JP2000234042A - Copolymer-containing composition for surface modification - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a copolymer-containing composition which can be uniformly dissolved in an aqueous carrier to form a coating fluid capable of forming a coating film having excellent water resistance and plasticity and being desirable for surface treatment by using a copolymer comprising two specified (meth) acrylate monomers. SOLUTION: This composition contains a copolymer comprising at least one member selected from monomers represented by formula I and at least one member selected from monomers represented by formula II and having plasticity and is useful for cosmetics, coating materials, fiber treating agents, etc. In formula I, R1 is hydrogen or a 1-4C alkyl; and R2 is a 1-20C (fluoro)alkyl. In formula II, R3 is hydrogen or a 1-4C alkyl; R4 is an alkyloxy, acyloxy or a 2-4C (hydroxy)alkyl; R5 is hydrogen, an aromatic or aliphatic 1-8C hydrocarbon group or an acyl; and (n) is a number of 1-40.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to cosmetics and the like, which are suitable for surface treatment and the like, have improved solubility in water, do not require a plasticizer such as a phthalate ester, and contain a polymer having plasticity. The composition of

[0002]

2. Description of the Related Art In processing various materials, surface treatment is an important factor for maintaining the material of each member. For this reason, various varnishes, paints, and the like have been developed as construction materials, and cosmetics that form a water-retaining film can be recognized as a kind of surface treatment agent from such a viewpoint. As materials usually used in such surface treatment, there are usually many polymers and many water-insoluble materials. This is because the coating is often intended to block off aqueous components. Therefore, in such a treatment, the polymer is usually used by dispersing it in an aqueous carrier or the like, or by dissolving it in an organic solvent or the like. However, in the case of dispersion in an aqueous carrier or the like, the usability of the composition may be significantly reduced due to agglomeration or the like, and the organic solvent system has a problem that the use of the organic solvent itself is restricted. In particular, in the field of cosmetics for the skin, hair, and nails, it was an essential condition to be able to apply using an aqueous carrier. That is, there has been a demand for a polymer which is uniformly dissolved in an aqueous carrier and forms a film having excellent water resistance after coating. Furthermore, conventional polymers require a plasticizer because of their hard film properties, but some of these plasticizers are suspected of acting as endocrine disruptors, such as phthalates. There was something. In recent years, the need for the development of polymers having plasticity and not requiring the use of such plasticizers has been increasing in recent years.

On the other hand, the compound represented by the following general formula (I) and the compound represented by the following general formula (II) are already known in the literature, and are commercially available as monomers for producing polymers. These have not been combined to form a polymer that forms a film having excellent water resistance and plasticity after application by dissolving in an aqueous carrier. Further, a water-soluble and plastic polymer containing the compound represented by the general formula (I) and the compound represented by the general formula (II) as constituent monomers has not been known at all. Therefore,
Compositions containing these polymers, such as cosmetics and paints, have never been known to be suitable for surface treatment.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a coating film having excellent water resistance and plasticity after application, which is useful as a cosmetic, paint, or fiber treatment agent and is uniformly dissolved in an aqueous carrier. An object of the present invention is to provide a composition such as a cosmetic suitable for surface treatment or the like, which contains a polymer to be formed.

[0005]

In view of such circumstances, the present inventors have found that the present inventors have found that water-soluble carriers, which are useful as cosmetics, paints and fiber treatment agents, are uniformly dissolved and have excellent water resistance after application. As a result of diligent research efforts for a polymer that forms a functional film, 1 is selected from monomers represented by the general formula (I).
One or more kinds, preferably one or more kinds selected from the compound represented by the general formula (III) and the monomer represented by the general formula (II), preferably the general formula (IV)
It has been found that a polymer containing the compound represented by the formula (1) as a constituent monomer has such characteristics, and by including this in a composition such as a cosmetic, a cosmetic suitable for forming a film can be provided. This led to the completion of the invention. For example, among such compositions, basic cosmetics have an excellent protective film forming action, hair cosmetics have an excellent treatment effect on hair, and foundations have an excellent treatment effect. It has properties that make it hard to lose makeup, and when it is mixed with nail polish, it is uniformly dissolved in an aqueous carrier, and after coating, it forms a film with excellent water resistance. Hereinafter, the present invention will be described in detail focusing on embodiments.

[0006]

Embedded image General formula (I) (wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 represents an alkyl group having 1 to 20 carbon atoms which may have a fluorine atom.)

[0007]

Embedded image Formula (II) (wherein, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 may have an alkyloxy group, an acyloxy group, or a hydroxyl group, and has 2 to 4 carbon atoms. R5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and n represents 1 to 4
Represents a numerical value of 0. )

[0008]

Embedded image General formula (III) (wherein, R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, O and P each independently represent a numerical value of 1 to 10, and R7 represents a fluorine atom or a hydrogen atom. .)

