JP6467127B2 - Resin and cosmetic base materials - Google Patents

Description

  The present invention is, for example, a resin that can be used as a base resin for skin cosmetics such as foundations, moisturizing cosmetics, and emulsions, and hair cosmetics such as hair mist, hair gel, and hair cream, and cosmetics containing this resin The present invention relates to a substrate for use.

  A synthetic resin composed of a polymer can be designed in a wide variety of molecular structures and three-dimensional structures by selecting monomer types at the time of synthesis, combining different types of monomers, or selecting a polymerization method. Resins synthesized in this way exhibit their specific functions and have a wide variety of uses.

  In recent years, in the cosmetic field such as skin cosmetics and hair cosmetics, the above resins are used as additives. For example, in Patent Document 1, a resin comprising a polymer of an ethylenically unsaturated monomer component containing a polyethylene glycol (meth) acrylate type monomer and an anionic monomer is used as a base material resin for cosmetics. Has been proposed. In Patent Document 2, a resin in which a repeating unit having an anionic group, a repeating unit containing an alkyl group having a specific carbon number, and a polysiloxane repeating unit are bonded to each other via a diisocyanate residue having a specific structure is used. It has also been proposed to be used as a base resin for use. In particular, in cosmetics to which the base resin proposed in Patent Document 2 is added, the extension of the base resin-derived film (hereinafter sometimes referred to as “film”) formed when applied to the skin is improved. Therefore, a good feeling of use is given to the skin.

JP 2006-28509 A JP 2005-104973 A

  However, in the resin as described above, since the hardness of the film formed when applied to the skin is not appropriate, the film gradually collapses with the passage of time, and makeup loss is likely to occur. In addition, since the resin structure does not take into account stickiness at the time of use, there is also a problem that the feeling of use decreases with the passage of time.

  The present invention has been made in view of the above points, and is excellent in film properties and can suppress stickiness of the film. For example, when used as a cosmetic base material in cosmetics, It aims at providing the resin base material which can provide the outstanding usability, and the cosmetics base material containing this resin.

  The resin according to the present invention comprises a polymer of an ethylenically unsaturated monomer component, and the polymer is represented by the repeating unit (A1) represented by the following formula (Ia) and the following formula (Ib). A molecule comprising at least one of the repeating unit (A2) shown and at least one of the repeating unit (B1) shown by the following formula (II-a) and the repeating unit (B2) shown by the following formula (II-b) It is characterized by including in.

In formula (Ia), R ₁ is H or CH ₃ , R ₂ is H or an alkyl group having 1 to 8 carbon atoms, R ₃ is H, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. A hydroxyalkyl group;

In the formula (Ib), R ₁ represents H or CH ₃ . M and n each independently represent an integer of 0 to 3.

In formula (II-a), R ₁ represents H or CH ₃ , R ₄ represents H or an alkyl group having 1 to 18 carbon atoms, and A ₁ represents O or NH. X, y, and z are each independently an integer of 0 to 100, and x + y + z ≧ 2. (EO) represents (C ₂ H ₄ O), (PO) represents (C ₃ H ₆ O), and (BO) represents (C ₄ H ₈ O).

In formula (II-b), R ₁ represents H or CH ₃ , R ₄ represents H or an alkyl group having 1 to 18 carbon atoms, and A ₁ represents O or NH. X, y, and z are each independently an integer of 0 to 100, and x + y + z ≧ 2. (EO) represents (C ₂ H ₄ O), (PO) represents (C ₃ H ₆ O), and (BO) represents (C ₄ H ₈ O). [-(EO) x- (PO) y- (BO) z-] in the formula (II-b) represents that each repeating unit of EO, PO, and BO is randomly arranged, that is, EO , PO and BO are random copolymers.

  In the resin, the ethylenically unsaturated monomer component contains 30 to 70% by mass of at least one of the monomers represented by the following formulas (1-a) and (1-b), The polymer preferably has a weight average molecular weight of 3,000 to 100,000 and a glass transition temperature of 10 to 60 ° C.

In formula (1-a), R ₁ is H or CH ₃ , R ₂ is H or an alkyl group having 1 to 8 carbon atoms, R ₃ is H, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. A hydroxyalkyl group;

In formula (1-b), R ₁ represents H or CH ₃ . M and n each independently represent an integer of 0 to 3.

  Moreover, the base material for cosmetics which concerns on this invention contains said resin.

  Since the resin of the present invention is composed of a polymer having a molecular structure including a repeating unit having a specific structure, when the film is formed with the above resin, the film has appropriate flexibility and adhesiveness. It becomes.

  In particular, since the resin of the present invention has excellent film properties on the skin (easiness of film formation and resistance to collapse of the film), if used as a cosmetic base material, the makeup lasts well and the feeling of use is good. It becomes possible to provide excellent cosmetics. In addition, since the resin is made of a polymer having a molecular structure containing a repeating unit having a specific structure, the stickiness after makeup is suppressed, and an excellent feeling of use can be maintained for a long time. .

  Hereinafter, modes for carrying out the present invention will be described.

  The resin of the present invention is a polymer (polymer or oligomer) obtained by polymerizing a polymerizable monomer (monomer) such as an ethylenically unsaturated monomer component. In this specification, the said polymer is described with the "polymer P" as needed.

  The polymer P includes one or both of the repeating unit represented by the formula (Ia) and the repeating unit represented by the formula (Ib), the repeating unit represented by the formula (II-a) and the formula ( It has a molecular structure having one or both of the repeating units represented by II-b). The formulas (Ia), (Ib), (II-a), and (II-b) are shown in [Chemical Formula 1] to [Chemical Formula 4], respectively.

  Here, the repeating unit represented by the formula (Ia) and the repeating unit represented by the formula (Ib) are referred to as a repeating unit (A1) and a repeating unit (A2), respectively, and the repeating unit (A1), (A2) is generically referred to as a repeating unit (A). The repeating unit (A) may be either one or both of the repeating unit (A1) and the repeating unit (A2). Further, the repeating unit represented by the formula (II-a) and the repeating unit represented by the formula (II-b) are respectively represented as a repeating unit (B1) and a repeating unit (B2), and the repeating unit (B1), ( B2) is generically referred to as the repeating unit (B). The repeating unit (B) may be either one or both of the repeating unit (B1) and the repeating unit (B2).

In the formula (Ia), when R ₂ is an alkyl group having 1 to 8 carbon atoms, specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert- Examples thereof include, but are not limited to, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, and an octyl group. In this case, the alkyl group may be linear, branched, or an alicyclic hydrocarbon group.

In the formula (Ia), when R ₃ is an alkyl group having 1 to 8 carbon atoms, specific examples thereof are the same as those for R ₂ described above.

In the formula (Ia), when R ₃ is a hydroxyalkyl group having 1 to 8 carbon atoms, specific examples thereof include a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 1-hydroxypropyl group, A 3-hydroxypropyl group, a 2-hydroxybutyl group, a 4-hydroxybutyl group and the like can be mentioned. The alkyl group of the hydroxyalkyl group may be linear or branched, or an alicyclic hydrocarbon group. Moreover, the said C1-C8 hydroxyalkyl group may have 2 or more of hydroxyl groups.

On the other hand, in the formulas (II-a) and (II-b), when R ₄ is an alkyl group having 1 to 18 carbon atoms, specific examples thereof include a methyl group, an ethyl group, an n-propyl group, and isopropyl. Group, n-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, lauryl group, stearyl group, palmityl group and the like. . In this case, the alkyl group may be linear, branched, or an alicyclic hydrocarbon group.

  The polymer P may have a molecular structure in which repeating units other than the above repeating unit (A) and repeating unit (B) are included in the molecule. Examples of such a repeating unit include a repeating unit represented by the formula (III-a) in [Chemical Formula 7] (hereinafter referred to as “repeating unit (C1)”), or a formula (III-b) in [Chemical Formula 8]. ) (Hereinafter referred to as “repeat unit (C2)”). The repeating unit (C1) and the repeating unit (C2) may be collectively referred to as a repeating unit (C). The repeating unit (C) may be either one of the repeating unit (C1) or the repeating unit (C2), or both.

In formula (III-a), R ₁ represents H or CH ₃ , and R ₅ represents a hydroxyalkyl group having 1 to 8 carbon atoms.

