JP2003171428A - Polymer having melting point, method for producing the same and cosmetic using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polymer for providing a cosmetic having excellent touch, water resistance and durability, to provide a method for producing the same and to obtain a cosmetic containing the polymer. <P>SOLUTION: This polymer is a polymer which comprises ≥30 wt.% of a constituent unit derived from a hydrophobic vinyl monomer and ≥30 wt.% of constituent unit derived from a hydrophilic vinyl monomer. The difference between the melting point of the polymer and that of a polymer composed of a constituent unit of the hydrophobic vinyl monomer alone is ≤10°C. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer used in cosmetics, and more particularly to a polymer used in cosmetics having excellent feeling in use, water resistance and durability.

[0002]

2. Description of the Related Art Cosmetics such as creams, hair rinses, treatments, and waxes contain higher alcohols, surfactants, and higher alcohols so that they have a good feel and water resistance during application.
Contains oil, etc. However, the cosmetics containing such higher alcohols, surfactants, oils, etc. have not been sufficiently durable against contact and friction.

On the other hand, cosmetics containing a hydrophilic gelling agent having good durability against contact and friction were not sufficiently water resistant.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a polymer which gives a cosmetic having good feel, water resistance and durability.
An object of the present invention is to provide a method for producing the same, and a cosmetic containing the polymer.

[0005]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that the constitutional unit derived from a hydrophobic vinyl monomer is 30% by weight or more, and the constitutional unit derived from a hydrophilic vinyl monomer. A polymer containing 30% by weight or more of structural units, wherein the difference between the melting point of the polymer and the melting point of the polymer having only the hydrophobic vinyl monomer as the structural unit is 10 ° C or less. The present invention has completed the present invention, and found that the polymer to give a cosmetic having good feel, water resistance and durability, and that the polymer can be easily produced by conducting a polymerization reaction in a specific solvent. .

That is, the gist of the present invention is a polymer containing 30% by weight or more of structural units derived from a hydrophobic vinyl monomer and 30% by weight or more of structural units derived from a hydrophilic vinyl monomer. A polymer characterized in that the difference between the melting point of the polymer and the melting point of the polymer having only the hydrophobic vinyl monomer as a constitutional unit is 10 ° C. or less, its production method, and this polymer, It is the cosmetics contained.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The polymer according to the present invention can be obtained by copolymerizing a hydrophobic vinyl monomer, a hydrophilic vinyl monomer, and optionally other copolymerizable monomer in a specific solvent.

The hydrophobic vinyl monomer has a solubility in distilled water at 20 ° C. (g / 100 g water) of 0.2 or less. Among them, those exhibiting water solubility of 0.1 or less are preferable. Some of them are exemplified by (meth) acryl of alcohols such as cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate and isobornyl (meth) acrylate. Acid ester; 2-ethylhexyl (meth) acrylamide, octyl (meth) acrylamide, lauryl (meth) acrylamide, cetyl (meth) acrylamide,
Stearyl (meth) acrylamide, behenyl (meth)
Amine (meth) acrylamides such as acrylamide, cyclohexyl (meth) acrylamide, benzyl (meth) acrylamide, and isobornyl (meth) acrylamide; aromatic hydrophobic unsaturated monomers such as styrene, chlorostyrene and vinyltoluene. To be

Of these, a hydrophobic vinyl monomer whose homopolymer has a melting point of 20 to 90 ° C. is preferable. Of these, preferred are (meth) acrylates of alcohols having 14 to 40 carbon atoms or (meth) acrylamides of amines having 14 to 40 carbon atoms, particularly cetyl (meth) acrylate, stearyl (meth) acrylate or behenyl (meth) acrylate. Is.

The hydrophobic vinyl monomer may be used alone,
You may use in combination of multiple. When a plurality of them are used in combination, the difference between the melting point of the polymer having only the plurality of hydrophobic vinyl monomers as a constitutional unit and the melting point of the obtained polymer may be within 10 ° C. The hydrophobic vinyl monomer may be used so that the content of the structural unit derived from the hydrophobic vinyl monomer in the polymer is 30 to 70% by weight. It is preferable to use it so that the content of this structural unit is 35 to 65% by weight, particularly 40 to 60% by weight. Content of structural units derived from hydrophobic vinyl monomer is 30% by weight
When it is less than the above range, the hydrophobicity of the polymer is lowered and good water resistance cannot be obtained. On the other hand, if it exceeds 70% by weight, the solubility or dispersibility of the polymer in water decreases, and it becomes difficult to use it in an aqueous system.

