JPH05255041A - Film-forming cosmetic - Google Patents

Abstract

PURPOSE:To obtain a film-forming cosmetic having excellent spreading properties and drying properties and sufficient film strength. CONSTITUTION:A film-forming cosmetic blended with an aqueous resin emulsion composed of a resin comprising >=30wt.% one more polymerizable monomers selected from a polymerizable unsaturated monomer containing a hydrogen bond-forming group (except base-forming group) and a polymerizable unsaturated monomer containing a salt-forming group, having >=30,000 weight-average molecular weight, as a constituent unit or a water dispersion of self-dispersion type polymer fine particles obtained by copolymerizing a polymerizable unsaturated monomer mixture having 0.5-70mol% at lease one polymerizable unsaturated monomer containing a salt-forming group to give a copolymer having >=30,000 molecular weight, purifying a solution of the copolymer in an organic solvent and adding water to the solution or adding water to the solution and then purifying the solution and distilling away the organic solvent as a film-forming agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-forming cosmetic composition, particularly a pack cosmetic composition, and more specifically, it has a high film strength enough to withstand use as a pack even if it is blended alone, and has a good coating property, drying property, and The present invention relates to a film-forming cosmetic composition containing an aqueous resin emulsion excellent in odor and the like as a main film-forming agent.

[0002]

2. Description of the Related Art Almost all peel-off type pack cosmetics, which are currently the mainstream of the film-forming cosmetics market such as packs, contain partially saponified polyvinyl alcohol (PVA). It is added as a main film forming agent. PVA has very good properties in terms of film strength and safety, but it has applicability (stickiness, poor elongation, dripping), dryness (slow dryness), odor (acetic acid odor), and film moisture. It has been pointed out that there is a problem in terms of permeability (the moisture permeation rate is fast and a sufficient moisturizing effect cannot be obtained), and in recent years, several attempts have been made to solve these problems related to peel-off type pack cosmetics. Is beginning to be done.

One is mainly related to the improvement of odor. P
By using other water-soluble polymers instead of VA, such as natural polysaccharides, which have a high film strength comparable to PVA typified by pullulan and are highly safe, as the main film forming agent, long-term storage It is also a method of obtaining a pack cosmetic that is stable and has no acetic acid odor. However,
Many of these water-soluble polymers do not have an acetic acid odor but have a peculiar unpleasant odor, and since they do not exceed PVA in terms of coating properties and drying properties, they are hardly used in actual products.

The other is mainly related to improvement of coating property and drying property, and an aqueous resin emulsion having high thixotropic property and capable of high concentration is blended alone or in combination with PVA or the above water-soluble polymer. This is a method for obtaining a pack-like cosmetic that is creamy, easy to apply, and quick-drying. As the water-based resin emulsion, there are various water-based resin emulsions synthesized by emulsion polymerization or dispersion polymerization such as vinyl resin emulsion, synthetic rubber latex, and acrylic resin emulsion, or soap-free emulsion polymerization (Japanese Patent Publication No. 51-12939). , Japanese Examined Sho 55-3817
JP-B No. 57-77611, JP-B No. 59-62512 and JP-A No. 1-261318), and especially synthetic rubber latex is said to have a low moisture permeability and a high moisturizing effect. However, most of the above water-based resin emulsions have low film strength, so it is almost impossible to use them alone. In practice, a large amount of PVA and other water-soluble polymers must be used in combination. Is barely utilized. In addition, many water-based resin emulsions have problems such as dispersion stability and odor derived from residual impurities. Therefore, it is necessary to solve the above problems in order to prepare a film-forming cosmetic such as a pack cosmetic using an aqueous resin emulsion as a main film-forming agent.

[0005]

In view of the above situation, the present inventors have earnestly studied to obtain a film-forming cosmetic having excellent coatability and drying property and having sufficient film strength, particularly a pack cosmetic. As a result of stacking, it was found that it is effective to use a specific water-based resin emulsion or an aqueous dispersion of self-dispersing polymer particles obtained by a specific method as a film-forming agent. When a liquid was used, it was found that the stability was excellent and a high degree of purification was possible, and the present invention was completed.

