol-modified silicone (linking group: —CH ₂ CH ₂ CH ₂ —C ₆ H ₄ —O—) Phenol-modified silicone (trade name; BY16-752, manufactured by Toray Dow Corning Co., Ltd.) , Hydroxyl equivalent: 1500) 150 g was added to a flask, and 5.61 g of potassium methoxide (30% methanol solution) was added. The mixture was heated to 60 ° C. under reduced pressure with stirring, all the methanol was distilled off, and a yellow oily substance was obtained. As a result, potassium-modified phenol-modified silicone was obtained. The temperature was raised to 95 ° C., and 39.9 g (5.4 equivalents) of glycidol was added over 3.5 hours under a stream of argon with vigorous stirring over a period of 3.5 hours. After further heating and stirring for 20 minutes and cooling to room temperature, a pale yellowish white solid product was obtained. Ethanol (500 mL) was added to the obtained branched polyglycerol-modified silicone, potassium was removed and concentrated using a cation exchange resin, and branched polyglycerol-modified silicone A was obtained as a slightly yellow oily substance. (Yield 98%).
The obtained branched polyglycerol-modified silicone was analyzed from the presence of a signal (78.0 to 81.0 ppm) derived from the methine carbon of the group (1) by analyzing the ¹³ C-NMR spectrum. It was confirmed to be glycerol-modified silicone. Further, by analysis of the ¹ H-NMR spectrum, the average number of glycerol groups (G) = 10.9 (one side 5.5), the average number of silicon atoms (Si) = 31.9, and the G / Si ratio is 0.34, According to GPC analysis (column: KF-804L (× 2), aliphatic amine / chloroform solution, 40 ° C., polystyrene conversion), the number average molecular weight (Mn) was 4100.

Examples 1-13, Comparative Examples 1-11
According to the production process of the present invention, the silicone composition shown in Table 2 was obtained in Step 1. The results are shown in Table 2.

Production (step 1) and evaluation of silicone composition Mixed state: Mixing predetermined amount of component (A) and component (B) shown in Table 2 or other components at 60C for 3 hours, at room temperature The state after standing for 24 hours was observed.
○: A uniform state is maintained.
X: Separation is recognized.
Viscosity: Viscosity at 30 ° C. was measured with a BM viscometer for those in which a uniform state was maintained in the above evaluation. (Measurement time 1 minute, rotor 2 or 3)

  From Table 2, it can be seen that the silicone compositions of Examples 1 to 13 are uniformly mixed and have a lower viscosity than the component (B) (Comparative Example 1) not containing the component (A). In addition, as shown in Comparative Examples 2 to 9, when the component (B) is mixed with a compound generally used in hair cosmetics other than the component (A), it has a viscosity reducing effect even if it is separated or not separated. It turns out that it is low. Further, as shown in Comparative Examples 10 and 11, it can be seen that the component (A) is separated even when mixed with silicone other than the component (B).

  Next, the hair shampoo was manufactured in the process 2 using the silicone composition of Examples 1-6 and Comparative Examples 1-3 which obtained the uniform silicone composition. The evaluation results are shown in Table 3.

Production (Step 2) and Evaluation of Cosmetic (Hair Shampoo) A shampoo (pH 6) having the following composition was prepared and evaluated by the following method.
After mixing 56.7 parts of Emar E-27C (polyoxyethylene lauryl ether sulfate Na: effective 27% by weight [manufactured by Kao)] and 40.8 parts of water, the mixture was heated to 70 ° C. and aminone C-11S ( After adding and mixing 1.0 part of palm oil fatty acid monoethanolamide ([Kao Co., Ltd.]), 0.7 part of Calcoal 6098 (cetyl alcohol [Kao Co., Ltd.]) and 0.3 part of sodium benzoate, 40 ° C. Then, the mixture was mixed with 0.5 part of the silicone composition or polyglycerol-modified silicone, citric acid was added so that the pH was 6, and water was added so that the total amount was 100 parts, thereby obtaining a shampoo. .