The hydrophilic vinyl monomer has a solubility in distilled water at 20 ° C. (g / 100 g water) of 20 or more. Examples of hydrophilic vinyl monomers include hydrophilic vinyl monomers containing anionic, cationic, nonionic, amphoteric, and semipolar groups. Any of these can be used in the invention, and if desired, they can be used in combination.

As the anionic hydrophilic vinyl monomer,
Unsaturated carboxylic acid compounds such as (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, crotonic acid; polybasic acids such as succinic acid and phthalic acid and hydroxyl group containing (meth) hydroxyethyl (meth) acrylate A half ester compound with acrylate; a compound having a sulfonic acid group such as styrene sulfonic acid and sulfoethyl (meth) acrylate; a compound having a phosphoric acid group such as 2-phosphonoethyl (meth) acrylate. These anionic hydrophilic vinyl monomers, during the copolymerization reaction,
Either the acid form or the partially neutralized or fully neutralized form can be used. It is also possible to subject the copolymerization reaction in the form of an acid to a partial or complete neutralization. For the neutralization, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide or an amine compound such as aqueous ammonia, mono-di-triethanolamine or trimethylamine can be used.

As the cationic hydrophilic vinyl monomer,
N- (meth) acryloyloxyethyl-N, N, N-
Trimethylammonium chloride, N- (meth) acryloyloxyethyl-N-ethyl-N, N-dimethylammonium = monoethylsulfate, N- (meth) acryloyloxyethyl-N, N, N-triethylammonium chloride, N- ( (Meth) acryloyloxyethyl-
N, N, N-triethylammonium = monoethylsulfate, N- [3- (N ′-(meth) acryloyloxyethyl-N ′, N′-dimethylammonium) -2-hydroxypropyl] -N, N, N -Trimethylammonium chloride, N- [3- (N '-(meth) acryloyloxyethyl-N', N'-diethylammonium)-
2-Hydroxypropyl] -N, N, N-triethylammonium chloride or other cationic group-containing (meth) acrylic acid ester; N- (meth) acryloylaminopropyl-N, N-dimethyl-N-laurylammonium chloride, N -(Meth) acryloylaminopropyl-N
-Ethyl-N, N-dimethylammonium = monoethylsulfate, N- (meth) acryloylaminopropyl-
N, N-diethyl-N-methylammonium chloride,
N- (meth) acryloylaminopropyl-N-methyl-N, N-diethylammonium = monomethylsulfate,
N- [3- (N '-(meth) acryloylaminopropyl-N', N'-dimethylammonium) -2-hydroxypropyl] -N, N, N-trimethylammonium chloride, N- [3- (N ' -(Meth) acryloylaminopropyl-N ', N'-diethylammonium)-
Examples include cationic group-containing (meth) acrylamides such as 2-hydroxypropyl] -N, N, N-trimethylammonium chloride.

As the nonionic hydrophilic vinyl monomer,
Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate; methoxypolyethyleneglycol (meth) acrylate, methoxypoly (ethyleneglycol / propyleneglycol) mono (meth) acrylate, ethoxypoly (ethyleneglycol / propyleneglycol) mono (meth ) Acrylate, polyethylene glycol di (meth) acrylate,
Poly (ethylene glycol / propylene glycol) di (meth) acrylate, triethylene glycol dimethacrylate, or other polyalkylene glycol mono- or di (meth) acrylates; N-polyalkyleneoxy (meth) acrylamides, N- (meth) acryloylmorpholines , Amide compounds such as acrylamide; N-vinylpyrrolidone and the like.

As the amphoteric hydrophilic vinyl monomer, a monomer having a betaine structure in which one alkyl group bonded to the nitrogen atom of the above-mentioned cationic hydrophilic vinyl monomer is substituted with a carboxymethyl group is used. Can be mentioned. Specifically, N- (meth) acryloyloxyethyl-N, N-
Dimethyl-N-carboxymethyl ammonium, N-
(Meth) acryloyloxyethyl-N-ethyl-N-
Methyl-N-carboxymethylammonium, N- (meth) acryloyloxyethyl-N, N-diethyl-N
-Carboxymethyl ammonium and the like.

Examples of the semipolar hydrophilic vinyl monomer include compounds having an amine oxide group. Specifically, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate Acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminopropionate vinyl, p-dimethylaminomethylstyrene, p-dimethylaminoethylstyrene, p-diethylaminomethylstyrene, p-diethylaminoethylstyrene, etc. Examples thereof include amine oxide compounds obtained by oxidizing

Of the above hydrophilic vinyl monomers, ionic hydrophilic vinyl monomers, particularly cationic hydrophilic vinyl monomers are preferred. Of these, cationic group-containing (meth) acrylic acid ester, particularly N- (meth) acrylic acid is preferable.
Acryloyloxyethyl-N, N, N-trimethylammonium chloride, N- (meth) acryloyloxyethyl-N-ethyl-N, N-dimethylammonium =
It is monoethyl sulfate.