That is, the present invention is selected from the group consisting of a polymerizable unsaturated monomer having a group capable of forming a hydrogen bond (excluding a salt-forming group) and a polymerizable unsaturated monomer having a salt-forming group. A water-based resin emulsion containing a resin having a weight average molecular weight of 30,000 or more and containing 30% by weight or more of one or more kinds of polymerizable unsaturated monomers as a constitutional unit and being blended as a film forming agent. The present invention provides a film forming cosmetic.

The present invention also has a weight average molecular weight of 30,000 or more obtained by copolymerizing a polymerizable unsaturated monomer mixture containing 0.5 to 70 mol% of at least one polymerizable unsaturated monomer having a salt-forming group. The organic solvent solution of the copolymer which is is purified and then water is added, or water is added and then purified and the organic solvent is distilled off to obtain an aqueous dispersion of self-dispersing polymer particles, which is a film. The present invention provides a film-forming cosmetic composition characterized by being blended as a forming agent.

The present invention further relates to a polymerizable unsaturated monomer having 0.5 to 70 mol% of at least one polymerizable unsaturated monomer having a salt-forming group and a group capable of forming a hydrogen bond (excluding the salt-forming group). An organic solvent solution of a copolymer having a weight average molecular weight of 30,000 or more obtained by copolymerizing a polymerizable unsaturated monomer mixture containing 30 to 99% by weight of a monomer is added with water after purification, or A film-forming cosmetic comprising a water-dispersed liquid of self-dispersing polymer particles obtained by distilling an organic solvent after purification by adding water as a film-forming agent. It is a thing.

In the present invention, the group capable of forming a hydrogen bond is a functional group other than a salt-forming group capable of forming a relatively strong hydrogen bond. Specific examples thereof include a hydroxyl group, an amide group, a polyether group and a sugar residue. In general, (meth) acrylic acid ester-based polymerizable unsaturated monomers are often used in water-based resin emulsions, but a film made from a water-based resin emulsion containing (meth) acrylic acid ester as a main component is used. The strength is insufficient for use in film-forming cosmetics such as pack cosmetics. Therefore, although ester groups are also known to form weak hydrogen bonds, the groups capable of forming hydrogen bonds in the present invention do not include ester groups.

The polymerizable unsaturated monomer having a group capable of forming a hydrogen bond (excluding a salt-forming group) used in the present invention (hereinafter abbreviated as a hydrogen-bonding monomer) is (meth) acryl. Acid 2-hydroxyethyl, (meth) acrylic acid 3-
Hydroxypropyl, (meth) acrylic acid 3-oxa-
Hydroxyl group-containing monomers such as 5-hydroxypentyl, N- (2,2,2-trishydroxymethyl) ethylmethacrylamide; (meth) acrylamide, N- (1,1-dimethyl-3)
-Oxobutyl) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, Nt-
Butyl acrylamide, N-i-propyl acrylamide, N- methylol (meth) amide group-containing monomers such as acrylamide; equation _{CH 2 = CHCOO- (CH 2 CH} 2 O) n -R (n = 1~300; R = H or CH
_{3) CH 2 = C (CH} 3) COO- (CH 2 CH 2 O) n -R (n = 1~300; R = H or CH ₃₎ polyethylene oxide group represented by, and has a polypropylene oxide group Polyether group-containing monomers such as (meth) acrylic acid ester; sugar residue-containing monomers such as glucosylethyl methacrylate. As these hydrogen-bonding monomers, (meth) acrylamide-based monomers are preferable, and N- (1,1-dimethyl-3-oxobutyl) acrylamide is particularly preferable.