In formula (III-b), R ₁ represents H or CH ₃ , and R ₆ represents an alkyl group having 1 to 18 carbon atoms. N is an integer of 1-8.

Specific examples of the hydroxyalkyl group having 1 to 8 carbon atoms (R ₅ ) in the formula (III-a) include 2-hydroxyethyl group, 2-hydroxypropyl group, 1-hydroxypropyl group, 3-hydroxypropyl group, 4 -Hydroxybutyl group, 6-hydroxyhexyl group, 8-hydroxyoctyl group and the like. The alkyl group of the hydroxyalkyl group may be linear or branched, or an alicyclic hydrocarbon group.

Specific examples of the alkyl group having 1 to 18 carbon atoms (R ₆ ) in the formula (III-b) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, dodecyl group, octadecyl group and the like. Can be mentioned. In this case, the alkyl group may be linear or branched, or an alicyclic hydrocarbon group.

  The polymer P can further contain a repeating unit represented by the formula (IV) in [Chemical 9] (hereinafter referred to as “repeating unit (D)”) in the molecule.

In formula (IV), R ₁ represents H or CH ₃ , and R ₇ represents an alkyl group having 1 to 22 carbon atoms.

Specific examples of the alkyl group (R ₇ ) in the formula (IV) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group and cyclohexyl group. , Heptyl group, octyl group, nonyl group, decyl group, undecyl group, lauryl group, stearyl group, nonadecyl group, eicosyl group, behenyl group, 2-ethylhexyl group and the like. In this case, the alkyl group may be linear or branched or alicyclic.

  The polymer P can contain the above repeating units (C1), (C2), and (D) as repeating units other than the repeating units (A) and (B), but to the extent that the effects of the present invention are not inhibited. If present, it may further have another repeating unit (hereinafter referred to as “repeating unit (E)”).

  Examples of the repeating unit (E) include (meth) acrylic acid or a salt thereof, 2- (dimethylamino) ethyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, and (meth) acrylic. Multifunctionals such as repeating units formed when polymerizing 2- (dimethylamino) ethylmethyl chloride salt of acid, polyethylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, etc. Examples thereof include a repeating unit derived from a monomer, that is, a crosslinked structure formed by copolymerizing the polyfunctional monomer with another monofunctional monomer. In the present specification, “(meth) acryl-)” means “acryl-” and / or “methacryl-”.

  The polymer P is required to contain a repeating unit (A) and a repeating unit (B) in the molecule, and at least selected from the group of repeating units (C1), (C2), (D) and (E). One or more repeating units can be included.

  Since the polymer P has a molecular structure having at least a repeating unit (A) and a repeating unit (B) in the molecule, it has excellent film properties. For example, a film can be easily formed from a solution in which a resin made of the polymer P is dissolved in a solvent. In particular, since the repeating unit (A) has a property of having high affinity for human skin, hair, etc., the polymer P containing the repeating unit (A) has a film having high affinity for skin and hair. Can be formed.

  Moreover, since the polymer P contains a repeating unit (A) and a repeating unit (B) in a molecule | numerator, it can suppress that the film | membrane formed from the polymer P becomes too hard or becomes too soft. This is because the polymer P molecules (hereinafter sometimes simply referred to as polymer molecules) include both a repeating unit (A) having a property of hardening the film and a repeating unit (B) that gives the film flexibility. It is caused by having. As described above, when the hardness of the film formed from the polymer P is appropriately adjusted, the film is less likely to collapse. Therefore, if the resin made of the polymer P is used as a cosmetic additive, that is, a cosmetic base material for cosmetic applications, a stable film state can be maintained for a long time.

  The adjustment of the hardness and softness of the polymer P in the film state is determined by introducing the repeating unit (A) and the repeating unit (B) into the polymer molecule, that is, the repeating unit (A) per molecule of the polymer. It can be carried out by appropriately adjusting the molar ratio with the repeating unit (B). In the present invention, the molar ratio (unit molar ratio) between the repeating unit (A) and the repeating unit (B) per molecule of the polymer is not particularly limited, and may be appropriately set according to the intended use. . For example, in applications where hardness is required for the film, the number of introduction of the repeating unit (A) may be increased, and in applications where flexibility is required, the number of introduction of the repeating unit (B) should be increased. That's fine.

  For example, in skin cosmetics (for example, foundations), a film formed by applying to the skin often requires both hardness and softness. Therefore, a resin made of the polymer P containing the repeating units (A) and (B) can be suitably employed as a film-forming resin (that is, a base resin) in skin cosmetics.

  Moreover, the film formed from the polymer P comprising the repeating unit (A) and the repeating unit (B) in the molecule is sticky even immediately after the film formation or after a long time has passed. A feeling is hard to occur. Therefore, if the resin made of the polymer P is used as a base material resin for cosmetics, a good feeling of use can be given to the cosmetics.

  When the resin comprising the polymer P is used as a base resin for skin cosmetics and hair cosmetics, in addition to the repeating units (A) and (B), any one of the repeating units (C1) and (C2) Either or both (that is, the repeating unit (C)) is preferably contained in the polymer molecule. In this case, the intermolecular interaction of the polymer is strengthened, whereby the durability and flexibility of the film are improved, and the collapse of the film is further suppressed. Further, the hardness of the polymer P can be adjusted by appropriately selecting the side chain structure of the repeating unit (C). Further, since the repeating unit (C1) has a hydroxyl group in the side chain and the repeating unit (C2) has an alkoxyl group in the side chain, the presence of such a functional group makes the film sticky. It becomes possible to give moderate moisture without giving.

Moreover, when using resin which consists of polymer P as base resins, such as skin cosmetics and hair cosmetics, in addition to repeating unit (A) and (B), repeating unit (D) is further added in a polymer molecule. It is also preferable to include. In this case, it becomes possible to adjust the intermolecular force of the polymer by selecting the type of alkyl group (R ₇ ), and the film collapses by giving the film appropriate hardness, flexibility and durability over time. Can be further suppressed. In particular, in the repeating unit (D), when R ₇ represented by the formula (IV) is an alkyl group having 4 to 12 carbon atoms, the coating can be made more difficult to collapse.

  From the above, among the cosmetics for skin containing such a polymer P, for example, makeup cosmetics have particularly improved makeup retention (makeup sustainability), and even after time has passed since the cosmetic treatment. Make-up breakage is less likely to occur. Among skin cosmetics, for example, skin care cosmetics can continue to give the skin firmness without losing for a long time. In hair cosmetics, hair styling can be provided by a film having both flexibility and hardness.

When the polymer P includes a repeating unit (A1) in which R ₂ and R ₃ in the formula (Ia) are both methyl groups, a repeating unit (A1) other than the repeating unit (A1) is a polymer P It is preferable that it is contained. In this case, it is because the effect mentioned above can further be heightened.

  The polymer P may contain both the repeating units (C) and (D) in addition to the repeating units (A) and (B), and the repeating units (A) to (E). Of all of them. Further, the repeating unit (A) contained in the polymer molecule may be two or more different types. The same applies to the repeating units (B) to (E).

  The polymer P may be a random copolymer in which the above repeating units (A) and (B) are randomly arranged, or may be a block copolymer or an alternating copolymer. The same applies to the case where other repeating units are included in addition to the repeating units (A) and (B). As will be described later, when the polymer P is produced by radical polymerization in the presence of a polymerization initiator, it can usually be a random copolymer. Moreover, as long as the effect of the present invention is not inhibited, the polymer P may have a crosslinked structure or a graft polymer (a polymer having a branched molecular structure).

  The weight average molecular weight of the polymer P is not particularly limited. However, when the resin comprising the polymer P is used as a base material for cosmetics such as skin cosmetics and hair cosmetics, 3,000 to 100, 000 is preferred. The weight average molecular weight here refers to a value measured in terms of polystyrene by gel permeation chromatography. If the upper limit of the weight average molecular weight is 100,000, it becomes easy to prevent the film from becoming too hard, and the effect of suppressing the collapse of the film is enhanced, and the viscosity of the solution of the polymer P does not become too high. For example, handling properties when blended into cosmetics are improved. Further, if the lower limit of the weight average molecular weight is 3,000, the stickiness of the film can be further suppressed, and an appropriate film feeling can be given, so that the feeling of use of the cosmetic can be further enhanced. it can. A more preferable upper limit of the weight average molecular weight is 50,000, and a more preferable lower limit is 5,000.

