JP2020075964A - Hair cosmetic (co)polymer, method for producing the same, and hair cosmetic - Google Patents

Abstract

To provide a vinyl(co)polymer for hair cosmetic that gives a good cohesiveness during use and can maintain its keeping-power even in a high humidity environment, and to provide a hair cosmetic.SOLUTION: Provided is a hair cosmetic (co)polymer obtained by polymerizing 100 pts.mass of (A) one or more water-soluble vinyl monomers selected from the group consisting of vinyl acetate, N-vinyl lactam, (meth)acrylic acid, hydroxyalkyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dialkyl (meth)acrylamide and (meth)acryloylethyldialkylbetaine, 0.01 to 10 pts.mass of (B) an organic peroxide having a particular structure including a hydroxyl group and a tertiary peroxycarboxylic acid group, and 0.01 to 10 pts.mass of (C) one or more reducing agents selected from the group consisting of thioglycolates, cysteines, salts of cysteines, cysteamines, salts of cysteamines, sulfites and 2-hydroxy-2-sulfinoacetates.SELECTED DRAWING: None

Description

  The present invention relates to a (co) polymer for hair cosmetics, a method for producing the same, and a hair cosmetic.

  Hair cosmetics are mainly composed of a vinyl copolymer containing a water-soluble vinyl monomer and water, a solvent such as alcohol, and among them, the vinyl copolymer is used as a hair cosmetic for moisturizing hair, setting hairstyle, etc. It plays an important role in expressing functions.

  Particularly in hair styling agents, vinyl copolymers are required to have an appropriate moisturizing power for gathering hair. However, if the moisturizing power is increased, it becomes difficult to set the hair by absorbing moisture in a high humidity environment such as in summer or in the rain. The current hair styling agent balances the setting power and the keeping power, so the amount of the water-soluble vinyl monomer is adjusted to balance these.

  Apart from this, regarding the polymerization method of vinyl copolymer, an aqueous solution polymerization method without using an organic solvent has been performed in recent years from the viewpoint of reducing the environmental load, and a polymerization method of a vinyl copolymer composition for hair cosmetics has been performed. Is also considered (Patent Document 1).

  On the other hand, a method of polymerizing a water-soluble vinyl monomer composition in an aqueous solution using an organic peroxide having a hydroxyl group at the terminal and a reducing agent is disclosed (Patent Document 2).

JP-A-2000-248004 JP, 2017-082081, A

  However, the hair cosmetic using the vinyl copolymer described in Patent Document 1 has a problem of insufficient keeping power when used in a high humidity environment. In addition, the vinyl copolymer described in Patent Document 2 has a problem that the versatility as a hair cosmetic is poor and the performance is poor.

  An object of the present invention is to provide a vinyl (co) polymer for hair cosmetics and a hair cosmetic that have good cohesion during use and can maintain the keeping power even in a high humidity environment.

（式（１）において、Ｒは水素またはメチル基である。）

（２） （１）の毛髪化粧料用（共）重合体を０．５〜５０質量％含有することを特徴とする、毛髪化粧料。

（３） （Ａ）酢酸ビニル、Ｎ−ビニルラクタム、（メタ）アクリル酸、（メタ）アクリル酸ヒドロキシアルキル、（メタ）アクリル酸ジメチルアミノエチル、ジアルキル（メタ）アクリルアミドおよび（メタ）アクリロイルエチルジアルキルベタインからなる群より選ばれた一種以上の水溶性ビニル単量体１００質量部と、
（Ｂ）下記一般式（１）で示される水酸基含有有機過酸化物０．０１〜１０質量部と、
（Ｃ）チオグリコール酸塩類、システイン類、システイン類の塩、システアミン類、システアミン類の塩、亜硫酸塩類および２−ヒドロキシ−２−スルフィノ酢酸塩類からなる群より選ばれた一種以上の還元剤０．０１〜１０質量部とを水中で重合することを特徴とする、毛髪化粧料用（共）重合体の製造方法。 The present invention is as follows.
(1) (A) Vinyl acetate, N-vinyl lactam, (meth) acrylic acid, hydroxyalkyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dialkyl (meth) acrylamide and (meth) acryloylethyldialkylbetaine 100 parts by mass of one or more water-soluble vinyl monomers selected from the group consisting of
(B) 0.01 to 10 parts by mass of a hydroxyl group-containing organic peroxide represented by the following general formula (1):
(C) one or more reducing agents selected from the group consisting of thioglycolates, cysteines, salts of cysteines, cysteamines, salts of cysteamines, sulfites and 2-hydroxy-2-sulfinoacetates. (Co) polymer for hair cosmetics, characterized by being polymerized with 01 to 10 parts by mass.