As the polymerizable unsaturated monomer having a salt-forming group used in the present invention, as a cationic monomer,
There are unsaturated tertiary amine-containing monomers, unsaturated ammonium salt-containing monomers, and the like. Specifically, vinyl pyridine,
Monovinylpyridines such as 2-methyl-5-vinylpyridine and 2-ethyl-5-vinylpyridine; Styrenes having a dialkylamino group such as N, N-dimethylaminostyrene and N, N-dimethylaminomethylstyrene;
N, N-Dimethylaminoethyl acrylate, N, N-Dimethylaminoethyl methacrylate, N, N-Diethylaminoethyl acrylate, N, N-Diethylaminoethyl methacrylate, N, N-Dimethylaminopropyl acrylate, N, N-Dimethylaminopropyl Methacrylate,
N, N-diethylaminopropyl acrylate, N, N-diethylaminopropyl methacrylate, such as esters of acrylic acid or methacrylic acid having a dialkylamino group; vinyl ethers having a dialkylamino group such as 2-dimethylaminoethyl vinyl ether; N-
(N ', N'-dimethylaminoethyl) acrylamide, N-
(N ', N'-dimethylaminoethyl) methacrylamide, N
-(N ', N'-diethylaminoethyl) acrylamide, N
-(N ', N'-diethylaminoethyl) methacrylamide,
N- (N ', N'-dimethylaminopropyl) acrylamide, N- (N', N'-dimethylaminopropyl) methacrylamide, N- (N ', N'-diethylaminopropyl) acrylamide, N- (N' , N'-Diethylaminopropyl) methacrylamide such as acrylamide or methacrylamide having a dialkylamino group, or alkyl halides thereof (alkyl group having 1 to 18 carbon atoms, chlorine as halogen, bromine, iodine), benzyl halide , For example, benzyl chloride or benzyl bromide, alkyl or aryl sulfonic acids such as alkyl esters of methane sulfonic acid, benzene sulfonic acid or toluene sulfonic acid (alkyl groups having 1 to 18 carbon atoms), and dialkyl sulphates (carbon number of alkyl groups). 1 to 4) and the like which are quaternized with a known quaternizing agent. . The anionic monomer includes unsaturated carboxylic acid monomer, unsaturated sulfonic acid monomer, unsaturated phosphoric acid monomer, and the like.
Specifically, as the unsaturated carboxylic acid monomer, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, 2-methacryloyloxymethylsuccinic acid, or the like, or their anhydrides and salts are used. As the unsaturated sulfonic acid monomer, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylic acid ester, bis- (3-sulfopropyl) -itaconic acid ester, etc. And salts thereof, and other sulfuric acid monoesters of 2-hydroxyethyl (meth) acrylic acid and salts thereof, and unsaturated phosphoric acid monomers include vinylphosphonic acid, vinylphosphate, bis (methacryloxyethyl) phosphate, Diphenyl-2-acryloyloxyethyl phosphate , Diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate, dioctyl-2- (meth) acryloyloxyethyl phosphate, and the like.

Polymerizable unsaturated copolymerizable with a polymerizable unsaturated monomer selected from the group consisting of a hydrogen-bonding monomer and a polymerizable unsaturated monomer having a salt-forming group used in the present invention. As the monomer, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate,
Acrylic esters such as isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, dodecyl acrylate; methyl methacrylate, Ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, decyl methacrylate, Methacrylic acid esters such as dodecyl methacrylate; styrene, vinyltoluene, 2
-Styrene monomers such as methylstyrene and chlorostyrene; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; CH ₂ ═CHCOOC ₂ H ₄ C ₆ F ₁₃ , CH ₂ ═CHCOOC ₂ H ₄ C ₈ F ₁₇ , CH ₂ = C
HCOOC ₂ H ₄ C ₁₀ F ₂₁ , CH ₂ = CHCOOC ₂ H ₄ C ₁₂ F ₂₅ , CH ₂ = C (CH
₃ ) COOC ₂ H ₄ C ₆ F ₁₃ , CH ₂ = C (CH ₃ ) COOC ₂ H ₄ C ₈ F ₁₇ , CH ₂ = C (C
H ₃ ) COOC ₂ H ₄ C ₁₀ F ₂₁ , CH ₂ = C (CH ₃ ) COOC ₂ H ₄ C ₁₂ F ₂₅ , CH _{2
= CHCOOC 2 H 4 - (CF} 2) 6 -H, CH 2 = CHCOO- (CF 2) 8 -H, CH 2 = C
_{(CH 3) COOC 2 H 4} - (CF 2) 6 -H, CH 2 = C (CH 3) COO- (CF 2) having a fluorinated alkyl group represented by ₈ -H, etc. (meth) acrylic acid ester And acrylonitrile and the like,
It is not limited to these.