  Further, the glass transition temperature (Tg) of the polymer P is not particularly limited, but when the resin made of the polymer P is used as a base resin for skin cosmetics, hair cosmetics, etc., 10-60. It is preferable that it is ° C. The glass transition temperature here is a value that is theoretically calculated from the composition ratios of the various components of the ethylenically unsaturated monomer used in obtaining the polymer P by polymerization of the ethylenically unsaturated monomer component. This is a value calculated by the following Fox equation.

1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ +... + W _n / Tg _n
Here, the above formula is a calculation formula when the polymer P is obtained by polymerization of n types (n is an integer of 1 or more) of ethylenically unsaturated monomer components. W _{1, W} 2, · · · _{W n,} respectively, show the respective weight fraction of n kinds of the ethylenically unsaturated monomer _component, Tg _1, Tg 2, respectively · · · Tg _n is one It is a so-called homopolymer glass transition temperature obtained by polymerization of an ethylenically unsaturated monomer component. The unit of glass transition temperature in the Fox equation is the absolute temperature “K”. However, the above calculation in the present invention is applied only to a monofunctional monomer, and among the monomer components (e) described later, a polyfunctional monomer (single amount that gives a crosslinked structure by polymerization) Body (eg, polyethylene glycol diacrylate) is not considered a component in this calculation and is excluded. That is, even if the polyfunctional monomer is contained in the ethylenically unsaturated monomer component, it is assumed that the polyfunctional monomer is not contained, and Tg is calculated by the above formula. Shall. A method for obtaining the polymer P by polymerization of the ethylenically unsaturated monomer component will be described later.

  If the upper limit of the said glass transition temperature is 60 degreeC, it can prevent that a film | membrane becomes hard too much and collapse of a film | membrane is suppressed. Therefore, it is possible to improve the longevity of the cosmetic. Furthermore, an excessive feeling of tension when blended in the cosmetic for skin can be suppressed. Moreover, if the minimum of glass transition temperature is 10 degreeC, the stickiness of a film | membrane can be suppressed further and the usability | use_condition of cosmetics can be raised more. Furthermore, in order to give moderate film forming property, when it mix | blends with skin cosmetics, it can give a favorable feeling of elasticity, and when it mix | blends with hair cosmetics, moderate hair styling property can be provided. The upper limit with a more preferable glass transition temperature is 50 degreeC, and a more preferable minimum is 20 degreeC.

  The polymer P can be synthesized by performing a polymerization reaction of the ethylenically unsaturated monomer component.

  Hereinafter, the ethylenically unsaturated monomer component and the polymerization method thereof will be described in detail.

  The ethylenically unsaturated monomer component includes a monomer represented by the formula (1-a) of [Chemical Formula 5] (hereinafter referred to as “monomer component (a1)”) and a formula of [Chemical Formula 6] ( One or both of the monomers represented by 1-b) (hereinafter referred to as “monomer component (a2)”) may be included. Hereinafter, the monomer component (a1) and the monomer component (a2) are collectively referred to as “monomer component (a)”.

  The monomer component (a) is a monomer that can introduce the repeating unit (A) into the molecule of the polymer P (polymer molecule) by polymerization. Specifically, the monomer component (a1) corresponds to the monomer that gives the repeating unit (A1) and the monomer component (a2) gives the repeating unit (A2) to the molecule.

  Specific examples of the monomer component (a1) include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N- Examples include t-butyl (meth) acrylamide, N-octylacrylamide, Nt-octylacrylamide, N- (2-hydroxyethyl) (meth) acrylamide and the like. When the monomer component (a1) contains N, N-dimethyl (meth) acrylamide, it is preferably a mixture further containing another monomer component (a1). In this case, from the stability of the film improves.

  Specific examples of the monomer component (a2) include acryloylmorpholine.

  The ethylenically unsaturated monomer component includes a monomer represented by the formula (2-a) of [Chemical Formula 10] (hereinafter referred to as “monomer component (b1)”) and [Chemical Formula 11]. Either or both of the monomers represented by the formula (2-b) (hereinafter referred to as “monomer component (b2)”) may be included. Hereinafter, the monomer component (b1) and the monomer component (b2) are collectively referred to as “monomer component (b)”.

In formula (2-a), R ₁ represents H or CH ₃ , R ₄ represents H or an alkyl group having 1 to 18 carbon atoms, and A ₁ represents O or NH. X, y, and z are each an integer of 0 to 100, and x + y + z ≧ 2. (EO) represents (C ₂ H ₄ O), (PO) represents (C ₃ H ₆ O), and (BO) represents (C ₄ H ₈ O).

In formula (2-b), R ₁ represents H or CH ₃ , R ₄ represents H or an alkyl group having 1 to 18 carbon atoms, and A ₁ represents O or NH. X, y, and z are each an integer of 0 to 100, and x + y + z ≧ 2. (EO) represents (C ₂ H ₄ O), (PO) represents (C ₃ H ₆ O), and (BO) represents (C ₄ H ₈ O). [-(EO) x- (PO) y- (BO) z-] in the formula (2-b) means that each repeating unit of EO, PO, and BO is randomly arranged, that is, EO , PO and BO are random copolymers.

  The monomer component (b) is a monomer that can introduce the repeating unit (B) into the polymer molecule by polymerization. Specifically, the monomer component (b1) corresponds to the monomer that gives the repeating unit (B1) and the monomer component (b2) gives the repeating unit (B2) to the molecule.

  The monomer component (b1) is a repeating unit of oxyethylene (also referred to as ethylene oxide, expressed as EO), oxypropylene (also referred to as propylene oxide, expressed as PO), and oxybutylene (also referred to as butylene oxide, expressed as BO). The block copolymer which consists of has the structure couple | bonded with the side chain.

  Specific examples of the monomer component (b1) include polyethylene glycol-polypropylene glycol monomethacrylate (x = 5, y = 2, z = 0) (Blenmer 70PEP-350B manufactured by NOF Corporation), propylene glycol polybutylene glycol. Monomethacrylate (x = 0, y = 1, z = 6) (Blenmer 10PPB-500B manufactured by NOF Corporation), Octoxy polyethylene glycol polypropylene glycol monomethacrylate (x = 8, y = 6, z = 0) (Sun Monofunctional unsaturated single amount such as Blemmer 50POEP-800B manufactured by Oil Co., Ltd., Octoxy polyethylene glycol polypropylene glycol monoacrylate (x = 8, y = 6, z = 0) (Blenmer 50AOEP-800B manufactured by NOF Corporation) The body is mentioned.

  The monomer component (b2) has a structure in which a random copolymer composed of repeating units of oxyethylene (EO), oxypropylene (PO), and oxybutylene (BO) is bonded to a side chain.

  Specific examples of the monomer component (b2) include poly (ethylene glycol-propylene glycol) monomethacrylate (x = 3.5, y = 2.5, z = 0) (Blenmer 50PEP-300 manufactured by NOF Corporation). ), Poly (ethylene glycol-tetramethylene glycol) monomethacrylate (x = 5, y = 0, z = 2) (Blenmer 55PET-400 manufactured by NOF Corporation), poly (ethylene glycol-tetramethylene glycol) monomethacrylate ( x = 6, y = 0, z = 10) (Blenmer 30PET-800 manufactured by NOF Corporation), poly (ethylene glycol-tetramethylene glycol) monomethacrylate (x = 10, y = 0, z = 5) (Sun Buremer 55PET-800 manufactured by Oil Co., Ltd., poly (propylene glycol-tetramethylene glycol) No methacrylate (x = 0, y = 4, z = 8) (Blenmer 30PPT-800 manufactured by NOF Corporation), poly (propylene glycol-tetramethylene glycol) monomethacrylate (x = 0, y = 7, z = 6) ) (Blenmer 50PPT-800 manufactured by NOF Corporation), poly (propylene glycol-tetramethylene glycol) monomethacrylate (x = 0, y = 10, z = 3) (Blenmer 70PPT-800 manufactured by NOF Corporation), etc. A monofunctional unsaturated monomer is mentioned.