[0009]

Embedded image General formula (IV) (wherein, R8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R9 represents an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom, Q represents a numerical value of 5 to 30.)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION (1) The compound represented by the general formula (I) used in the polymer of the present invention The polymer of the present invention is a compound selected from the compounds represented by the general formula (I) One or more species are contained as constituent monomers. In the general formula (I), R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 represents an alkyl group having 1 to 20 carbon atoms which may have a fluorine atom. R1
Is particularly preferably a hydrogen atom or a methyl group. This is the structure of acrylic acid or methacrylic acid, which is widely used in polymers and the like, because many things such as safety have already been confirmed, and many commercial products are easily available as raw materials. . Also, as R2,
It preferably contains a fluorine atom, and particularly preferably contains, as a partial structure, a methylene group having a structure substituted with a fluorine atom except for a bond to carbon. this is,
This is because, in the polymer of the present invention, the partial structure of R2 realizes the water resistance of the coating film after application. In the case where a fluorine atom is not contained, it is necessary to embody water resistance instead, and it is necessary that the alkyl group has a long-chain, branched or cyclic structure. The long chain here means
A compound having 12 or more carbon atoms. Among these, it is preferable that the compound represented by the general formula (III) is contained as one kind or two or more kinds selected from the general formula (I). Specific examples of preferred alkyl groups represented by R2 in the general formula (I) include 2,2.
2,2-trifluoroethyl group, 2,2,3,3,4.
4,5,5-octafluoropentyl group, 3.3,4,
4,5,5,6,6,7,7,8,8,9,9,10,
10,10-heptadecafluorodecanyl group, 2,2,
Examples thereof include a 2,2 ′, 2 ′, 2′-hexafluoroisopropyl group, a 2,2,3,3-tetrafluoropropyl group, an isopalmityl group, an isostearyl group, and a 3-cyclohexylpentyl group. Of these, particularly preferred are 2,2,3,3,4.4,5,5-octafluoropentyl and 3.3,4,4,5,5,6,6,7,
7,8,8,9,9,10,10,10-heptadecafluorodecanyl group. Among them, 3.3, 4, 4,
5,5,6,6,7,7,8,8,9,9,10,1
A 0,10-heptadecafluorodecanyl group is particularly preferred. This is because, in order to exhibit water solubility in a solution and hydrophobicity as a film, it is preferable to introduce a group having high hydrophobicity into the molecule to a minimum necessary. Such a compound represented by the general formula (I), which is a constituent monomer of the polymer of the present invention, is obtained by reacting an acid chloride of acrylic acid or methacrylic acid with a corresponding alkali metal alcoholate. It can be obtained in yield. Further, it can also be obtained by treating the corresponding alcohol with thionyl chloride, phosphorus oxychloride or the like, converting it to chloride, and reacting it with sodium acrylate or sodium methacrylate. Since there are already many commercially available products of such compounds, such commercially available products can also be used. In the polymer of the present invention, the content of the compound represented by the general formula (I) as a constituent monomer is 5 to 9.9% by weight in total, more preferably 7 to 9.5% by weight. It is preferably contained in the molecule. This is because the water resistance of the polymer is caused by this portion, and if the portion caused by the compound of the general formula (I) is too small, the water resistance of the polymer film is reduced. . If the amount is too large, the solubility in water may be impaired.

(2) Compound represented by the general formula (II) used in the polymer of the present invention The polymer of the present invention contains a compound represented by the general formula (II) as a constituent monomer. Features. Here, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 represents an alkyl group having 2 to 4 carbon atoms, which may have an alkyloxy group, an acyloxy group or a hydroxyl group, R5 is a hydrogen atom, aromatic or aliphatic carbon number 1
Represents a hydrocarbon group or an acyl group of 8 to 8, and n represents a numerical value of 1 to 40. R3 is particularly preferably a hydrogen atom or a methyl group. This is the structure of acrylic acid or methacrylic acid, which is widely used in polymers, etc., and safety and many others have already been confirmed.
This is because many commercial products are easily available as raw materials. R
4 is a polyoxyethylene group, a polyoxypropylene group,
Examples thereof include a polyoxybutene group, a polyoxy (hydroxypropylene) group, a part or all of an acylated product thereof, and an alkyl ether. The acyl group preferably has 1 to 20 carbon atoms such as an acetyl group, a benzoyl group, a stearoyl group and an oleoyl group, and the alkyl group preferably has 1 to 4 carbon atoms. Among these, a polyoxyethylene group is preferable. This terminal hydroxyl group may be left free, or it may be blocked with an acyl group or an alkyl group. Preferred examples of such an acyl group include an acetyl group, a benzoyl group, an acryloyl group and a methacryloyl group, and preferred examples of the alkyl group include those having 1 to 4 carbon atoms. Preferred R4 groups are methylpolyoxyethylene (9) group and methylpolyoxyethylene (2
3) group, methoxyethyl group, 3-methoxybutyl group, ethylpolyoxyethylene (2) group, phenoxytyl group,
Preferable examples include a phenyl polyoxyethylene (2) group, a methyl polyoxyethylene (3) group, an acryl polyoxyethylene (4) group, an acryl polyoxypropylene (3) group, and an acryl polyoxypropylene (7) group. As the compound represented by the general formula (II), a compound represented by the general formula (IV) is particularly preferable.
In the polymer of the present invention, a monomer represented by the general formula (II):
Is 30 to 90.1% by weight, more preferably 40 to 70% by weight, as the average weight percentage of the total amount in one molecule. This is because the solubility of the polymer of the present invention in water depends on the component represented by the general formula (II). If the amount is too small, the solubility of the polymer in water and the plasticity during film formation are impaired. May be
If the amount is too large, the water resistance of the formed film may be impaired.