For the production of an aqueous resin emulsion containing as a constituent unit a polymerizable unsaturated monomer selected from the group consisting of a hydrogen bondable monomer and a polymerizable unsaturated monomer having a salt-forming group, One or two selected from the group consisting of a hydrogen-bonding monomer and a polymerizable unsaturated monomer having a salt-forming group.
One or more polymerizable unsaturated monomers and, if necessary, one or two or more polymerizable unsaturated monomers copolymerizable therewith can be used, and the production method is a conventional emulsion polymerization. , Soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, and a method for synthesizing self-dispersion type polymer particles. The content in the polymer of the polymerizable unsaturated monomer selected from the group consisting of a polymerizable unsaturated monomer having a hydrogen-bonding monomer and a salt-forming group, as a film-forming cosmetic such as a pack In order to develop the film strength, it is necessary to be 30% by weight or more, preferably 40% by weight or more.

Known anionic, cationic or nonionic emulsifiers are used in emulsion polymerization, and known water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone and cationized cellulose are used in suspension polymerization and dispersion polymerization. Used. A known radical polymerization initiator is used as the polymerization initiator. For example, persulfates represented by sodium persulfate, hydroperoxides represented by t-butyl hydroperoxide, dialkyl peroxides represented by di-t-butyl peroxide, represented by lauroyl peroxide. Diacyl peroxides, peresters typified by t-butyl peracetate, ketone peroxides typified by methyl ethyl ketone peroxide, and 2,2′-azobis (isobutyronitrile), 2,2′-azobis ( 2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), and other azo-based polymerization initiators, redox-based radical polymerization initiators, and the like.

The resin containing 30% by weight or more of the polymerizable unsaturated monomer having a hydrogen-bonding monomer and / or a salt-forming group as a constitutional unit of the present invention has a weight average molecular weight of 30,000 or more, preferably 100,000. That is all. The weight average molecular weight is
If it is less than 30,000, sufficient film properties cannot be obtained.
The particle size of the water-based resin emulsion containing 30% by weight or more of the polymerizable unsaturated monomer having a hydrogen-bonding monomer and / or a salt-forming group as a constituent unit is not particularly limited, but is preferably 10 to 10000 nm. The range is.

The production method of the self-dispersing polymer fine particles used in the present invention excluding the purification step is described in JP-A-63-280702, and a polymerizable unsaturated monomer having a salt-forming group, and those From the polymerizable unsaturated monomers that can be copolymerized with, one kind or two or more kinds can be selected and used. Further, as a polymerization method for obtaining a copolymer from these several types of polymerizable unsaturated monomer mixture,
Using the above radical polymerization initiator, conventionally known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be appropriately used. The organic solvent solution of the copolymer is
(i) after isolating the copolymers obtained by various methods,
It can be obtained by a method of dissolving in the solvent, (ii) a method of carrying out solution polymerization in an organic solvent, or the like, but the method (ii) is preferable in consideration of the ease of the production process.

The organic solvent used in the production of the self-dispersible polymer fine particles of the present invention is preferably a hydrophilic organic solvent, and specific examples thereof include alcohol type, ketone type and ether type solvents. Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, isobutanol, diacetone alcohol and the like, but isopropanol is preferable. Examples of the ketone solvent include acetone,
Examples thereof include methyl ethyl ketone, diethyl ketone, dipropyl ketone, methyl isobutyl ketone, methyl isopropyl ketone and the like. Examples of the ether solvent include diethyl ether, dibutyl ether, tetrahydrofuran, dioxane and the like. These hydrophilic organic solvents are 1
Or a mixture of two or more species, and if necessary,
A high boiling hydrophilic organic solvent may be used in combination. As the high boiling hydrophilic organic solvent, phenoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, 3-methyl-3- Butoxybutanol and the like.