  The ethylenically unsaturated monomer component includes a hydroxyalkyl (meth) acrylate (hereinafter referred to as “monomer component (c1)”) and an alkoxyalkyl (meta) represented by the formula (3) of [Chemical Formula 12]. ) Acrylate (hereinafter referred to as “monomer component (c2)”) or both. Hereinafter, the monomer component (c1) and the monomer component (c2) are collectively referred to as “monomer component (c)”.

In Formula (3), R ₁ represents H or CH ₃ , and R ₆ represents an alkyl group having 1 to 18 carbon atoms. N is an integer of 1-8.

  The monomer component (c) is a monomer that can introduce the repeating unit (C) into the polymer molecule by polymerization. Specifically, the monomer component (c1) corresponds to the monomer that gives the repeating unit (C1) and the monomer component (c2) gives the repeating unit (C2) to the molecule.

  In the hydroxyalkyl (meth) acrylate of the monomer component (c1), the hydroxyalkyl has 1 to 8 carbon atoms. Specific examples of such hydroxyalkyl (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylate. 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, and the like.

  Specific examples of the monomer component (c2) (monomer represented by the formula (3)) include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and (meth) acrylic acid. (Meth) acrylic acid alkoxyalkyl esters such as 3-methoxypropyl may be mentioned.

  In addition to the above, the ethylenically unsaturated monomer component is an ester of (meth) acrylic acid and a monoalcohol having a linear, branched or alicyclic hydrocarbon group having 1 to 22 carbon atoms. The compound may contain an alkyl (meth) acrylate (hereinafter referred to as “monomer component (d)”).

  Specific examples of the monomer component (d) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) ) Acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodesi (Meth) acrylate, undecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) ) Acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate and the like.

  In addition to the above, the ethylenically unsaturated monomer component may be any other monomer (other than the monomer components (a) to (d)) as long as the effects of the present invention are not inhibited. Monomer component (e) "). The monomer component (e) is a monofunctional or polyfunctional monomer capable of introducing the repeating unit (E) into the polymer molecule by polymerization.

  Specific examples of the monomer component (e) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and 1,6-hexane. Polyfunctional monomers such as diol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate; glycidyl ( Examples thereof include cyclic ether (meth) acrylates such as (meth) acrylate and tetrahydrofurfuryl (meth) acrylate.

  Moreover, an ionic unsaturated monomer is mentioned as another specific example of a monomer component (e). The ionic unsaturated monomer includes an anionic unsaturated monomer, a cationic unsaturated monomer, and an amphoteric unsaturated monomer. The amphoteric unsaturated monomer may include a precursor of the amphoteric unsaturated monomer, that is, a monomer that becomes an amphoteric unsaturated monomer by amphoteric conversion.

  Among the ionic unsaturated monomers, examples of the anionic unsaturated monomer include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; unsaturated dicarboxylic acids such as itaconic acid and maleic acid; Monoalkyl esters of unsaturated dicarboxylic acids such as acid monoalkyl esters, fumaric acid monoalkyl esters, itaconic acid monoalkyl esters, 2-methacryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, β-carboxy Ethyl acrylate; acryloyloxyethyl succinate, 2-propenoic acid, 3- (2-carboxyethoxy) -3-oxypropyl ester, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid, 2- (meth) acryloyloxy Ethyl hexahydrophthal , Vinyl sulfonic acid, alkene sulfonic acid such as (meth) allyl sulfonic acid, aromatic vinyl group-containing sulfonic acid such as α-methylstyrene sulfonic acid; sulfonic acid group-containing (meth) acrylic ester monomer, 2- ( Sulphonic acid group-containing monomers such as (meth) acrylamide-2-methylpropanesulfonic acid and other methacrylic monomers, and methacryloyloxyalkyl phosphates such as (meth) acryloyloxyethyl phosphate Examples thereof include phosphate group-containing unsaturated monomers such as monoesters.

  Among the ionic unsaturated monomers, examples of the cationic unsaturated monomer include a primary to tertiary amino group-containing unsaturated monomer and a quaternary ammonium base-containing unsaturated monomer. .

  Among the above-mentioned cationic unsaturated monomers, the primary to tertiary amino group-containing unsaturated monomers include, for example, (meth) allylamine, aminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, methylaminoethyl ( Amino group-containing fragrances such as alkylaminoalkyl (meth) acrylates such as meth) acrylate, dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and N, N-dimethylaminostyrene Group vinyl monomers and the like.

  Among the cationic unsaturated monomers, as the quaternary ammonium base-containing unsaturated monomer, for example, the above-mentioned tertiary amino group-containing unsaturated monomer is converted into a quaternizing agent (carbon number is 1). And quaternized with -12 alkyl chloride, dialkyl sulfuric acid, dialkyl carbonate, benzyl chloride and the like. Specifically, as the quaternary ammonium base-containing unsaturated monomer, for example, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, Alkyl (meth) acrylate quaternary ammonium salts such as (meth) acryloyloxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminoethyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyl Alkyl (meth) acryloylamide quaternary ammonium salts such as dimethylbenzylammonium chloride, dimethyl Allyl ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  Examples of amphoteric unsaturated monomers include amine derivatives of (meth) acrylic acid such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate; dimethylaminoethyl (meth) acrylamide , (Meth) acrylamide derivatives such as dimethylaminopropyl (meth) acrylamide, halogenated fatty acid salts such as aminomethyl propanol salt of monochloroacetic acid, triethanolamine salt of monochloroacetic acid, potassium monochloroacetate, sodium monobromopropionate; Examples include lactones such as propiolactone; unsaturated monomers modified with sultone such as propane sultone, and the like.

  In the case where the ethylenically unsaturated monomer component contains a precursor of an amphoteric unsaturated monomer, after the polymerization of the ethylenically unsaturated monomer component, the precursor in the polymer obtained by this polymerization Are amphotericized with amphoteric agents (monochloroacetic acid, monobromopropionic acid, lactones such as propiolactone; sultones such as propane sultone). The salt generated as a result of amphotericization is removed by an appropriate method such as filtration or ion exchange as necessary. When the precursor of the amphoteric unsaturated monomer is used in this way, the polymerization reaction of the ethylenically unsaturated monomer component is more stable than when a previously amphoteric monomer is used.

  When the monomer component (e) is contained in the ethylenically unsaturated monomer component, the hardness of the film formed from the polymer of the ethylenically unsaturated monomer component (polymer P), flexibility, It becomes possible to adjust moisture resistance, hydrophilicity, adhesion to skin and hair, adhesiveness, and the like.

  The ethylenically unsaturated monomer component may contain additives such as a polymerization inhibitor, a light stabilizer, and a diluting solvent as long as the effects of the present invention are not inhibited.

  The mixing ratio of each monomer component of the ethylenically unsaturated monomer component can be adjusted as appropriate. In particular, when a resin (polymer P) comprising a polymer of an ethylenically unsaturated monomer component is used for a cosmetic base material, the monomer component (a) is an ethylenically unsaturated monomer component. The total mass can be 30 to 70% by mass. If the upper limit of the content of the monomer component (a) is 70% by mass, it is easy to prevent the polymer P film from becoming hard, the film is less likely to disintegrate over time, and the cosmetic durability is improved. . Moreover, if the lower limit of the content of the monomer component (a) is 30% by mass, it becomes easy to prevent the film of the polymer P from being softened, and stickiness when blended in a cosmetic is suppressed. A good usability can be obtained, and a decrease in the water solubility of the polymer P can be suppressed. Therefore, for example, it can be easily blended into an emulsifier type aqueous phase.

  The monomer component (b) is 1 to 50% by mass relative to the total mass of the ethylenically unsaturated monomer component, and the monomer component (c) is the total ethylenically unsaturated monomer component. 1 to 40% by mass with respect to the mass, the monomer component (d) is 1 to 40% by mass with respect to the total mass of the ethylenically unsaturated monomer component, and the monomer component (e) is ethylenic. It is preferable that it is 0.1-5 mass% with respect to the total mass of an unsaturated monomer component.