(3) Polymer which is an essential component of the composition of the present invention The polymer which is an essential component of the composition of the present invention is one or two selected from the compounds represented by the above general formula (I). It is characterized by containing, as constituent monomers, at least one kind and at least one kind selected from the compounds represented by the general formula (II). That is, it is characterized by having the following partial structural formula 1 and partial structural formula 2 in one molecule. The polymer of the present invention may contain, in addition to these essential constituent monomers, monomers commonly used in copolymers as constituent monomers as long as the effects of the present invention are not impaired. Such optional monomers include, for example, acrylic acid, methacrylic acid, vinyl acetate, vinyl alcohol, alkyl ether of vinyl alcohol, styrene,
Examples include α-alkylstyrene, butadiene, isoprene, propene, vinyl chloride, acrylonitrile and the like.
The polymer of the present invention can be produced by treating these monomers according to a conventional method. That is, the monomers may be dissolved in a solvent or the like, a polymerization initiator or the like may be added, and heating may be performed. The polymerization initiator can be used without any particular limitation as long as it is generally used.For example, peroxides such as benzoyl peroxide, azobisisobutyronitrile, etc. The polymerization may be started using a suitable azo compound, a persulfate, a persulfate and a sulfite (redox-based initiator), or the like. Since the polymer of the present invention has water solubility, if the solvent is miscible with water, it can be concentrated as it is, or if the solvent is immiscible with water, after the reaction, water can be added to flush. The macromolecules migrate toward the water. Thereafter, the aqueous phase is taken and concentrated to obtain the polymer of the present invention. Here, the water-soluble referred to in the present invention means a solution state in water,
Specifically, when a uniform system is prepared by adding 99 parts by weight of water to 1 part by weight of a polymer, this means that the liquid has a transmittance of 90% or more to visible light. The polymer of the present invention may be a random type copolymer, a graft type copolymer, a block type or a combination thereof. The polymer thus obtained is not only water-soluble, but also has the property of forming a flexible film without a plasticizer when a film is formed. It is not necessary to use an acid ester or the like as a plasticizer. Further, since it has water solubility as described above, water can be used as a solvent in formulating, and a composition without an organic solvent can be prepared. Therefore, it can be used in cosmetics such as hair cosmetics, skin cosmetics, nail cosmetics, and the like, and can also be used as a surface treatment agent for aqueous paints, metals, glass, fibers, and the like. At present, there is no known substance capable of forming such a water-soluble, hydrophobic film after drying and film formation. In the composition of the present invention, only one of these can be used, or two or more can be used in combination. The preferred content of the polymer in the composition of the present invention is 0.1% in total.
It is preferable to prepare an aqueous solution in advance and use the aqueous solution to contain it. Hereinafter, the polymer, which is an essential component of the composition of the present invention, will be described in more detail with reference to production examples.

[0013]

Embedded image Partial structural formula 1 (wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 represents an alkyl group having 1 to 20 carbon atoms which may have a fluorine atom.)

[0014]

Embedded image Partial structural formula 2 (wherein, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 is an alkyl having 2 to 4 carbon atoms which may have an alkyloxy group, an acyloxy group or a hydroxyl group. R5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and n represents 1 to 4
Represents a numerical value of 0. )

Production Example 1 26.6 g of methyl polyoxyethylene (9) methacrylate, 11.4 g of methacrylic acid,
10, 10, 9, 9, 8, 8, 7, 7, 6, 6, 6, 5,
5,4,4,3,3-heptadecafluorodecanyl acrylate 2.0 g and isopropyl alcohol 100
A mixed solvent of 100 ml of water and 100 ml of water was taken and mixed by stirring. After a solution of 0.1 g of ammonium persulfate dissolved in 10 ml of water was added thereto, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. The polymerization was carried out by heating to 80 ° C. for 12 hours. After adding and mixing an aqueous solution in which 5.2 g of sodium hydroxide was dissolved, isopropyl alcohol was removed to obtain an aqueous solution of a desired copolymer. This was freeze-dried to obtain polymer 1.

[0016]

Embedded image Methyl polyoxyethylene (9) methacrylate

[0017]

Embedded image 10, 10, 10, 9, 9, 8, 8, 7, 7, 6, 6, 6,
5,5,4,4,3,3-heptadecafluorodecanyl acrylate

<Production Example 2> 19.6 g of methyl polyoxyethylene (23) methacrylate, 8.4 g of hydroxyethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate were placed in a flask equipped with a condenser, a stirrer and a nitrogen inlet tube. A mixed solvent of 12.0 g, 120 ml of isopropyl alcohol and 80 ml of water was taken and mixed with stirring. After sufficient replacement with a nitrogen stream while continuing to stir, the mixture was heated to 60 ° C., a solution of 0.1 g of ammonium persulfate and 0.1 g of sodium sulfite dissolved in 10 ml of water was added, and heating was continued for 6 hours to carry out polymerization. . After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain polymer 2.