The hydrophilic vinyl monomer may be used alone,
You may use in combination of multiple. The hydrophilic vinyl monomer may be used so that the content of the constituent units derived from the hydrophilic vinyl monomer in the polymer is 30 to 70% by weight. It is preferably used so as to be 35 to 65% by weight, particularly 40 to 60% by weight. When the content of the constituent unit derived from the hydrophilic vinyl monomer is less than 30% by weight, the solubility or dispersibility in water is lowered, and when it exceeds 70% by weight, the hydrophilicity is increased and the water resistance is lowered.

Further, in place of the hydrophilic vinyl monomer, a non-hydrophilized hydrophilizable vinyl monomer which is a precursor thereof is polymerized with a monomer component forming another structural unit. Then, the polymer according to the present invention can also be obtained by hydrophilizing the precursor monomer in the obtained precursor-containing polymer. For example, in place of the cationic hydrophilic vinyl monomer, the precursor amino group-containing vinyl monomer is copolymerized with a monomer forming another structural unit,
The polymer of the present invention can also be obtained by cationizing or amino-oxidizing the amino group in the obtained polymer by a conventional method.

In the production of the polymer according to the present invention, it is possible to copolymerize the hydrophobic vinyl monomer and the hydrophilic vinyl monomer with other copolymerizable monomers.
Other copolymerizable monomers include monomers having a solubility in water of more than 0.2 and less than 20 (g / 100 g water). Specifically, methyl (meth) acrylate,
Examples thereof include (meth) acrylic acid esters such as ethyl (meth) acrylate and t-butyl methacrylate.

The other copolymerizable monomer has a content of constituent units derived from the other monomer in the polymer of 4 or less.
It may be used so as to be 0% by weight or less. It is preferably used so as to have a content of 30% by weight or less, particularly 0.1 to 20% by weight. If it exceeds 40% by weight, the crystallinity is lowered, so that it becomes difficult to obtain a polymer having a melting point.

In the polymer according to the present invention, the difference between the melting point of the polymer and the melting point of the polymer having a hydrophobic vinyl monomer as a constituent unit is 10 ° C. or less. In general, cosmetics containing a polymer having high crystallinity are said to exhibit a good feel when used. This is believed to be due to the hydrophobic feel of the polymer as crystals. The higher the crystallinity of the polymer according to the present invention, the smaller the difference in melting point from the polymer having only a hydrophobic vinyl monomer as a structural unit. When the crystallinity decreases and the difference between the melting points of the both exceeds 10 ° C., the feel at the time of application is deteriorated. 5 ° C difference in melting point
It is particularly preferable that the temperature is 3 ° C. or less.

Taking advantage of the fact that the amount of absorbed heat (ΔH) at the melting point increases when the crystallinity of the polymer is high, the degree of crystallinity can be evaluated by measuring ΔH. In order to produce the polymer according to the present invention, as the hydrophobic vinyl monomer, a hydrophobic vinyl monomer having ΔH at the melting point of 4 J / g or more in the polymer consisting of the hydrophobic vinyl monomer alone is used. It is preferably used.

The polymer according to the present invention generally comprises a hydrophobic vinyl monomer, and if desired, a hydrophilic vinyl monomer and other copolymerizable monomers, which are radically dissolved in a hydrophilic solvent. It can be obtained by polymerization in the presence of a polymerization initiator by a known method such as batch polymerization or drop polymerization. In order to produce a polymer having a melting point from a hydrophobic vinyl monomer and a hydrophilic vinyl monomer, one of the hydrophobic vinyl monomer and the hydrophilic vinyl monomer has high solubility and the other The copolymer may be copolymerized in a solvent having low solubility. By using such a solvent, not a random polymer but a block-like polymer having a biased arrangement of repeating units of each monomer can be obtained. A completely random polymer does not have a melting point, but it is considered that when it is a block-like polymer, it has a melting point.

From the viewpoint of reaction operation, a hydrophilic solvent having a high solubility of the hydrophilic vinyl monomer is preferable as the polymerization solvent. When the copolymerization reaction is carried out using a hydrophilic solvent, the hydrophilic vinyl monomer is dissolved but the hydrophobic vinyl monomer is not completely dissolved. Therefore, the polymerization reaction system exhibits phase separation or an opaque state. In this state, complete random polymerization does not proceed and a polymer having a biased arrangement of repeating units of each monomer is obtained. As the solvent, water; alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; fatty acid esters such as ethyl acetate can be used. Of these, a mixed solvent of water and ethanol is preferable. The mixing ratio (weight ratio) of water / ethanol may be 1/99 to 50/50. 3 / 95-30 / 70, especially 5 / 95-20 /
80 is preferred.