Shampoo composition (wt%)
Silicone compositions (Examples 1-6, Comparative Examples 2-3) or
Polyglycerol-modified silicone (Comparative Example 1) 0.5
Emar E-27C [Made by Kao Corporation]
(Polyoxyethylene lauryl ether sulfate Na: effective 27% by weight) 56.7
Aminone C-11S [manufactured by Kao Corporation]
(Coconut oil fatty acid N-methylethanolamide) 1.0
Calcoal 6098 [manufactured by Kao Corporation] (cetyl alcohol) 0.7
Sodium benzoate 0.3
Citric acid appropriate amount
Purified water residue
Total 100

Evaluation of dispersibility In the above shampoo production, the silicone composition or the polyglycerol-modified silicone was mixed, and the dispersibility of the polyglycerol-modified silicone in the mixture before adding citric acid or water was evaluated by the following judgment.
1: Dispersed easily by mixing and stirring. (Disperses uniformly within 10 minutes.)
2: It takes considerable stirring time for dispersion. (It takes 30 minutes or more to uniformly disperse.)

Shampoo performance evaluation About the shampoo of Examples 1-6 and the comparative example 1, the shampoo performance was evaluated based on the following evaluation. The results are listed in Table 4.
For the performance evaluation of shampoo (measurement of hair mass, gloss, and stickiness), test panel using Japanese hair (20 g, length 20 cm) was used, and sensory evaluation was performed by four panelists. That is, after using an adult female hair with no history of chemical treatment and black straight hair of about 40 cm in length as a specimen, immersing it in a sodium lauryl sulfate solution at 40 to 50 ° C. for 10 minutes and washing it with running water. Air dry. About 4 g of this hair sample is aligned to a width of 3 cm so as not to overlap, and one end of which is fixed to a 3 cm wide plastic plate with an adhesive so that the length of the hair is 35 cm is used as a test trace. The test tress produced in this way was used.

operation:
After thoroughly moistening the tress with warm water of 35-40 ° C., it is washed with a plain shampoo. After thoroughly rinsing with warm water, the hair bundle is lightly squeezed to remove excess moisture, washed with 1 g of the above shampoo, rinsed, dried with warm air from the dryer, and finished with a comb for finishing. Evaluate each item at the time.

Plain shampoo (% by weight)
Emar E-27C [Made by Kao Corporation]
(Polyoxyethylene lauryl ether sulfate Na (effective content 27 wt%)) 42
Aminone C-11S [manufactured by Kao Corporation]
(Coconut oil fatty acid N-methylethanolamide) 3
Citric acid 0.2
Methylparaben 0.3
Purified water residue
Total 100

Evaluation criteria are shown below.
Hair mass (assessed visually)
Evaluation criteria:
5: There is no splash hair and it is gathered up.
4; Almost no jump hairs are collected.
3; There is a slight amount of jumping hair, and it is a little lacking in unity.
2; There are splash hairs and they are not organized.
1; There are many jumping hairs and no unity.

Hair gloss evaluation criteria:
5; There is a very clear gloss.
4; There is clear gloss.
3; There is some clear gloss.
2; Shiny but not very clear.
1: The gloss is not recognized at all.

Hair stickiness (Evaluation by touching hair with hand)
Evaluation criteria:
5: There is no sticky feeling at all.
4; There is almost no sticky feel.
3; Slightly sticky.
2;
1;

  In all cases, the average score was 4 or more, ◎, less than 4, 3 or more, ◯, less than 2, 2 or more, Δ, and less than 2, x.

The shampoo using the silicone composition of the present invention was excellent in hair performance after drying.
Although the silicone compositions of Comparative Examples 2 and 3 were somewhat low in viscosity, they could not be easily dispersed in the shampoo. On the other hand, if the silicone composition of the present invention was used, polyglycerol-modified silicone could be easily blended.

Manufacture and evaluation of cosmetics (hair conditioning agent) The hair conditioning agents of Example 14 and Comparative Example 12 were prepared and evaluated by the following methods.