[0019]

Embedded image Methyl polyoxyethylene (23) methacrylate

[0020]

Embedded image Hydroxyethyl methacrylate

[0021]

Embedded image 2,2,3,3-tetrafluoropropyl acrylate

<Production Example 3> 60.0 g of methyl polyoxyethylene (23) methacrylate, 40.0 g of 2,2,2-trifluoroethyl methacrylate, and 100 ml of isopropyl alcohol were placed in a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube. A mixed solvent of 100 ml of ethyl acetate was taken and mixed with stirring. After adding a solution of 0.1 g of benzoyl peroxide dissolved in 10 ml of isopropyl alcohol, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Polymerization was carried out at the boiling point of the solvent for 10 hours. The mixed solvent was flushed with water to obtain an aqueous solution of the copolymer. This was freeze-dried to obtain polymer 3.

[0023]

Embedded image 2,2,2-trifluoroethyl methacrylate

<Production Example 4> 21.0 g of methyl polyoxyethylene (9) methacrylate, 8.0 g of 2,2,2-trifluoroethyl methacrylate were placed in a flask equipped with a condenser, a stirrer and a nitrogen inlet tube. , 9,9,
Mixing of 8,8,7,7,6,6,5,5,4,4,3,3-heptadecafluorodecanyl acrylate 2.0 g, hydroxyethyl methacrylate 9.0 g, isopropyl alcohol 120 ml, and water 80 ml The solvent was taken and mixed with stirring. After a solution of 0.1 g of ammonium persulfate dissolved in 10 ml of water was added thereto, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. The polymerization was carried out by heating to 80 ° C. for 12 hours. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of a copolymer. This is freeze-dried,
Polymer 4 was obtained.

<Production Example 5> 10 g of 2-hydroxy-3-phenoxypropyl acrylate and methylpolyoxyethylene (2
3) Methacrylate 50.0 g, styrene 4 g, 2,
2,2-trifluoroethyl methacrylate 35.0
g, and a mixed solvent of 100 ml of isopropyl alcohol and 100 ml of ethyl acetate were taken and mixed with stirring. to this,
0.1 g of benzoyl peroxide in isopropyl alcohol 1
After adding a solution dissolved in 0 ml, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Polymerization was carried out at the boiling point of the solvent for 10 hours. The mixed solvent was flushed with water to obtain an aqueous solution of the copolymer. This was freeze-dried to obtain Polymer 5 of the present invention.

[0026]

Embedded image 2-hydroxy-3-phenoxypropyl acrylate

<Production Example 6> 5 g of polyoxypropylene (2) acrylate, 5 g of vinyl alcohol, 50.0 g of methyl polyoxyethylene (23) methacrylate, 4 g of α-methylstyrene were placed in a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube. 35.0 g of 2,2,2-trifluoroethyl methacrylate and isopropyl alcohol 100
and a mixed solvent of 100 ml of ethyl acetate. After adding a solution of 0.1 g of benzoyl peroxide dissolved in 10 ml of isopropyl alcohol, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Polymerization was carried out at the boiling point of the solvent for 10 hours. The mixed solvent was flushed with water to obtain an aqueous solution of the copolymer. This was freeze-dried to obtain polymer 6.

[0028]

Embedded image Polyoxypropylene (2) acrylate

Production Example 7 19.6 g of methyl polyoxyethylene (23) methacrylate, 8.4 g of hydroxyethyl methacrylate, 12.0 g of stearyl acrylate, and 120 ml of isopropyl alcohol were placed in a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube. A mixed solvent of 80 ml of water was taken and mixed with stirring. After performing sufficient replacement with a nitrogen stream while continuing stirring, the mixture was heated to 60 ° C., and 0.1 g of ammonium persulfate and 0.1 g of sodium sulfite were added to each of 10 parts of water.
A solution dissolved in ml was added, and heating was continued for 6 hours to carry out polymerization. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain polymer 7.

[0030]

Embedded image Stearyl acrylate

Production Example 8 20.0 g of methyl polyoxyethylene (23) methacrylate, 16.4 g of hydroxyethyl methacrylate, 2,2,2,2 ', 2', A mixed solvent of 3.6 g of 2'-hexafluoroisopropyl acrylate, 120 ml of ethyl alcohol and 80 ml of water was taken and mixed with stirring. Thereafter, the mixture was sufficiently replaced with a nitrogen stream while continuing to stir, and then heated to 60 ° C. to form ammonium persulfate 0.1 ml.
1 g, sodium bisulfite 0.1 g and water 10 ml each
Was added thereto, and heating was continued for 6 hours to carry out polymerization. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, ethyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain Polymer 8 of the present invention.

<Production Example 9> In a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube, 24.3 g of methyl polyoxyethylene (23) methacrylate, 12.0 g of hydroxyethyl methacrylate, 18.0 g of methyl methacrylate, 1
0,10,10,9,9,8,8,7,7,6,6
5.7 g of 5,5,4,4,3,3-heptadecafluorodecanyl acrylate and isopropyl alcohol 1
A mixed solvent of 80 ml and 120 ml of water was taken and mixed with stirring. 0.7 g of ammonium persulfate was added to 10 ml of water.
After the addition of the solution dissolved in, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. The mixture was heated to 80 ° C. and polymerized for 12 hours. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain Polymer 9 of the present invention.