As the radical polymerization initiator, 2,2'-
Azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'- Azobisisobutyrate,
Dimethyl-2,2'-azobisisobutyrate, 2,
2'-azobis (2-methylbutyronitrile), 1,
1'-azobis (1-cyclohexanecarbonitrile)
And azo compounds such as benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, and other peroxides can be used. The polymerization initiator is usually 0.0 based on the total amount of all monomers.
It is used in the range of 1 to 5% by weight.

The polymerization reaction is usually carried out in an inert gas atmosphere such as nitrogen or argon at 30 to 120 ° C., preferably 40 to 120 ° C.
It is preferable to carry out at 100 ° C. for 1 to 30 hours. When a precursor monomer is used instead of the hydrophilic vinyl monomer, it may be copolymerized under the same conditions. The molecular weight of the obtained polymer is the polymerization conditions such as the type and amount of the initiator, the polymerization temperature, the type of the solvent, the monomer concentration during the polymerization reaction, the batch, the selection of division or dropwise addition, and the amount of the chain transfer agent used. By selecting appropriately,
It can be any level. The weight average molecular weight of the polymer is preferably 5,000 to 2,000,000. When the molecular weight is low, the film-forming property and film strength are lowered, and when the molecular weight is high, industrial production becomes difficult.

The hydrophilization of the precursor polymer obtained by using the precursor monomer in place of the hydrophilic vinyl monomer is carried out by adding a hydrophilizing agent to the polymer solution in the range of 20 to 100 ° C. 1-2
It is performed by hydrophilizing for 0 hours. Isolation of the polymer according to the present invention from the obtained polymer solution can be carried out by a known method such as addition of a poor solvent or evaporation of the solvent. The isolated polymer can be further purified if necessary by reprecipitation, solvent washing, membrane separation, and column chromatography. The hydrophilicity of the precursor polymer described above is
It is also possible to isolate the precursor polymer from the polymerization reaction solution and dissolve or disperse it in a solvent again to carry out. Further, when using the polymer according to the present invention in the production of cosmetics,
It may be used in the form of a solution, or may be isolated from this. When used in a solution state, it may be replaced with an appropriate solvent by a known method such as solvent replacement, if necessary.

[0029]

EXAMPLES The present invention will be described in more detail based on examples, but the present invention is not limited to the following examples. The melting point is measured by a differential scanning calorimeter (DSC) DSC7 (PE
It was measured using RKIN ELMER, TAC7 / DX). In order to cancel the history due to the drying process of the polymer, the temperature was raised from −40 ° C. to 100 ° C. at 10 ° C./min, held at 100 ° C. for 1 minute, and then cooled from 100 ° C. to −40 ° C. at 10 ° C./min, Hold at -40 ° C for 1 minute, then
The peak when the temperature was raised from −40 ° C. to 100 ° C. at 10 ° C./min was taken as the melting point.

Example 1 140 parts by weight of ethanol and dimethylaminoethyl methacrylate methyl chloride salt (methacryloyloxyethyl trimethyl ammonium chloride) in a reactor equipped with a reflux condenser, a dropping funnel, a thermometer, a nitrogen gas introducing tube and a stirrer. 60 parts by weight of 80% by weight aqueous solution, 39 parts by weight of stearyl methacrylate, 1 part by weight of 1,6-hexanediol diacrylate, and 0.2 parts by weight of dimethyl-2,2′-azobisisobutyrate were charged. After nitrogen substitution, 2
The temperature was raised to 80 ° C. for 10 hours, the reaction was performed at 80 ° C. for 10 hours, and then the temperature was cooled to room temperature. In addition, 0.5 hours by weight of dimethyl-2,2′-azobisisobutyrate was added 4 hours and 7 hours after the start of heating to accelerate the reaction.

The solvent was distilled off from the polymerization product solution under reduced pressure to obtain a polymer (1). The melting point of the obtained polymer (1) was 34.
It was ℃. Examples 2 to 5, Comparative Example 1, and Comparative Example 2 Polymers (2) to (7) were produced in the same manner as in Example 1 using the monomers and solvents having the compositions shown in Table 1. did.