  As a polymerization method for the ethylenically unsaturated monomer component, a solution copolymerization method using a hydrophilic solvent or a mixed solvent of water and a hydrophilic solvent may be employed. In this case, for example, a reaction solution is prepared by dissolving an ethylenically unsaturated monomer component in a hydrophilic solvent or a mixed solvent and adding a radical polymerization initiator, and at a boiling point of the solvent or a temperature in the vicinity thereof under a nitrogen stream. By stirring, the ethylenically unsaturated monomer component can be polymerized. In the reaction solution, all types and amounts of the monomer components contained in the ethylenically unsaturated monomer component may be dissolved from the beginning of the reaction, but depending on the type, amount, etc. of the monomer component The ethylenically unsaturated monomer component may be dividedly added to the reaction solution while the polymerization reaction proceeds. Alternatively, the ethylenically unsaturated monomer component may be continuously dropped into the reaction solution while the polymerization reaction proceeds. The amount of the solvent used is preferably adjusted so that the polymer (resin) solid concentration in the solution at the end of the polymerization reaction is in the range of 20 to 80% by mass.

  As described above, the solvent used for the solution copolymerization is a hydrophilic solvent or a mixed solvent of water and a hydrophilic solvent. The hydrophilic solvent is preferably an organic solvent having a solubility in water of 10 g / 100 g of water (25 ° C.) or more. Examples of such hydrophilic solvents include aliphatic 1-4 tetrahydric alcohols having 1 to 4 carbon atoms such as methanol, ethanol, 2-propanol, butanol, ethylene glycol and glycerin; acetone; methyl cellosolve; ethyl cellosolve, butyl cellosolve. Glycol ethers such as dioxane; methyl acetate; ethyl acetate; dimethylformamide and the like. A hydrophilic solvent may be used individually by 1 type, and may use 2 or more types together. In view of using the polymer P as a base material for cosmetics, ethanol or 2-propanol is used alone in consideration of the possibility that the remaining solvent during polymerization may adhere to the human skin. Or it is good to use together.

  Any suitable radical polymerization initiator may be used. For example, peroxides such as benzoyl peroxide, lauroyl peroxide and hydrogen peroxide; persulfates such as ammonium persulfate and potassium persulfate; 2,2′- Azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis-1-cyclohexanecarbonitrile, 4 , 4'-azobis-4-cyanovaleric acid, 2,2'-azobis- (2-amidinopropane) -dihydrochloride and the like are preferably used.

  In addition, a chain transfer agent may be added to the reaction solution as necessary for adjusting the weight average molecular weight. The chain transfer agent is not particularly limited, and examples thereof include compounds having a mercaptan group such as lauryl mercaptan, dodecyl mercaptan, and thioglycerol; inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of the chain transfer agent used is appropriately determined so that the molecular weight of the polymer P falls within the desired range, but is usually 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the ethylenically unsaturated monomer components. A range of parts by weight is preferred.

  Moreover, you may polymerize an ethylenically unsaturated monomer component by a living radical polymerization method. In this case, adjustment of the weight average molecular weight of the polymer P becomes easy, and a polymer P having a narrower molecular weight distribution than when a chain transfer agent is used is generated.

  Of course, the polymerization method for obtaining the polymer P is not limited to the above-mentioned solution copolymerization method, and other methods such as suspension polymerization, bulk polymerization, and dispersion polymerization may be employed. In addition to radical polymerization, the polymerization reaction can be performed by ionic polymerization or the like.

  The polymerization conditions such as temperature and time during the polymerization of the ethylenically unsaturated monomer component are such that the polymerization reaction proceeds at a high reaction rate depending on the type of the ethylenically unsaturated monomer component and the radical polymerization initiator. Is set as appropriate. The polymerization reaction may be performed in an atmosphere of an inert gas such as nitrogen gas or argon gas. The smaller the amount of unreacted monomer remaining at the end of the polymerization reaction, the better.

  By such a polymerization reaction of the ethylenically unsaturated monomer component, a solution containing a resin composed of the polymer P of the ethylenically unsaturated monomer component is generated. In this invention, since repeating unit (A) and (B) are included in a molecule | numerator, resin produced | generated by the said polymerization reaction is a copolymer.

  Depending on the type of resin produced, it may be neutralized with a basic compound. In this case, good water solubility can be imparted to the resin. In particular, the resin is used as a base material for cosmetics. Suitable for the case.

  An appropriate organic or inorganic basic compound can be used as the basic compound. The organic basic compound is preferably water-soluble. Examples of the organic basic compound include morpholine, N, N-dimethylamine, N, N-diethylamine, ethanolamine, N, N-diethanolamine, N, N, N-triethanolamine, and 2-amino-2. Examples include methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, and triisopropanolamine. Examples of the inorganic basic compound include ammonia, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Among these basic compounds, particularly those which can be generally used as cosmetic raw materials, ethanolamine, N, N-diethanolamine, N, N, N-triethanolamine, 2-amino-2methyl-1-propanol 2-amino-2-methyl-1,3-propanediol, triisopropanolamine, sodium hydroxide, potassium hydroxide and the like are preferably used.

  These basic compounds may be used alone or in combination of two or more. Although the neutralization rate of the polymer P is set as appropriate, the neutralization rate is preferably in the range of 50 to 100% in order to impart sufficiently high water solubility to the resin.

  The polymer P may be produced by a method other than the above. For example, a polymer or an oligomer such as polyacrylic acid or polyacrylamide is prepared in advance, and a polymer having a predetermined molecular structure is reacted with the side chain of the polymer or oligomer to synthesize a polymer P to form a resin. You can also get

  The resin made of the polymer P can be used for various purposes, but as described above, it has excellent film properties on the skin (easiness of formation and resistance to collapse). It is suitably used as a material. The base material for cosmetics refers to an additive for forming a film when the cosmetic is applied. In particular, since the component for forming the film here corresponds to a resin, The resin component in the base material for use may be referred to as a base material resin. Moreover, a film | membrane means the film | membrane derived from the said base resin formed in skin etc.

  The cosmetic base material may contain known additives such as a solvent, a dispersion stabilizer, a preservative, and a light stabilizer in addition to the resin made of the polymer P, if necessary.

  Below, the specific example in case resin using the polymer P is used as a base material for cosmetics is demonstrated.

  The cosmetic base material can be applied to skin cosmetics. In this case, the resin composed of the polymer P contained in the cosmetic base corresponds to the base resin of the skin cosmetic (hereinafter referred to as “skin cosmetic resin”).

  The skin cosmetic containing the above-mentioned resin for skin cosmetics is not particularly limited. For example, makeup cosmetics such as liquid foundation and cream foundation, moisturizing beauty liquid, milky lotion, moisturizing cream, etc. It can be applied to skin care cosmetics.

  The makeup cosmetic is blended with the skin cosmetic resin and other necessary raw materials.

  The raw materials other than the skin cosmetic resin contained in the makeup cosmetics are not particularly limited as long as they are raw materials conventionally used in makeup cosmetics. Examples include extender pigments, colorants (color pigments), pearl agents, lame agents, oils, waxes, moisturizers, and the like.

  As extender pigments, pulverized products of viscous minerals such as mica, sericite, talc, kaolin, silicic anhydride, cerium oxide, silica, zinc stearate, fluorinated phlogopite, synthetic talc, barium sulfate, boron nitride, oxychloride Examples include bismuth, alumina, magnesium carbonate and the like.

  Examples of the colorant include bengara, yellow iron oxide, black iron oxide, red iron oxide, ultramarine blue, titanium oxide, zinc oxide, and salmon.

  As the pearl agent, titanium dioxide coated mica (titanium mica), iron oxide coated mica titanium, carmine coated mica titanium, carmine / konjo coated mica titanium, iron oxide / carmine-treated mica titanium, conger-treated mica titanium, iron oxide / konjo-treated mica Titanium, chromium oxide-treated mica titanium, black titanium oxide mica titanium, acrylic resin coated aluminum powder, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, titanium oxide coated synthetic mica, oxidation Examples include titanium-coated silica, titanium oxide-coated alumina, titanium oxide-coated glass powder, polyethylene terephthalate / polymethyl methacrylate laminated film powder, bismuth oxychloride, fish scale foil, and the like.

  Resin and metal powder can be used as lame agent, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / aluminum laminated powder, polyethylene terephthalate / gold laminated powder, polyethylene terephthalate / polyolefin laminated film powder, polyethylene terephthalate / Examples thereof include polymethyl methacrylate laminated film powder, polyethylene / polyester laminated powder, polyethylene / polyethylene terephthalate laminated powder, acrylic resin-coated aluminum powder, and the like. Further, those powders colored with legal dyes or inorganic pigments can also be used.