<Production Example 10> In a flask equipped with a condenser, a stirrer, and a nitrogen introducing tube, 20.0 g of methyl polyoxyethylene (9) methacrylate, 12.8 g of 2-hydroxy-3-phenoxypropyl acrylate, and n-butyl acrylate 4. 0 g, 5,5,4,4,3,3,2,2-octafluoropentyl methacrylate 3.4 g, isopropyl alcohol 100 ml, ethyl acetate 100 m
1 mixed solvent was taken and mixed with stirring. A solution of 0.2 g of benzoyl peroxide dissolved in 10 ml of isopropyl alcohol was added thereto, and the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. Polymerization was carried out at the boiling point of the solvent for 10 hours. Flushing from the mixed solvent to water was performed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain Polymer 10 of the present invention.

<Production Example 11> 24.0 g of methyl polyoxyethylene (23) methacrylate and methyl methacrylate were placed in a flask equipped with a cooler, a stirrer and a nitrogen inlet tube.
1 g, 3.9 g of 2,2,3,3-tetrafluoropropyl acrylate, and 150 m of isopropyl alcohol
A mixed solvent of 50 ml of water was taken and mixed with stirring. After a solution of 0.3 g of ammonium persulfate dissolved in 10 ml of water was added thereto, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued. The mixture was heated to 80 ° C. and polymerized for 8 hours. After adjusting the pH to 7.0 with an aqueous sodium hydroxide solution, isopropyl alcohol was removed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain the polymer 11 of the present invention.

<Production Example 12> In a flask equipped with a condenser, a stirrer, and a nitrogen inlet tube, 16.0 g of methyl polyoxyethylene (9) methacrylate, 12.0 g of methacrylic acid, 8.4 g of methyl methacrylate, 2, 2, 2, and 2 ', 2',
2'-hexafluoroisopropyl acrylate 3.6
g, and a mixed solvent of 100 ml of isopropyl alcohol and 100 ml of ethyl acetate were taken and mixed with stirring. to this,
After a solution of 0.2 g of 2,2-azobis (isobutyronitrile) dissolved in 10 ml of isopropyl alcohol was added, the mixture was sufficiently replaced with a nitrogen stream while stirring was continued.
Polymerization was carried out at the boiling point of the solvent for 6 hours. Flushing from the mixed solvent to water was performed to obtain an aqueous solution of the desired copolymer. This was freeze-dried to obtain Polymer 6 of the present invention.

The physical properties (water repellency and oil repellency) of the polymer of the present invention will be described with reference to examples. A 5% aqueous solution of polymers 1 to 12 is dropped on filter paper and dried, and a polymer film is cast on the filter paper. Water and oil (olive oil) were dropped on the polymer film cast on the filter paper, and the contact angle was measured. Polymer 1
6, 8 to 12 measured values are 60 for water and oil
The temperature did not change at all from 70 degrees to 48 degrees for 48 hours. Polymer 7
One hour after the oil was dropped, the oil was absorbed by the filter paper.
Also, there was no change in water up to 4 hours.
Within hours the filter paper had absorbed it. This indicates that it is preferable that a fluorine atom be contained in the molecule of the polymer, which is an essential component of the composition of the present invention.

For the polymers 1 to 12, polymer films are cast on filter paper in the same manner as described above. The filter paper was set in a Fritz diffusion cell, and the lower portion was filled with water (aqueous solution of 0.5% sodium polyacrylate) and glyceryl triisooctanoate. Dye (R102) aqueous solution (sodium polyacrylate 0.5% aqueous solution), dye (R502)
A glyceryl triisooctate solution was added, and the mixture was left for 30 minutes while stirring the lower part. The lower solution was taken and the absorbance was measured, but almost no permeation of the dye was observed. This indicates that the polymer film, which is an essential component of the composition of the present invention, has excellent water repellency and oil repellency and suppresses water and oil permeation. This shows that such a film is useful as a protective film.

A cast film was prepared in the same manner as described above, gently squeezed twice, and tested in the same manner. It is apparent from the above that the polymer film, which is an essential component of the composition of the present invention, has sufficient plasticity without a plasticizer. That is, it is understood that the composition of the present invention does not require the use of a plasticizer that may be an endocrine disrupting substance.

The same test as above was performed with the filter paper replaced with a cloth (Tetron), but similar results were obtained.

Films of polymers 1 to 12 were formed on the metal surface, and water and oil were dropped to measure the contact angle. The results were the same as above.