(In the formula (1), R is hydrogen or a methyl group.)

(2) A hair cosmetic, comprising 0.5 to 50 mass% of the (co) polymer for hair cosmetic of (1).

(3) (A) Vinyl acetate, N-vinyl lactam, (meth) acrylic acid, hydroxyalkyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dialkyl (meth) acrylamide and (meth) acryloylethyldialkylbetaine 100 parts by mass of one or more water-soluble vinyl monomers selected from the group consisting of
(B) 0.01 to 10 parts by mass of a hydroxyl group-containing organic peroxide represented by the following general formula (1):
(C) one or more reducing agents selected from the group consisting of thioglycolates, cysteines, salts of cysteines, cysteamines, salts of cysteamines, sulfites and 2-hydroxy-2-sulfinoacetates. A method for producing a (co) polymer for hair cosmetics, which comprises polymerizing 01 to 10 parts by mass in water.

Advantageous Effects of Invention According to the present invention, it is possible to provide a vinyl (co) polymer for hair cosmetics, which has a good cohesiveness during use and is capable of maintaining a keeping power even in a high humidity environment, and a hair cosmetic.
It should be noted that the vinyl (co) polymer for hair cosmetics of the present invention is difficult or impractical to clearly and generally define the structure of the polymer, and is defined by the composition of the composition to be polymerized. The invention is specified.

The details of the present invention will be described below. In addition, in this invention, "(meth) acrylic acid" is a concept containing both acrylic acid and methacrylic acid. Further, "XX to XX parts by mass" means XX parts by mass or more and XX parts by mass or less.
The (co) polymer for hair cosmetics may be a homopolymer of one type of (A) water-soluble vinyl monomer, or a copolymer of two or more types of (A) water-soluble vinyl monomer. It may be a copolymer of one or more kinds of (A) water-soluble vinyl monomer and other monomer.

((A) Water-soluble vinyl monomer)
The water-soluble vinyl monomer (A) is a main component constituting a vinyl (co) polymer for hair cosmetics. By using the water-soluble vinyl monomer, a cohesive feeling of hair can be obtained as a hair cosmetic, particularly as a hair styling agent.

  The water-soluble vinyl monomer means a monomer having a solubility in water at 20 ° C. of 10 g / L or more.

In the water-soluble vinyl monomer (A), the hydroxyalkyl (meth) acrylate preferably has 1 to 4 or less carbon atoms. The carbon number of the dialkyl (meth) acrylamide is preferably 1 to 4 or less. The carbon number of the alkyl group of the (meth) acryloylethyldialkylbetaine is preferably 1 to 4 or less.
Specific examples of the water-soluble vinyl monomer (A) include (A) vinyl acetate, N-vinyl-2-pyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, (meth) acrylic acid, and (meth). Hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth) acryloylethyldimethylbetaine, (meth) acryloylethyldiethylbetaine, Etc. These may be used alone or in combination of two or more.

((B) Hydroxyl group-containing organic peroxide)
The (B) hydroxyl group-containing organic peroxide is a polymerization initiator for polymerizing a vinyl (co) polymer for hair cosmetics, and is composed of an organic peroxide. Specific examples include 3-hydroxy-1,1-dimethylbutyl hydroperoxide and 3-hydroxy-1,1-dimethylpropyl hydroperoxide. These may be used alone or in combination of two kinds.

  The amount of the hydroxyl group-containing organic peroxide (B) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the water-soluble vinyl monomer (A). By using the (B) hydroxyl group-containing organic peroxide, a hydroxyl group is introduced into the terminal of the vinyl (co) polymer for hair cosmetics. Therefore, the vinyl (co) polymer for hair cosmetics can have an increased moisturizing power, while maintaining the keeping power in a high humidity environment. From this viewpoint, the amount of the (B) hydroxyl group-containing organic peroxide is preferably 0.1 part by mass or more, and more preferably 0.5 part by mass or more. The amount of the (B) hydroxyl group-containing organic peroxide is preferably 5 parts by mass or less, more preferably 2 parts by mass or less.

((C) reducing agent)
(C) The reducing agents are thioglycolates, cysteines, salts of cysteines, cysteamines, salts of cysteamines, sulfites, 2-hydroxy-2-sulfinoacetates, and (B) hydroxyl group-containing organic peroxides. It acts as an auxiliary agent for generating radicals from oxides. By using (C) a reducing agent, radicals are generated from the hydroxyl group-containing organic peroxide (B) even at a polymerization temperature of 30 to 80 ° C. to polymerize a vinyl (co) polymer for hair cosmetics. You can

  (C) The reducing agent specifically includes sodium thioglycolate, potassium thioglycolate, cysteine, sodium cysteine, cysteamine, cysteamine hydrochloride, sodium sulfite, potassium sulfite, 2-hydroxy-2-sulfinoacetic acid. Sodium salt, 2-hydroxy-2-sulfinoacetic acid / 2 potassium salt and the like can be mentioned.