  Examples of oils include hydrocarbon oils, ester oils, silicone oils and the like, specifically, hydrocarbon oils such as squalane, liquid paraffin, petrolatum, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, Higher fatty acids such as behenic acid, higher alcohols such as cetyl alcohol, stearyl alcohol, oleyl alcohol, batyl alcohol, cetyl-2-ethylhexanoate, 2-ethylhexyl palmitate, 2-octyldodecyl myristate, neopentyl glycol-2- Ethyl hexanoate, glyceryl trioctanoate, pentaerythritol tetraoctanoate, glyceryl stearate, glyceryl triisostearate, glyceryl diisostearate, isopropyl myristate, myristyl myris Oils such as salt, glyceryl trioleate, olive oil, avocado oil, jojoba oil, sunflower oil, safflower oil, coconut oil, macadamia nut oil, mink oil, lanolin, liquid lanolin, lanolin acetate, castor oil, dimethyl Polysiloxane, methylphenyl polysiloxane, high-polymerized gum-like dimethylpolysiloxane, polyether-modified silicone, amino-modified silicone and other silicone oils, fluorine-modified dimethylpolysiloxane, fluorine-modified methylphenylpolysiloxane, perfluoropolyether, Fluorine oil such as perfluorocarbon is included.

  Examples of the wax include carnauba wax, candelilla wax, bees wax, mole, ceresin wax, microcrystalline wax, and solid paraffin wax.

  Examples of the humectant include polyhydric alcohol humectants such as glycerin, propylene glycol, and 1,3-butylene glycol.

  In addition to the above additives, makeup cosmetics include dimethicone, methicone, silane coupling agents, silicone compounds such as alkyl-modified silicones and silicone resins, perfluoroalkyl phosphates and salts thereof, perfluoroalkyl silanes, Teflon ( (Registered trademark), fluorine compounds such as perfluoroalkyl carboxylic acid, dimethicone-derived surfactants such as PEG10-dimethicone, preservatives, antioxidants, and fragrances. The silicone compound can be used as an emollient.

  Moreover, as long as the effect of the said resin for skin cosmetics is not inhibited, resin and oligomer components other than the resin for skin cosmetics may be contained in makeup cosmetics.

  The preparation method of makeup cosmetics is not specifically limited, A well-known method is employable. For example, makeup cosmetics can be prepared by mixing each raw material, dispersing or dissolving in a solvent or the like as necessary, and wet molding. In blending the resin for skin cosmetics, it may be mixed in a solid state, or may be mixed in a solution or dispersion state. Moreover, you may use the reaction liquid after the polymerization reaction of resin for skin cosmetics as it is.

  Makeup cosmetics containing the above skin cosmetic resin can be selected by appropriately selecting the type and amount of raw materials to be blended, for example, powder foundations such as powder foundations and cake foundations, cream foundations, O / W emulsifying foundations, It can be used as a cosmetic for base makeup such as an emulsified foundation such as a W / O emulsified foundation, a liquid foundation or an oily foundation. Among these, in particular, it can be suitably used as a liquid type foundation.

  On the other hand, skin care cosmetics such as moisturizing cosmetic liquid and milky lotion can also be carried out by mixing the above-mentioned skin cosmetic resin and other necessary raw materials. As other raw materials, known raw materials conventionally added to skin care cosmetics can be used. For example, polyhydric alcohols, vegetable oils, amino acids, peptides, proteins, sugars, emulsifiers, humectants, alkaline agents , Thickeners, colorants, fragrances and the like.

  Since the makeup cosmetic contains the above-mentioned resin for skin cosmetics, the makeup cosmetics have a good feeling of use for a long time, are not easily broken, and have excellent makeup. Further, since the skin care cosmetic contains the above-mentioned resin for skin cosmetics, the firmness of the skin is maintained for a long time, and at the same time, the sticky feeling is suppressed. This is because, as described above, the film formed of the above-described resin for skin cosmetics is unlikely to collapse, and even after a long time after makeup, the sticky feeling is suppressed.

  Although content in particular for skin cosmetics of resin for skin cosmetics is not restrict | limited, For example, 0.01-30 mass% with respect to the total amount of all the components of skin cosmetics, Preferably 0.1-20 masses %, Particularly preferably 0.5 to 15% by mass, the above-described effects of the skin cosmetics are sufficiently exhibited.

  The cosmetic base material can also be applied to hair cosmetics. In this case, the resin composed of the polymer P contained in the cosmetic base corresponds to the base resin of the hair cosmetic (hereinafter referred to as “hair cosmetic resin”).

  Hair cosmetics can be performed by mixing the above-mentioned hair cosmetic resin and other necessary raw materials. In mixing the hair cosmetic resin, it may be mixed in a solid state, or may be mixed in a solution or dispersion state.

  Other necessary raw materials in hair cosmetics are not particularly limited as long as they are raw materials conventionally used in hair cosmetics. For example, various components, such as a polyhydric alcohol, surfactant, silicone, an ultraviolet-ray inhibitor, antioxidant, a hair nourishing agent, are mentioned. Moreover, as long as the effect of the said resin for hair cosmetics is not inhibited, resin and oligomer components other than the resin for hair cosmetics may be contained in the hair cosmetic resin.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, and 2-methyl-1,3-trimethylene diol. 1,5-pentamethylenediol, neopentylglycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, glycerin, tri Examples include methylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol, sorbitol, etc.) and the like.

  Hair cosmetics containing the above hair cosmetic resins include, for example, hair spray agents, hair mists, hair gels, hair creams, hair waxes, hair lotions, non-gas aerosol agents (hair mist agents), hair styling foams (hair mousses), and curler water. It can be used as a hair treatment. What is necessary is just to prepare these various cosmetics for hair by a well-known method.

  A hair cosmetic blended with a resin for hair cosmetics has excellent usability and excellent hairstyle retention over a long period of time. This is due to the durability over time and the high flexibility and low stickiness of the film formed of the resin for hair cosmetics.

  The content of the hair cosmetic resin with respect to the hair cosmetic is not particularly limited. For example, the content is 0.01 to 30% by mass, preferably 0.1 to 20% by mass, based on the total amount of all the components of the hair cosmetic. Particularly preferably, if the content is 1 to 15% by mass, the above-described effects of the cosmetic for hair are sufficiently exhibited.

  In addition to the above, the resin comprising the polymer P may be other cosmetics such as antiperspirants, protective agents, skin deodorants, whitening cosmetics, point makeup cosmetics (lipstick, eye shadow, etc.), deodorant cosmetics. It can also be applied to cleaning cosmetics.

  Hereinafter, the present invention will be specifically described by way of examples. Unless otherwise indicated, all% described below are based on mass.

(Examples and comparative examples)
As a reaction vessel, a 5-liter flask with a capacity of 1 liter equipped with a reflux condenser, a thermometer, a nitrogen replacement tube, a dropping funnel and a stirrer was used. The temperature increased. When the ethanol in the reaction vessel was refluxed, 2,2′-azobisisobutyronitrile (AIBN) in the amount shown in Tables 1 and 2 was added to the ethanol. Immediately after the addition, a mixture containing the ethylenically unsaturated monomers in the amounts shown in Tables 1 and 2 was continuously dropped into the reaction vessel from the dropping funnel for 2 hours to prepare a reaction solution. After completion of the dropwise addition, the polymerization reaction was allowed to proceed by maintaining the reflux state of the reaction solution for 2 hours. Next, the solvent was distilled off from the solution in the reaction vessel, and ethanol was added to the reaction solution to adjust the solvent content in the solution to obtain a resin solution having a solid content concentration of 70%.

  Tables 1 and 2 show the glass transition temperature and the weight average molecular weight of the resins obtained together with the blending conditions. The glass transition temperatures shown in Tables 1 and 2 are values calculated using the above Fox equation. In addition, the blank in the column of each compounding amount of Tables 1 and 2 indicates 0.

  Here, the kind of ethylenically unsaturated monomer used in each Example and Comparative Example is as follows. In Tables 1 and 2, (a1), (a2), (b1), (b2), (c1), (c2), (d) and (e) are the monomer component (a1), Monomer component (a2), monomer component (b1), monomer component (b2), monomer component (c1), monomer component (c2), monomer component (d) and monomer Represents component (e). In addition, “Tg” of each monomer component is a so-called homopolymer obtained by polymerization of a monofunctional component among the monomer components (a1) to (d) and the monomer component (e). The glass transition temperature is shown.