The content of the polymerizable unsaturated monomer having a salt-forming group in the monomer mixture used for producing the self-dispersible polymer fine particles of the present invention is 0.5 to 70 mol%, and 0.5 to 70 mol%.
60 mol% is preferred. If the value exceeds or falls below this range, self-dispersing polymer particles having good dispersion stability cannot be obtained. The polymerizable unsaturated monomer that can be copolymerized with the polymerizable unsaturated monomer having a salt-forming group used in the present invention is not particularly limited as described above, but when obtaining a copolymer Polymerization stability, dispersion stability of the resulting self-dispersing polymer particles, safety of the film-forming cosmetic composition after compounding, mechanical properties or storage stability in good condition, and sufficient use as a pack In order to obtain a copolymer with a possible high film tensile strength,
It is preferable to contain 30 to 99% by weight of the hydrogen-bonding monomer in the polymerizable unsaturated monomer as described above, particularly (meth) acrylamide-based monomer as the hydrogen-bonding monomer,
The content of the polymerizable unsaturated monomer in the mixture is preferably 30 to 99.5 mol%, more preferably 40 to 99.5 mol%. Further, among the (meth) acrylamide type monomers, N- (1,1-dimethyl-3-oxobutyl) acrylamide is most preferable.

The weight average molecular weight of the copolymer forming the self-dispersible polymer fine particles of the present invention is 30,000 or more, preferably 50,000 or more, more preferably 100,000 or more. If the weight average molecular weight is less than 30,000, sufficient film physical properties cannot be obtained.

In order to obtain the aqueous dispersion of self-dispersible polymer particles of the present invention, the organic solvent solution of the copolymer obtained by the above method is purified. Purification can also be carried out by a method such as azeotropic distillation under reduced pressure in the state of a polymer aqueous dispersion after phase inversion to an aqueous system, as in the case of a conventional aqueous dispersion polymer obtained by emulsion polymerization or the like. However, in addition to this, a state characteristic of the self-dispersing polymer fine particles of the present invention, which is not present in other water-dispersed polymers, that is, obtained by an arbitrary polymerization method from a mixture of several kinds of polymerizable unsaturated monomers Hydrophobic or hydrophilic organic solvent solution of the obtained copolymer, and hydrophilic organic solvent solution of the copolymer neutralized as necessary, or hydrophilic organic solvent / water mixed solution Is. In this case, it is possible to apply various methods that can be expected to have a higher degree of purification than the vacuum distillation method, for example, methods such as ultrafiltration and reprecipitation of the polymer. Considering the convenience of, it is most preferable to use the ultrafiltration method.

Although the specific conditions for ultrafiltration are not particularly limited, examples of the material of the ultrafiltration membrane to be used include hydrophobic and hydrophilic organic solvents represented by ceramics and the like, neutralization and the like. It is preferable to use a material that is not corroded by the acid or base used for the above, residual monomer, various impurities and decomposition products, and the like. The amount of impurities such as residual monomers contained in the aqueous dispersion of the phase inversion type self-dispersion polymer particles produced through the purification step by ultrafiltration is a general purification method for conventional dispersion polymers. Compared with the case of performing purification only by the reduced pressure distillation method by boiling, even for low boiling point substances that can be removed by the reduced pressure distillation method, it is equal or less, further, high boiling point substances and ionic substances, Alternatively, substances that are very difficult to remove by the vacuum distillation method, such as substances that are easily dissolved in polymer fine particles, can be highly purified similarly to low-boiling substances.