(4) Composition of the Present Invention The composition of the present invention comprises one or more monomers selected from the monomers represented by the above general formula (I) and a monomer represented by the general formula (II) And a polymer having a polymer structure containing at least one selected from the group consisting of: As the composition of the present invention, those used for surface treatment are preferable, and the surface to be treated is preferably skin surface, nail surface, hair surface, fiber surface, glass surface or metal surface. it can.
That is, as the composition of the present invention, specifically, an external preparation for skin, a fiber treatment agent, a paint and the like can be suitably exemplified, and it is particularly preferable to apply the composition to an external preparation for skin. Examples of the skin external preparation include cosmetics, skin external medicines, and external bactericides, among which cosmetics are particularly preferred. This is because the function of the polymer, which is an essential component of the composition of the present invention, matches well with the quality required of the cosmetic. Here, the cosmetics are cosmetics generally referred to as, for example, creams, emulsions, lotions, basic cosmetics for purifying the skin such as packs, under makeup, foundation, lip color, Teak color,
Make-up cosmetics with the function of clothes such as nail colors, hair tonics, hair liquids, hair creams, etc. Examples thereof include cleaning cosmetics having an effect. Any of these can be applied to the cosmetic of the present invention. If it is a basic cosmetic, it exhibits an excellent skin protection effect, and if it is a make-up cosmetic, it has good make-up and good make-up. Express the effect,
Hair cosmetics exhibit excellent functions such as excellent comb protection and good combability at the same time. A feature of the composition of the present invention is that it does not require a plasticizer, and has conventionally been used as a film-forming agent, such as diester phthalate, triethyl citrate, glyceryl monocaprylate, and propyl carbonate. The plasticizer may not be contained, and it is particularly preferable not to contain the plasticizer component in consideration of environmental problems and the like.

The composition of the present invention may contain, in addition to the above-mentioned essential component, a polymer, optional components usually used in such a composition as long as the effects of the present invention are not impaired. I can do it. Such optional components include, for example, in the case of cosmetics, hydrocarbons such as petrolatum and microcrystalline wax, esters such as jojoba oil and gay wax, triglycerides such as tallow, olive oil, cetanol, and oleyl alcohol. Higher alcohols such as
Fatty acids such as stearic acid and oleic acid, polyhydric alcohols such as glycerin and 1,3-butanediol, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, ethanol, carbopol, etc. Thickeners, preservatives, ultraviolet absorbers, antioxidants, dyes, powders, etc. can be exemplified. In the case of medicines, excipients, binders, coating agents, lubricants, sugar coatings, disintegrants , Extenders, flavoring agents, emulsifying / solubilizing / dispersing agents, stabilizers, pH adjusters, isotonic agents, etc., and in the case of paints, pigments, surfactants as dispersing agents, dispersing solvents, etc. In the case of a fiber treatment agent, examples thereof include a penetration promoting component such as a solvent and a surfactant. The composition of the present invention can be produced by treating these components according to a conventional method.

<Examples 1 to 8> Nail colors were prepared based on the following formulations. That is, the prescription components were well stirred and mixed and rolled to obtain a nail color. After coating, excellent water-resistant coatings were formed in all the formulation systems. This effect is compared with that of Comparative Example 1 in which the polymer 1 of Example 1, which is the cosmetic of the present invention, and a part of water are replaced with an acrylic resin emulsion which is usually used in an aqueous system so that the dry residue is equal. The results of the scratch test with a pencil having a hardness of H were evaluated as good (○), equivalently Δ and poor (×). The results are also shown in the table. This is because the polymer, which is an essential component of the present invention, forms a flexible film even without a plasticizer.

[0044]

[Table 1]

<Examples 9 to 16> Paints were prepared based on the following formulations. That is, the prescription components were well mixed with stirring and rolled to obtain a paint. After application, excellent water-resistant coatings were formed in all formulation systems despite the absence of plasticizer.

[0046]

[Table 2]

Examples 17 to 24 Waterproofing sprays were prepared based on the following formulations. That is, the prescription components were well stirred and mixed to obtain a waterproof spray. After spraying, in all the formulation systems, excellent water-resistant coatings were formed despite being water-based.

[0048]

[Table 3]

<Examples 25 to 32> Cosmetics for hair were prepared based on the following prescription. That is, after each of (a) and (b) was stirred and solubilized at 80 ° C., (b) was added to (a) while stirring well, and the mixture was stirred and cooled to obtain a hair cosmetic. After spraying,
Excellent water-resistant coatings were formed in all formulations. This is because the cosmetic 1 of Example 25 and a part of water, which is the cosmetic of the present invention, have the same dry residue as the content of the polymer 1 in terms of good combability and hair styling. The results were compared with Comparative Example 2 in which a normal acrylic resin emulsion was substituted and evaluated by a specialized panelist, and as shown in Tables 4 and 5, it is clear from the fact that all were obtained with excellent evaluations. Here, the evaluation criteria were: ：: better than Comparative Example 2, Δ: comparable to Comparative Example 2, ×: inferior to Comparative Example 2.