(Monomer component (a1))
Acrylamide (Tg = 179 ° C)
・ N, N-dimethylacrylamide (Tg = 119 ° C)
・ N, N-diethylacrylamide (Tg = 81 ° C)
N- (2-hydroxyethyl) acrylamide (Tg = 98 ° C.)
(Monomer component (a2))
4-acryloylmorpholine (Tg = 145 ° C.)
(Monomer component (b1))
Polyethylene glycol acrylate (10) (Blenmer AE-400 manufactured by NOF Corporation (in the formula (2-a), x = 10, y = 0, z = 0)) (Tg = −67 ° C.)
-Polypropylene glycol acrylate (6) (Blenmer AP-400 manufactured by NOF Corporation (in the formula (2-a), x = 0, y = 6, z = 0)) (Tg = -59 ° C.)
-Methoxypolyethylene glycol methacrylate (9) (Shin Nakamura Chemical Co., Ltd. NK ester M-90G (in the formula (2-a), x = 9, y = 0, z = 0)) (Tg = -69 ° C.)
Methacrylic acid (polyethylene glycol (5) -polypropylene glycol (2)) (Blenmer 70PEP-350B manufactured by NOF Corporation (in the formula (2-a), x = 5, y = 2, z = 0)) (Tg = −60 ° C.) (In Tables 1 and 2, methacrylic acid (denoted as PEG (5) -PPG (2))
Methacrylic acid (propylene glycol-polybutylene glycol (6)) (Blenmer 10PPB-500B manufactured by NOF Corporation (in the formula (2-a), x = 0, y = 1, z = 6)) (Tg =- 50 to -60 ° C: calculated in the examples as -55 ° C. (In Tables 1 and 2, methacrylic acid (indicated as PG-PBG (6))
(Monomer component (b2))
Polymethacrylate (ethylene glycol (10) -tetramethylene glycol (5)) (Blenmer 55PET-800 manufactured by NOF Corporation (in the formula (2-b), x = 10, y = 0, z = 5)) (Tg = −66 ° C.) (In Tables 1 and 2, expressed as polymethacrylate (EG (10) -TMG (5)))
(Monomer component (c1))
・ 2-hydroxyethyl acrylate (Tg = -15 ° C)
・ 2-hydroxyethyl methacrylate (Tg = 55 ° C)
・ 2-hydroxybutyl methacrylate (Tg = 115 ° C)
(Monomer component (c2))
・ 2-methoxyethyl methacrylate (Tg = -2 ° C)
・ 2-Ethoxyethyl methacrylate (Tg = −31 ° C.)
(Monomer component (d))
・ Methyl methacrylate (Tg = 105 ℃)
・ Butyl methacrylate (Tg = 20 ℃)
・ Lauryl acrylate (Tg = 15 ℃)
・ Lauryl methacrylate (Tg = -65 ° C)
・ Stearyl methacrylate (Tg = 38 ℃)
(Monomer component (e))
・ 2- (dimethylamino) ethyl methacrylate (Tg = 18 ° C.)
-Polyethylene glycol dimethacrylate (9) (chain length of polyethylene glycol moiety 9) (multifunctional)
・ Diacrylic acid 1,9-nonanediol (multifunctional)
[Measurement method of weight average molecular weight]
The solvent was evaporated from the resin solutions obtained in each of the examples and comparative examples to dryness to obtain a solid resin. This was dissolved in tetrahydrofuran (THF), and the weight average molecular weight was measured by gel permeation chromatography (SHODEX SYSTEM 11 manufactured by Showa Denko KK).

Details of the measurement conditions are as follows.
-Column: 4 series of SHODEX KF-800P, KF-805, KF-803, KF-801.
-Mobile phase: THF.
-Flow rate: 1 ml / min.
Column temperature: 40 ° C.
Detector: RI.
・ Molecular weight conversion: Polystyrene.

<Performance evaluation of resin>
An emulsified composition was prepared using each resin solution obtained in each Example and Comparative Example. In preparing the emulsified composition, the blending components (K) and (L) shown in Table 3 are prepared, and while the blending component (K) is being stirred, the blending component (L) is gradually added and coarsely dispersed. Then, it adjusted by emulsifying with a homomixer and defoaming. The blending composition ratios of the blending components (K) and (L) are shown in Table 3. Moreover, the detail of each raw material of a compounding component (K) is as follows.
Volatile oil: Shin-Etsu Chemical Co., Ltd. KF-995.
Surfactant: Shin-Etsu Chemical Co., Ltd. KF-6017.

[Evaluation when applied to skin]
0.1 g of the obtained emulsified composition was applied to the inner part of each forearm of 5 subjects, and the stickiness and film properties immediately after application, and the stickiness and film properties after 2 hours of application, Each subject judged according to the evaluation criteria shown below.

[Evaluation criteria]
2: Very good.
1: Good.
0: Normal.
-1: Somewhat bad.
-2: Bad.

  The average value of each subject's evaluation based on this evaluation standard is calculated, and the case where the average value is 1 or more and 2 or less is very good (◎), the case where it is 0 or more and less than 1 is good (◯), -1 or more and more The case of less than 0 was judged to be a little bad (Δ), and the case of -2 to less than −1 was judged to be bad (×).

  The results are shown in Tables 1 and 2 (see “Evaluation to Skin” in Tables 1 and 2).

  As is apparent from the results in Tables 1 and 2, the emulsion composition containing the resin of the present invention as a film-forming agent has low stickiness and excellent performance in that the film property can be maintained for a long time. Met.

[Evaluation when applied to hair]
Each of 5 subjects applied 1 g of the obtained emulsified composition to the stickiness when applied to a hair bundle having a length of 22 cm and a weight of 2 g, and the cohesiveness and flexibility of the hair bundle after being naturally dried overnight. Each of the five subjects was judged according to the evaluation criteria shown below.
[Evaluation criteria]
2: Very good.
1: Good.
0: Normal.
-1: Somewhat bad.
-2: Bad.

  The average value of each subject's evaluation based on this evaluation standard is calculated, and the case where the average value is 1 or more and 2 or less is very good (◎), the case where it is 0 or more and less than 1 is good (◯), -1 or more and more The case of less than 0 was judged to be a little bad (Δ), and the case of -2 to less than −1 was judged to be bad (×).

  The results are shown in Tables 1 and 2 (see “Evaluation for hair” in Tables 1 and 2).

  As is clear from the results in Tables 1 and 2, the emulsion composition containing the resin of the present invention as a film-forming agent was excellent in hair stickiness, cohesiveness and flexibility when applied to hair. It was.

<Prescription example>
Next, specific examples of cosmetics prepared using the resin of the present invention will be described.

  Here, cosmetics were prepared using the resin solution obtained in Example 1, and the performance was evaluated. The preparation methods (formulation examples 1 to 7) and the performance of each cosmetic are shown below.

[Prescription Example 1: Liquid Foundation]
Raw materials A to C (referred to as phase I) shown in Table 4 were mixed, and further, raw materials D to G (referred to as phase II) were added and dispersed uniformly. The raw material HL (it makes a III phase) uniformly mixed previously was gradually added there, and was made to disperse | distribute, Then, the liquid foundation was prepared by emulsifying with a homomixer. The blending ratio of each raw material is shown in Table 4.

  This liquid foundation had low stickiness at the time of application and after application, and persisted feeling after application.

[Prescription Example 2: Cream Foundation]
Raw materials A to D (referred to as phase I) shown in Table 5 were dissolved by heating at 70 ° C., and then raw materials E to H (referred to as phase II) were added and dispersed uniformly. While stirring this, a cream foundation was prepared by gradually adding and emulsifying raw materials I to L (referred to as phase III) that were previously heated and mixed at 70 ° C. The blending ratio of each raw material is shown in Table 5.

  This cream foundation had low stickiness at the time of application and after application, and persisted feeling after application.

[Prescription Example 3: Hair Styling Cream]
The raw materials A to C (referred to as phase I) shown in Table 6 were uniformly mixed, and the raw materials D to H (referred to as phase II) that were uniformly mixed therein were gradually added and dispersed. A hair styling cream was prepared by emulsification. Table 6 shows the blending ratio of each raw material.