  On the other hand, it is not preferable to use L-ascorbic acid or the like as the reducing agent, because the hair cosmetic will be colored. Further, since Rongalit generates formaldehyde, its use in hair cosmetics is not preferable.

  The amount of the reducing agent (C) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the water-soluble vinyl monomer (A). The amount of the reducing agent (C) is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass.

  The addition amount of the reducing agent (C) is defined by the molar ratio of component (B) / component (C). When the component (B) is 1 mol, the molar ratio of the component (C) is 0.8 to 1. 2, preferably 0.9 to 1.1, more preferably 0.95 to 1.05.

((D) Other vinyl monomers)
The (co) polymer for hair cosmetics may contain (D) another vinyl monomer in addition to the (A) water-soluble vinyl monomer, as long as the effect of the present invention is not impaired. The (D) other vinyl monomer is a vinyl monomer other than the water-soluble vinyl monomer defined as the component (A). Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Allyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and the like. These may be used alone or in combination of two or more.

  When the amount of the (A) water-soluble vinyl monomer is 100 parts by mass, the amount of the (D) other vinyl monomer is preferably 150 parts by mass or less, and preferably 50 parts by mass or less. More preferable. Further, (D) other vinyl monomers may not be contained.

(solvent)
The vinyl (co) polymer for hair cosmetics is used by diluting it with a solvent in order to improve handling when applied to hair. Examples of the solvent to be diluted include water, ethanol, liquid polyalkylene glycol and the like.

  When the total mass of the hair cosmetic composition is 100 mass%, the mass of the vinyl (co) polymer for hair cosmetic composition is preferably 0.5 to 50 mass%, more preferably 1 to 30 mass%. When the mass of the vinyl (co) polymer for hair cosmetics is more than 0.5% by mass, the cohesiveness of hair becomes good. By setting the mass of the vinyl (co) polymer for hair cosmetics to 50 parts by mass or less, unnecessary fixation of hair is unlikely to occur.

(Other additives)
The hair cosmetic may contain additives other than the components (A) to (D) and the solvent within a range that does not impair the effect. Additives include surfactants, conditioning agents, thickeners, viscosity modifiers, sequestering agents, ultraviolet absorbers, antioxidants, preservatives, powder components, antidandruff agents, hair growth agents, pH adjusters. , 1 or 2 or more such as dyes, fragrances and the like can be appropriately blended.

Hair cosmetics can be provided in various forms such as hair liquid, hair foam, hair mousse, hair spray, hair mist, hair gel, and hair wax.
Regarding the method for producing a vinyl (co) polymer for hair cosmetics, the polymerization temperature is 10 ° C to 90 ° C, preferably 30 ° C to 80 ° C, more preferably 50 ° C to 70 ° C. The higher the polymerization temperature, the faster the reaction proceeds, but if the polymerization is carried out at a temperature above the boiling point of the solvent or (A) water-soluble vinyl monomer, the concentration of (A) water-soluble vinyl monomer in the system will change and the polymerization reaction Is difficult to proceed, which is not preferable.
Each component is added by dissolving (C) a reducing agent in water, which is a solvent, while dissolving (A) a water-soluble vinyl monomer and (B) a hydroxyl group-containing polymerization initiator, either one or Both are obtained by continuously dropping them into a reaction vessel to carry out polymerization (dropping step).
In the main polymerization reaction, when the component (B) and the component (C) come into contact with each other, radicals are generated from the component (B) to cause the polymerization reaction. When the addition of each component is done in a batch, a large amount of radicals are generated at one time to start the polymerization, and the heat of polymerization becomes large and uncontrollable, and an unnecessary branched structure or vinyl (co) polymer is generated. Gelation occurs. Therefore, the intended vinyl (co) polymer for hair cosmetics cannot be obtained.
In the dropping step, the dropping time is 0.5 to 8 hours, preferably 1 to 6 hours, more preferably 2 to 5 hours.
After completion of the dropping step, it is preferable to perform an aging step for 0.5 to 4 hours. By performing the aging step, a vinyl (co) polymer for hair cosmetics can be obtained in which the polymerization reaction sufficiently proceeds and the molecular weight is in an appropriate range, that is, the number average molecular weight Mn = 10,000 to 50,000. ..
After the dropping step or after the aging step, it is preferable to carry out a post reaction at + 20 ° C. to 30 ° C. for 0.5 hours to 2 hours from the polymerization temperature for the purpose of reducing the residual monomer.