[0050]

[Table 4]

[0051]

[Table 5]

<Examples 33 to 40> Oil-in-water cream (cosmetics) which is a composition of the present invention according to the following formulation:
It was created. That is, the components (a) and (b) were each heated to 80 ° C., (b) was gradually added to (a), emulsified, and the particles were homogenized with a homogenizer, followed by stirring and cooling to obtain a cream. A comparative example 3 was prepared by replacing the polymer with sodium hyaluronate, which is known to have a high water retention, and a group of 10 people suffering from rough skin, using a total of 90 panelists, for 3 weeks The evaluation of the improvement of the rough skin in the continuous use of was evaluated. Table 6 shows the results as the number of appearance cases. From this, it can be seen that the cosmetic of the present invention is excellent in the effect of supplementing the damaged stratum corneum function and improving the rough skin due to the excellent coating. Here, the evaluation criteria for the skin roughness improving effect were ++: markedly improved, +: clearly improved, ±: slightly improved,-: not improved. In addition, when an acrylic polymer component is contained in a cosmetic or the like, and a plasticizer is not contained, a tactile feeling is often exhibited due to the film properties thereof. There was no such feeling of tension. This is because the polymer compound, which is an essential component of the cosmetic of the present invention, has excellent plasticity. A Sucrose fatty acid ester 0.5 parts by weight Vaseline 1 part by weight Lanolin 3 parts by weight Liquid paraffin 8 parts by weight Low viscosity silicone 10 parts by weight Stearyl alcohol 0.5 parts by weight Stearic acid 0.55 parts by weight Undecylenic acid monoglyceride 2 parts by weight Polyoxy Ethylene (20) behenyl ether 2 parts by weight b 1,3-butanediol 5 parts by weight Glycerin 5 parts by weight Polymer * 1 part by weight Potassium hydroxide 0.05 parts by weight Water 61.4 parts by weight * Details are shown in Table 6. .

[0053]

[Table 6]

<Examples 41 to 48> According to the following formulation, a foundation (cosmetic) as a composition of the present invention was prepared. That is, a, b, c and d are 80
The mixture was heated to 0 ° C., kneaded well with the mixture (a) and (b), and diluted by adding c to the mixture. E was dispersed therein, and the mixture was gradually added and emulsified, followed by stirring and cooling to obtain a foundation. With respect to these, the cosmetic moistness under the condition of the sauna for 30 minutes was evaluated by a specialized panelist in comparison with Control Example 1 in which the polymer was replaced with water. Evaluation criteria: ++: significantly better than control example 1, +: clearly better than control example 1, ±: control example 1
Slightly better,-: The same degree as that of Comparative Example 1 was used. Table 7 shows the results. From this, it is understood that the cosmetic of the present invention has extremely good stickiness. A 70% aqueous maltitol solution 5 parts by weight glycerin 2 parts by weight 1,3-butanediol 5 parts by weight b triglycerin diisostearate 5 parts by weight c liquid paraffin 15 parts by weight carnauba wax 2 parts by weight microcrystalline wax 3 parts by weight Isooctyl paramethoxycinnamate 2 parts by weight D 42.5 parts by weight Polymer ** 3.5 parts by weight E Iron-doped titanium dioxide 8 parts by weight Zinc oxide 1 part by weight Titanium dioxide 1 part by weight Talc 3 parts by weight Bengala 1 part by weight Yellow Iron oxide 1 part by weight

[0055]

[Table 7]

<Example 49> According to the following formulation,
A steroid cream which is a pharmaceutical composition for external use on the skin of the present invention was prepared. That is, A, B, C, and D were each heated to 80 ° C., and A and B were well kneaded, C was added and diluted, and D was gradually added and emulsified. This was stirred and cooled to obtain a steroid cream. When this product was used for one month by a patient suffering from atopic dermatitis, the symptoms were remarkably improved. This patient often did not respond to the steroid cream, but the dermatological composition of the present invention exerted a remarkable effect. A 70% aqueous malbitol solution 5 parts by weight glycerin 3 parts by weight 1,3-butanediol 5 parts by weight methyl paraben 0.3 parts by weight butyl paraben 0.1 parts by weight b triglycerin diisostearate 5 parts by weight c solid paraffin 2 parts by weight Microcrystalline wax 3 parts by weight Liquid paraffin 10 parts by weight Carnauba wax 2 parts by weight Light isoparaffin 5 parts by weight Prednisolone 1 part by weight D 58 parts by weight Polymer 1 0.6 parts by weight

<Example 50> According to the following formulation,
An antifungal cream which is a pharmaceutical composition for external use on the skin of the present invention was prepared. That is, A, B, C, and D were each heated to 80 ° C., and A and B were well kneaded, C was added and diluted, and D was gradually added and emulsified. This was stirred and cooled to obtain an antifungal cream. It exhibited excellent antifungal activity. This is due to the obstruction by the polymer film containing the compound of the general formula (I) and the compound of the general formula (II), which are essential components of the composition of the present invention, and the plasticity of the polymer film. It can be seen that this is due to the film maintenance. A 70% aqueous malbitol solution 5 parts by weight glycerin 3 parts by weight 1,3-butanediol 5 parts by weight methyl paraben 0.3 parts by weight butyl paraben 0.1 parts by weight b triglycerin diisostearate 5 parts by weight c solid paraffin 2 parts by weight Microcrystalline wax 3 parts by weight Liquid paraffin 10 parts by weight Carnauba wax 2 parts by weight Light isoparaffin 5 parts by weight Terbinafine 1 part by weight D Water 58 parts by weight Polymer 2 0.6 parts by weight

<Example 51> According to the following formulation,
A lotion, a composition of the present invention, was prepared. It has a skin-improving effect due to excellent water retention,
It is stable under severe storage conditions of 1 month and 5 ° C. for 1 month, which indicates that this is due to the excellent water solubility of the polymer of the present invention. Further, it can be seen that the skin improving effect is due to the action of forming a water-retaining film having plasticity of the polymer. Glycerin 3 parts by weight 1,2-pentanediol 5 parts by weight Ethanol 5 parts by weight Polymer of the present invention 9 0.1 parts by weight Water 86.9 parts by weight