The organic solvent solution of the copolymer after the above-described purification is first added with a neutralizing agent if necessary to ionize the salt-forming groups, and then water is added, followed by addition of the organic solvent. By distilling off part or all of the solvent and inversion into an aqueous system, an aqueous dispersion of self-dispersing polymer particles used in the present invention can be obtained. At this time, a known acid or base may be used as the neutralizing agent depending on the type of the salt-forming group. Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid, propionic acid, lactic acid, succinic acid and glycolic acid. Further, as the base, for example, trimethylamine,
Examples thereof include tertiary amines such as triethylamine, ammonia, sodium hydroxide, potassium hydroxide and the like, but are not limited to the above. Further, after the water is added, the above-mentioned purification treatment is carried out, and then a part or all of the organic solvent is distilled off to invert the phase into an aqueous system to disperse the self-dispersible polymer particles in the present invention in water. A liquid can be obtained.

The particle diameter of the self-dispersing polymer particles used in the present invention, which are uniform and have excellent mechanical and storage stability, is not particularly limited, but is preferably 10 to 10.
It is in the range of 1000 nm, and more preferably in the range of 10 to 300 nm.

Next, the formulation of film-forming cosmetics, particularly peel-off type pack cosmetics, using the above-mentioned water-based resin emulsion or an aqueous dispersion of self-dispersing polymer particles as a main film-forming agent will be described. The amount of the emulsion or self-water-dispersible polymer particles to be compounded is 10 to 60% by weight in terms of polymer solid content. Ten
When it is less than 60% by weight, it is difficult to obtain a film thickness that gives practically necessary strength, and when it exceeds 60% by weight, the viscosity of the pack cosmetic increases and the coating property deteriorates. To do. Further, the amount of the water-based resin emulsion or self-dispersion type polymer fine particles is preferably 25 to 60% by weight
With the above, it is possible to obtain a pack cosmetic having a high drying property, which is not present in pack cosmetics using a conventional water-soluble polymer.

The film-forming cosmetic of the present invention contains various medicinal ingredients which have been widely used in the cosmetics industry, moisturizers, oils, fragrances, colorants, dispersants, preservatives, preservatives and the like. It is possible to appropriately mix various additives, and further, other additives may be added as required. The film-forming cosmetic of the present invention, for hair, skin or medicated cosmetics, in addition to pack cosmetics, eye shadow,
Eye makeup cosmetics such as mascara and eyeliner,
It can be used for eyebrows, hair coloring agents, nail enamel and the like.

[0026]

EXAMPLES The present invention will be specifically described below with reference to synthesis examples and comparative synthesis examples of an aqueous resin emulsion of the present invention, an aqueous dispersion of self-dispersible polymer particles, and examples and comparative examples of film-forming cosmetics. As described, the present invention is not limited to these.

Synthesis Example 1 150 parts by weight of water, 0.5 parts by weight of ammonium persulfate and 2.0 parts of sodium polyoxyethylene lauryl ether sulfate as an emulsifier were placed in a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing tube. Part by weight was charged and nitrogen gas replacement was performed. On the other hand, 43.7 parts by weight of Nt-butylacrylamide, 38.5 parts by weight of n-butyl acrylate, 8.6 parts by weight of ethyl acrylate and 9.2 parts by weight of acrylic acid were charged in the dropping funnel as the polymerizable unsaturated monomer. Under a nitrogen atmosphere, the mixed solution in the reactor was heated to 70 ° C. with stirring, the mixed solution in the dropping funnel was gradually added dropwise over 3 hours, and the copolymer was aged at 70 ° C. for 3 hours. An aqueous dispersion of was obtained. After purification using a steam distillation method, the mixture was further heated under reduced pressure and concentrated to obtain an aqueous resin emulsion having a polymer solid content concentration of 40% by weight.

Synthetic Example 2 Under the same conditions as in Synthetic Example 1, as a polymerizable unsaturated monomer,
An aqueous resin emulsion was prepared by using 40.3 parts by weight of N- (1,1-dimethyl-3-oxobutyl) acrylamide, 29.5 parts by weight of n-butyl acrylate, 10.6 parts by weight of 2-ethylhexyl acrylate and 19.6 parts by weight of methyl methacrylate. Obtained.