[0032]

[Table 1]

Hydrophobic vinyl monomer SMA: Stearyl methacrylate Hydrophilic vinyl monomer DMC: Dimethylaminoethyl methacrylate methyl chloride salt DM: Dimethylaminoethyl methacrylate, DES:
Diethyl sulfate 3 EGA: Triethylene glycol dimethacrylate and other copolymerizable vinyl monomers TBA: t-butyl methacrylate Melting point (° C) ΔH: Endotherm (J / g)

Regarding the obtained polymers (1) to (7),
A 3% aqueous solution was prepared for each, and the feel on application, the feel after drying and the durability were evaluated. A cream having the following composition was used as a standard product. Cream (standard product) Polyoxyethylene (7EO) cetyl ether: 5% by weight Stearyl trimethyl ammonium chloride: 1% by weight Cetyl alcohol: 3% by weight Stearyl alcohol: 2% by weight Liquid paraffin: 0.5% by weight Octamethylcyclotetrasiloxane : 0.5% by weight Distilled water: 88% by weight.

1 g of the aqueous solution was placed on the back of the feeler at the time of application, and the smoothness when extended on the pad of the finger was compared with the standard product. Place 1 g of the aqueous solution on the back of the feeler's hand after drying, and measure about 5 cm x about 5 c with the pad of your finger
It was dried while being extended to m. After about 10 minutes, the non-stickiness when touched with the finger pad was evaluated as the touch. The results are shown in Table 2.

1 g of the above aqueous solution was applied to 2 g of a waterproof hair tress, and the humidity was adjusted at 23 ° C. and 80% relative humidity for 12 hours, and then the stickiness was evaluated. Those with no stickiness were considered good. 1 g of the above aqueous solution was applied to a durable hair bundle, the humidity was adjusted at 23 ° C. and a relative humidity of 60% for 12 hours, and then the appearance on the finger when rubbed on the finger pad was evaluated. Those with less reflection on the fingers were considered good.

Each of the evaluations was carried out in four stages, with 4 points being good and 1 point being bad. The results are shown in Table 2.

Each evaluation was performed as follows. +2 Much better than the standard product. +1 Superior to standard products. 0 Same as standard product. -1 Inferior to the standard product.

[0039]

[Table 2]

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4C083 AD091 AD092 CC02 CC33                       DD27 EE06 EE07 EE11 FF01                 4J011 JB14 JB27                 4J100 AB02P AB04P AB07Q AB08P                       AG08Q AJ01Q AJ02Q AJ09Q                       AK02Q AK03Q AK07Q AK08Q                       AK19Q AK20Q AL03R AL05P                       AL08P AL08Q AL09Q AL66Q                       AM15P AM15Q AM17P AM21P                       AM21Q AQ08Q BA02Q BA03Q                       BA05Q BA06Q BA08Q BA15Q                       BA16Q BA17Q BA31Q BA32Q                       BA56Q BA64Q BC04P BC07P                       BC43P BC43Q CA04 CA05                       DA24 FA21 FA30 JA61

Claims (8)

[Claims] 1. A structural unit derived from a hydrophobic vinyl monomer is 3 units.
A polymer containing 0% by weight or more and a structural unit derived from a hydrophilic vinyl monomer in an amount of 30% by weight or more, wherein the melting point of the polymer and the hydrophobic vinyl monomer are the only structural units. The polymer has a difference from the melting point of 10 ° C. or less. 2. A constitutional unit derived from a hydrophobic vinyl monomer is 3
0% by weight or more, 3 units of the structural unit derived from hydrophilic vinyl monomer
A polymer containing 0% by weight or more and 0.1 to 20% by weight of a constitutional unit derived from another copolymerizable monomer, wherein only the melting point of the polymer and the hydrophobic vinyl monomer are contained. A polymer having a difference from the melting point of the polymer as a constituent unit of 10 ° C. or less. 3. The polymer according to claim 1, which has a melting point in the range of 25 to 70 ° C. 4. The hydrophobic vinyl monomer has 14 to 4 carbon atoms.
The polymer according to claim 1, which is a (meth) acrylate of 0 alcohol. 5. The hydrophobic vinyl monomer has a Δ at the melting point of a polymer in which only the unit hydrophobic vinyl monomer is a structural unit.
H is 4 J / g or more, The polymer in any one of Claim 1 thru | or 4 characterized by the above-mentioned. 6. The polymer according to claim 1, wherein the hydrophilic vinyl monomer is a cationic vinyl monomer. 7. A monomer mixture containing 30% by weight or more of a hydrophobic vinyl monomer and 30% by weight or more of a hydrophilic vinyl monomer or a precursor thereof in an aqueous solvent containing water and ethanol. The polymerization reaction is carried out at
7. The method for producing a polymer according to any one of 6 to 6. 8. A cosmetic comprising the polymer according to any one of claims 1 to 6.