  This hair styling cream had excellent hair styling properties and was excellent in the flexibility of the hair after styling.

[Prescription Example 4: Hair Styling Mist]
A hair styling mist was prepared by uniformly mixing the raw materials A to C shown in Table 7. The blending ratio of each raw material is shown in Table 7.

  This hair styling mist had excellent hair styling retention, and the stickiness of the hair after hair styling by this hair styling mist was low.

[Prescription Example 5: Hair Gel]
Raw materials A to B (referred to as phase I), raw materials C to D (phase II), and raw materials E to G (phase III) shown in Table 8 were mixed and dispersed uniformly to prepare phases I to III, A hair gel was prepared by gradually adding the phases in the order of phase II and phase III with stirring. Table 8 shows the blending ratio of each raw material.

  This hair gel had excellent hair styling retention, and the stickiness of the hair after styling with this hair gel was low.

[Prescription Example 6: Moisturizing serum]
A moisturizing serum was prepared by uniformly mixing the raw materials A to J shown in Table 9. The blending ratio of each raw material is shown in Table 9.

  This moisturizing serum has little stickiness at the time of application and is excellent in touch, and the firmness of the skin after use is maintained for a long time.

[Prescription Example 7: Emulsion]
The raw materials A to F (referred to as phase I) and the raw materials GL (referred to as phase II) shown in Table 10 were prepared in advance by heating and dissolving at 70 ° C. respectively, and the phase II was stirred while stirring the phase I at 70 ° C. Was gradually added to emulsify. Next, while cooling this, raw materials M to N (referred to as phase III) were added and mixed uniformly to prepare an emulsion. The blending ratio of each raw material is shown in Table 10.

  This emulsion had little stickiness at the time of application and excellent feel, and the firmness of the skin after use was maintained for a long time.

Claims (4)

It consists of a polymer of ethylenically unsaturated monomer components,
The ethylenically unsaturated monomer component contains 30 to 70% by mass of at least one of the monomer represented by the following formula (1-a) and the monomer represented by (1-b),
The ethylenically unsaturated monomer component contains 1 to 50% by mass of at least one of a monomer represented by the following formula (2-a) and a monomer represented by the formula (2-b),
The polymer includes at least one of a repeating unit (A1) represented by the following formula (Ia) and a repeating unit (A2) represented by the following formula (Ib);
At least one of a repeating unit (B1) represented by the following formula (II-a) and a repeating unit (B2) represented by the following formula (II-b);
In the molecule,
The polymer has a weight average molecular weight of 3,000 to 100,000, and a glass transition temperature of Ri 10 to 60 ° C. der,

(In formula (Ia), R ₁ is H or CH ₃ , R ₂ is H or an alkyl group having 1 to 8 carbon atoms, R ₃ is H, an alkyl group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. Represents a hydroxyalkyl group.)

(In formula (Ib), R ₁ represents H or CH ₃ and m and n each independently represent an integer of 0 to _3. )

(In the formula (II-a), R ₁ is H or CH ₃ , R ₄ is H or an alkyl group having 1 to 18 carbon atoms, A ₁ is O or NH, and x, y, and z are independent of each other. And x + y + z ≧ 2. (EO) is (C ₂ H ₄ O), (PO) is (C ₃ H ₆ O), and (BO) is (C ₄ H _8). O).)

(In the formula (II-b), R ₁ is H or CH ₃ , R ₄ is H or an alkyl group having 1 to 18 carbon atoms, A ₁ is O or NH, and x, y and z are independent of each other. And x + y + z ≧ 2. (EO) is (C ₂ H ₄ O), (PO) is (C ₃ H ₆ O), and (BO) is (C ₄ H _8). In addition, [-(EO) _x- (PO) _y- (BO) _z- ] in the formula (II-b) represents a random arrangement of each repeating unit of EO, PO, and BO. That is, a random copolymer of EO, PO and BO.)

(In formula (1-a), R ₁ is H or CH ₃ , R ₂ is H or an alkyl group having 1 to 8 carbon atoms, R ₃ is H, an alkyl group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. Represents a hydroxyalkyl group.)

(In formula (1-b), R ₁ represents H or CH ₃ , and m and n each independently represents an integer of 0 to _3. )

(In Formula (2-a), R ₁ is H or CH ₃ , R ₄ is H or an alkyl group having 1 to 18 carbon atoms, A ₁ is O or NH, and x, y, and z are each 0. It is an integer of ˜100, and x + y + z ≧ 2. (EO) is (C ₂ H ₄ O), (PO) is (C ₃ H ₆ O), and (BO) is (C ₄ H ₈ O). Is shown.)

(In formula (2-b), R ₁ is H or CH ₃ , R ₄ is H or an alkyl group having 1 to 18 carbon atoms, A ₁ is O or NH, and x, y, and z are each 0. It is an integer of ˜100, and x + y + z ≧ 2. (EO) is (C ₂ H ₄ O), (PO) is (C ₃ H ₆ O), and (BO) is (C ₄ H ₈ O). [-(EO) _x- (PO) _y- (BO) _z- ] in formula (2-b) indicates that each repeating unit of EO, PO, and BO is randomly arranged. That is, it is a random copolymer of EO, PO, and BO.)
In the above formula (II-a), it contains two or more selected from the group consisting of (EO), (PO) and (BO), and the total value of x, y and z is in the range of 7 to 14 Yes,
In the above formula (II-b), it contains two or more selected from the group consisting of (EO), (PO) and (BO), and the total value of x, y and z is in the range of 6 to 15 Yes,
In the above formula (2-a), it contains two or more selected from the group consisting of (EO), (PO) and (BO), and the total value of x, y and z is in the range of 7 to 14 Yes
In the above formula (2-b), it contains two or more selected from the group consisting of (EO), (PO) and (BO), and the total value of x, y and z is in the range of 6 to 15 A resin characterized by being. The monomer represented by the formula (2-a) is a polyethylene glycol-polypropylene glycol monomethacrylate in which the x in the formula (2-a) is 5, the y is 2, and the z is 0, Propylene glycol polybutylene glycol monomethacrylate which is a monomer having x in formula (2-a) of 0, y of 1 and z of 6, x in formula (2-a) of 8, y of 6, octoxypolyethyleneglycolpolypropyleneglycol monomethacrylate, which is a monomer with z = 0, and octoxypolyethyleneglycolpolypropylene, which is a monomer with x = 8, y = 6, and z = 0 in the formula (2-a) Including one or more monomers selected from the group consisting of glycol monoacrylate,
The monomer represented by the formula (2-b) is a poly (ethylene glycol-) monomer in which x in the formula (2-b) is 3.5, y is 2.5, and z is 0. Propylene glycol) monomethacrylate, poly (ethylene glycol-tetramethylene glycol) monomethacrylate which is a monomer in which x in the above formula (2-b) is 5, y is 0, and z is 2, ), Poly (ethylene glycol-tetramethylene glycol) monomethacrylate which is a monomer having x of 6, y of 0 and z of 10, x of the above formula (2-b) is 10, y is 0, z Poly (ethylene glycol-tetramethylene glycol) monomethacrylate in which is a monomer of 5, poly (propylene glycol) in which x is 0, y is 4 and z is 8 in the above formula (2-b) -Tetramethylene glycol) monometac Relate, poly (propylene glycol-tetramethylene glycol) monomethacrylate, which is a monomer in which x in the formula (2-b) is 0, y is 7, and z is 6, and in the formula (2-b) 2. The composition according to claim 1 , comprising at least one selected from the group consisting of poly (propylene glycol-tetramethylene glycol) monomethacrylate, which is a monomer in which x is 0, y is 10, and z is 3. resin. The ethylenically unsaturated monomer component is a polyethylene glycol-polypropylene glycol monomethacrylate monomer in which x in the formula (2-a) is 5, y is 2, and z is 0, and the formula (2- a) propylene glycol polybutylene glycol monomethacrylate which is a monomer having x of 0, y of 1 and z of 6 in a) and x in the above formula (2-b) of 10, y of 0 and z of 5 poly is a monomer (ethylene glycol - tetramethylene glycol) resin according to claim 1 or 2, characterized in that it contains one or more kinds selected from the group consisting of mono-methacrylate. A cosmetic base material comprising the resin according to any one of claims 1 to 3 .