Example 14
Coatamine 60W (cetyltrimethylammonium chloride: effective 30% [manufactured by Kao Corporation]) 1.39 parts, water 94.20 parts and methylparaben 0.30 parts were mixed at room temperature, and this aqueous solution was heated to 80 ° C. In advance, a mixture prepared by mixing 1.62 parts of calcoal 6098 (cetyl alcohol [manufactured by Kao Co., Ltd.) and 1.72 parts of calcoal 8098 (stearyl alcohol [manufactured by Kao Co., Ltd.]) at room temperature was added to an aqueous solution heated to 80 ° C., After emulsification, it was cooled to 50 ° C. At 50 ° C., 0.267 parts of the silicone composition of Example 2 and BY11-040 (highly polymerized methylpolysiloxane [manufactured by Toray Dow Corning Co., Ltd.)] 0.25 part, SH200C (dimethylpolysiloxane [Toray Dow Corning Co., Ltd.) 0.25 parts) was added, water was further added so that the total amount was 100 parts, and the mixture was cooled to room temperature to produce a hair conditioning agent having a pH of 4.3.

Comparative Example 12
The hair conditioning agent of Comparative Example 12 was prepared in the same manner as in Example 14 except that 0.067 part of alkylene glycol ether 1 and 0.20 part of polyglycerol-modified silicone were used instead of the silicone composition of Example 2. pH 4.3) was prepared.

Performance evaluation of hair conditioning agents (measurement of hair mass, gloss, stickiness)
For the performance evaluation of hair conditioning agents (measurement of hair mass, gloss, and stickiness), a test tress using Japanese hair (20 g, length 20 cm) was used, and sensory evaluation was performed by four panelists.
operation:
After thoroughly moistening the tress with warm water of 35-40 ° C., it is washed with a plain shampoo. After thoroughly rinsing with warm water, the hair bundle is lightly squeezed to remove excess moisture and 1 g of the hair conditioning composition is applied. After evaluating each item at the time of application, rinse with warm water, remove moisture with a towel, and prepare a hair bundle with a comb. Then, it is dried with warm air from a dryer, the hair bundle is arranged with a comb for finishing, and each item at the time of finishing is evaluated.
The tress and plain shampoo used are the same as those used in the shampoo performance evaluation.
Evaluation criteria are shown below.
Hair mass (assessed visually)
Evaluation criteria:
5; There is no splash hair and it is well organized.
4; There is no splash hair and it is gathered up.
3; Almost no jump hairs are collected.
2; There are some bald hairs, but they are gathered.
1; There is a slight amount of jumping hair, and it is somewhat lacking in unity.

Hair gloss evaluation criteria:
5; There is a very clear gloss and the outline of the gloss is clear.
4: There is a clear gloss, and the outline of the gloss is clear.
3: There is a clear gloss, and the outline of the gloss is slightly clear.
2; There is a somewhat clear gloss, and the outline of the gloss is slightly clear.
1; There is some clear gloss.

Hair stickiness (Evaluation by touching hair with hand)
Evaluation criteria:
5; There is no sticky feeling at all, and it is smooth.
4; There is no sticky feeling at all, and it is a little smooth.
3: There is almost no sticky feeling, but there is a certain degree of smoothness.
2; Slightly sticky and weak feeling.
1; Slightly sticky.

  In all cases, the average score was 4 or more, ◎, less than 4, 3 or more, ◯, less than 2, 2 or more, Δ, and less than 2, x.

  The conditioning agent (Example 14) obtained by the production method of the present invention is superior to the conditioning agent (Comparative Example 12) obtained by the conventional production method and has excellent hair cohesiveness and gloss, and the sticky feeling is suppressed. I understand that

Dispersion state of component (B) in cosmetic (hair conditioning agent) Example 15
The dispersion state of component (B) in the hair conditioning agent of Example 14 and Comparative Example 12 was examined. In order to make it easy to see the dispersion state of the component (B) in the hair conditioning agent, a hair conditioning agent not using BY11-040 and SH200C was prepared. That is, the hair conditioning agents of Example 15 and Comparative Example 13 were prepared in the same manner as in Example 14 and Comparative Example 12 except that BY11-040 and SH200C were not used.