<Example 52> According to the following formulation,
A lotion, a composition of the present invention, was prepared. It has a skin-improving effect due to excellent water retention,
It is stable under severe storage conditions of 1 month and 5 ° C. for 1 month, which indicates that this is due to the excellent water solubility of the polymer of the present invention. Further, it can be seen that the skin improving effect is due to the action of forming a water-retaining film having plasticity of the polymer. Glycerin 3 parts by weight 1,2-pentanediol 5 parts by weight Ethanol 5 parts by weight Polymer 10 of the present invention 10 parts by weight Water 86.9 parts by weight

<Example 53> According to the following formulation,
A lotion, a composition of the present invention, was prepared. It has a skin-improving effect due to excellent water retention,
It is stable under severe storage conditions of 1 month and 5 ° C. for 1 month, which indicates that this is due to the excellent water solubility of the polymer of the present invention. Further, it can be seen that the skin improving effect is due to the action of forming a water-retaining film having plasticity of the polymer. Glycerin 3 parts by weight 1,2-pentanediol 5 parts by weight Ethanol 5 parts by weight Polymer 11 of the present invention 0.1 parts by weight Water 86.9 parts by weight

<Example 54> According to the following formulation,
A lotion, a composition of the present invention, was prepared. It has a skin-improving effect due to excellent water retention,
It is stable under severe storage conditions of 1 month and 5 ° C. for 1 month, which indicates that this is due to the excellent water solubility of the polymer of the present invention. Further, it can be seen that the skin improving effect is due to the action of forming a water-retaining film having plasticity of the polymer. Glycerin 3 parts by weight 1,2-pentanediol 5 parts by weight Ethanol 5 parts by weight Polymer of the present invention 12 0.1 part by weight Water 86.9 parts by weight

Example 55 According to the following formulation,
A lotion, a composition of the present invention, was prepared. It has a skin-improving effect due to excellent water retention,
Under harsh storage conditions of 5 months and 5 ° C. for 1 month, compared to the lotions of Examples 51 to 54, although a little turbidity was observed, it was almost stable, which was due to the excellent water solubility of the polymer of the present invention. It can be seen that this is the cause. Considering the slight clouding, the composition ratio of the compound represented by the general formula (I) in the polymer is 5 to 9.9% by weight, more preferably 7 to 9.5% by weight. % Is a particularly preferred range. Further, it can be seen that the skin improving effect is due to the action of forming a water-retaining film having plasticity of the polymer. Glycerin 3 parts by weight 1,2-pentanediol 5 parts by weight Ethanol 5 parts by weight Polymer 2 of the present invention 0.1 part by weight Water 86.9 parts by weight

[0063]

According to the present invention, it is useful that it is uniformly dissolved in an aqueous carrier,
It is possible to provide a polymer-containing composition that forms a coating having excellent water resistance after application.

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Claims (9)

[Claims] (1) one or more kinds selected from the monomers represented by the following general formula (I) and one or more kinds selected from the monomers represented by the general formula (II) A composition containing a polymer having plasticity, which is contained as a monomer. Embedded image General formula (I) (wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 represents an alkyl group having 1 to 20 carbon atoms which may have a fluorine atom.) Formula 2 Formula (II) (wherein, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R4 may have an alkyloxy group, an acyloxy group, or a hydroxyl group, and has 2 to 4 carbon atoms. R5 represents a hydrogen atom, an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and n represents 1 to 4
Represents a numerical value of 0. ) 2. A compound represented by the general formula (I):
The composition according to claim 1, comprising a compound represented by the general formula (III). Embedded image General formula (III) (wherein, R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, O and P each independently represent a numerical value of 1 to 10, and R7 represents a fluorine atom or a hydrogen atom. .) 3. The composition according to claim 1, wherein the compound represented by the general formula (II) contains a compound represented by the general formula (IV). Embedded image General formula (IV) (wherein, R8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R9 represents an aromatic or aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom, Q represents a numerical value of 5 to 30.) 4. One or more compounds selected from the compounds represented by the general formula (I), 5 to 9.9% by weight, and one or more compounds selected from the compounds represented by the general formula (II) The polymer-containing composition according to any one of claims 1 to 3, wherein the polymer contains two or more kinds as constituent monomers in an amount of 30 to 90.1% by weight. 5. The method according to claim 1, wherein when a uniform system is prepared by adding 99 parts by weight of water to 1 part by weight of the polymer, the transmittance of the liquid to visible light is 90% or more. ~ 4
The polymer-containing composition according to any one of the above. 6. The polymer-containing composition according to claim 1, which is for surface treatment. 7. The method according to claim 1, wherein the surface is a skin surface, a nail surface, a hair surface,
The polymer-containing composition according to any one of claims 1 to 6, wherein the composition is a fiber surface, a glass surface, or a metal surface. 8. It does not contain a plasticizer,
The polymer-containing composition according to claim 1. 9. The polymer-containing composition according to claim 1, which is a cosmetic.