Specific examples will be described below, but the present invention is not limited thereto.
(Example E)

  A 500 ml four-necked flask was charged with 325 parts by mass of water and 0.5 parts by mass of (C) sodium thioglycolate as a reducing agent, and heated to 60 ° C. with stirring. In a 200 ml beaker, (A) 60 parts by mass of vinyl acetate as a water-soluble vinyl monomer, 40 parts by mass of N-vinyl-2-pyrrolidone, and (B) 3-hydroxy-1,1 as a hydroxyl group-containing polymerization initiator. -0.5 parts by mass of dimethylbutyl hydroperoxide was mixed, continuously dropped at 60 ° C over 2 hours, and then polymerized at 60 ° C for 3 hours to give a (co) weight for hair cosmetic of Example E. Got united.

(Examples F to M and Comparative Examples N and O)
The types and blending amounts shown in Table 1 were changed for the (A) water-soluble vinyl monomer, (B) hydroxyl group-containing organic peroxide, and (C) reducing agent used in the polymerization. Further, in Examples J and K, (D) other vinyl monomers were blended. Except for this, the same operation as in Example E was performed to obtain (co) polymers for hair cosmetics of Examples F to M and Comparative Examples N and O. However, the numerical value of each compounding amount shown in Table 1 is a unit of "part by mass".

(Example 1)
15% by mass of the hair cosmetic (co) polymer of Example E, 40 parts by mass of water, 15% by mass of ethanol, and 30% by mass of LPG (polyethylene glycol (# 400)) at room temperature. The hair cosmetics of Example 1 as shown in Table 2 were obtained by mixing. However, each numerical value shown in Table 2 and Table 3 is a unit of "mass%".

(Examples 2-11 and Comparative Examples 1-2)
The hair cosmetic (co) polymer, water, ethanol and LPG (polyethylene glycol (# 400)) used were changed to the types and blending amounts shown in Tables 2 and 3. Otherwise by performing the same operations as in Example 1, the hair cosmetics of Examples 2-11 and Comparative Examples 1-2 were obtained.

The following properties were measured for the obtained hair cosmetics of each example, and the results are shown in Tables 2 and 3.
(Cohesive feeling)
Hair cosmetics were used as hair styling agents and evaluated according to the following criteria.

"○": Good hair set, and no stickiness or stickiness is felt "x": Any one item of hair set, stickiness, and stickiness is NG

(Keeping power)
"○": When using a hair cosmetic as a hair styling agent, after leaving it in a thermo-hygrostat at 30 ° C, 80% and RH for 1 hour, it feels cohesive as if touched with a finger. "×" ... When using hair cosmetics as a hair styling agent, leave them in a constant temperature and humidity tank at 30 ° C, 80%, RH for 1 hour, and then feel untouched with your fingers

  In each of Examples 1 to 11, it was possible to obtain a hair cosmetic composition having good cohesiveness and keeping power.

In Comparative Example 1, since the organic peroxide not containing a hydroxyl group was used as the polymerization initiator, the hair cosmetic had no keeping power.
In Comparative Example 2, since the water-soluble azo compound was used as the polymerization initiator, the hair cosmetic had no keeping power.

Claims (3)

(A) Vinyl acetate, N-vinyl lactam, (meth) acrylic acid, hydroxyalkyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dialkyl (meth) acrylamide and (meth) acryloylethyldialkylbetaine 100 parts by mass of one or more water-soluble vinyl monomers selected from
(B) 0.01 to 10 parts by mass of a hydroxyl group-containing organic peroxide represented by the following general formula (1):
(C) one or more reducing agents selected from the group consisting of thioglycolates, cysteines, salts of cysteines, cysteamines, salts of cysteamines, sulfites and 2-hydroxy-2-sulfinoacetates. (Co) polymer for hair cosmetics, characterized by being polymerized with 01 to 10 parts by mass.

(In the formula (1), R is hydrogen or a methyl group.)
Hair cosmetics comprising 0.5 to 50% by mass of the (co) polymer for hair cosmetics according to claim 1.
(A) Vinyl acetate, N-vinyl lactam, (meth) acrylic acid, hydroxyalkyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dialkyl (meth) acrylamide and (meth) acryloylethyldialkylbetaine 100 parts by mass of one or more water-soluble vinyl monomers selected from
(B) 0.01 to 10 parts by mass of a hydroxyl group-containing organic peroxide represented by the following general formula (1):
(C) one or more reducing agents selected from the group consisting of thioglycolates, cysteines, salts of cysteines, cysteamines, salts of cysteamines, sulfites and 2-hydroxy-2-sulfinoacetates. A method for producing a (co) polymer for hair cosmetics, which comprises polymerizing 01 to 10 parts by mass in water.

(In the formula (1), R is hydrogen or a methyl group.)