Measurement of dispersion state The hair conditioning agent of Example 15 and Comparative Example 13 was 450 to 1000 times using a digital microscope “VHX-100” (manufactured by Keyence Corporation) equipped with a high magnification zoom lens “VH-Z450”. Observed and photographed. For the particle size, the largest and smallest particles in the photographic image were measured using a scale inserted in the photographic image.
The obtained optical micrographs are shown in FIG. 1 (Example 15) and FIG. 2 (Comparative Example 13).
1 and 2, in the hair conditioning agent of Example 15 obtained by the production method of the present invention, the component (B) was dispersed with a particle size of 1 to 30 μm. On the other hand, in the hair conditioning agent of Comparative Example 13 obtained by the conventional production method, the component (B) could not be uniformly dispersed.

Example 16
A hair conditioning agent having the composition shown in Table 5 was produced by the following method.
That is, 3.50 parts of Cotamine E-80K (octadecyloxypropyltrimethylammonium chloride: effective 45% by weight [manufactured by Kao Corporation]), 86.1 parts of water and 0.30 part of methylparaben were mixed at room temperature, and this aqueous solution was mixed. Was heated to 80 ° C. In advance, 3.00 parts of calcoal 6098 (cetyl alcohol [manufactured by Kao Co., Ltd.) and 3.00 parts of calcoal 8098 (stearyl alcohol [manufactured by Kao Co., Ltd.]), synchro wax ERL-C (ethylene glycol fatty acid diester (manufactured by Croda) ) A mixture prepared by mixing 1.00 parts at room temperature was added to an aqueous solution heated to 80 ° C., emulsified, and then cooled to 50 ° C. At 50 ° C., 0.8 parts of the silicone composition of Example 2 and X -52-2127 (highly polymerized methylpolysiloxane [manufactured by Shin-Etsu Chemical Co., Ltd.)] is added, water is further added so that the total amount becomes 100 parts, the solution is cooled to room temperature, and the pH is 4.3 A conditioning agent was produced.

  By using the silicone composition of the present invention, polyglycerol-modified silicone can be easily blended into hair cosmetics, and the obtained hair conditioning agent has no stickiness when finished, is glossy, It was found to be excellent in softness and impart a good unity of hair and moisturizing feeling.

Claims (5)

A method for producing a cosmetic for hair having the following steps 1 and 2.
Step 1: The following components (A) and (B) are mixed at a weight ratio of (A) / (B) = 1/10 to 2/3, and the sum of components (A) and (B) A step of obtaining a silicone composition having a content of 90 to 100% by mass and a viscosity at 30 ° C. of 500 to 20000 mPa · s (A) General formula (I)
^{R 1 O- (PO) n /} (EO) m-R 2 (I)
(In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 3 to 10 carbon atoms, PO represents a propyleneoxy group, EO represents an ethyleneoxy group, and the average added mole number n is 1. A compound having a number of 0.5 to 5.0, an average added mole number m of 0 to 1.0, and R ² represents a hydrogen atom or a methyl group. Silicone step 2: The silicone composition obtained in step 1 and the surfactant and / or water other than component (A) are mixed at a mixing weight ratio of 1/10000 to 2/10 (silicone composition / [component (A Step of obtaining a cosmetic for hair by mixing with a surfactant other than) + water]) Component (A) is a raw material alcohol represented by R ¹ OH (wherein R ¹ represents a linear or branched alkyl or alkenyl group having 3 to 10 carbon atoms), propylene oxide, or propylene The production method according to claim 1, which is a compound obtained by reacting oxide and ethylene oxide and then distilling off the raw alcohol. The production method according to claim 1 or 2 , wherein the hair cosmetic is a shampoo or a hair conditioning agent. The cosmetic for hair obtained by the manufacturing method as described in any one of Claims 1-3 . Sum of components (A) and (B) obtained by mixing the following components (A) and (B) at a weight ratio of (A) / (B) = 1/10 to 2/3: Silicone composition for cosmetics for hair whose content is 90-100 mass%.
(A) General formula (I)
^{R 1 O- (PO) n /} (EO) m-R 2 (I)
(In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 3 to 10 carbon atoms, PO represents a propyleneoxy group, EO represents an ethyleneoxy group, and the average added mole number n is 1. A compound having a number of 0.5 to 5.0, an average added mole number m of 0 to 1.0, and R ² represents a hydrogen atom or a methyl group. silicone