Synthesis Example 3 150 parts by weight of water and partially saponified polyvinyl alcohol were placed in a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer.
1 part by weight (EG-30, manufactured by Nippon Gosei Co., Ltd.) was charged. Separately, 40.0 parts by weight of glucosylethyl methacrylate (manufactured by Nippon Seika Co., Ltd.) represented by the following formula (1), 2-methacrylic acid 2-
Hydroxyethyl 10.0 parts by weight, n-butyl acrylate 3
A solution consisting of 0.0 parts by weight, 20.0 parts by weight of 2-ethylhexyl acrylate, and 0.3 parts by weight of lauroyl peroxide was prepared and added to the above reactor to prepare a suspension with a homogenizer. Next, the suspension in the reactor was heated to 70 ° C. with stirring, reacted for 5 hours, and then purified in the same manner as in Synthesis Example 1,
By concentrating, an aqueous resin emulsion having a polymer solid content concentration of 40% by weight was obtained.

[0030]

[Chemical 1]

Synthesis Example 4 In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 500 parts by weight of water, 100 parts by weight of ethanol, 2 parts by weight of polyvinylpyrrolidone, 10 parts by weight of acrylic acid, N-
(2,2,2-Trishydroxymethyl) ethyl methacrylamide 30 parts by weight, 3-oxa-5-hydroxypentyl methacrylate 60 parts by weight, 2,2'-azobis (isobutyronitrile) 0.5 parts by weight, The mixture in the reactor was heated to 70 ° C. with stirring, reacted for 5 hours, then purified and concentrated in the same manner as in Synthesis Example 1 to obtain an aqueous resin emulsion having a polymer solid content concentration of 40% by weight. ..

Comparative Synthesis Example 1 Under the same conditions as in Synthesis Example 1, as the polymerizable unsaturated monomer, 28 parts by weight of methyl methacrylate, 25.5 parts by weight of n-butyl acrylate, 25.1 parts by weight of ethyl acrylate and 10.9 of acrylic acid were used. Parts by weight, 2-hydroxyethyl methacrylate 10.5
An aqueous resin emulsion was obtained using parts by weight.

Synthesis Example 5 In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube, 75 parts by weight of acetone as a polymerization solvent and Nt-as a polymerizable unsaturated monomer. Butylacrylamide 21.9 parts by weight, n-butyl acrylate 19.2 parts by weight, ethyl acrylate 4.3 parts by weight, acrylic acid 4.6 parts by weight, 2,2'-azobisisobutyronitrile as an initiator
0.34 parts by weight was charged and the nitrogen gas was replaced. On the other hand, in the dropping funnel, a mixed solution having exactly the same composition and the same amount as in the reactor was charged after sufficiently purging with nitrogen. Under a nitrogen atmosphere, the mixed solution in the reactor was heated to 80 ° C. with stirring, and the mixed solution in the dropping funnel was gradually added dropwise over 2 hours. Three hours after the completion of dropping, 0.68 parts by weight of 2,2'-azoisobutyronitrile was added, and the mixture was aged for 5 hours at 80 ° C to obtain a copolymer.

The copolymer solution is cooled to room temperature, and acetone is added.
The product diluted by adding 200 parts by weight was purified by the ultrafiltration method using a ceramic filtration device manufactured by Toshiba Ceramics Co., Ltd. At this time, acetone was used as a solvent to be added appropriately. After stirring, 74.5 parts by weight of 1 N sodium hydroxide was added to the purified copolymer solution to partially neutralize the salt-forming groups in the copolymer, and 400 parts by weight of deionized water was added. Acetone was completely distilled off at 70 ° C. under reduced pressure.
Concentration was carried out by distilling off some of the water to obtain an aqueous dispersion of self-dispersing polymer particles having a polymer solid content concentration of 40% by weight.

Synthesis Example 6 In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube, 30 parts by weight of methyl ethyl ketone as a polymerization solvent and N- (1, as a polymerizable unsaturated monomer) were used. 1-dimethyl-3-oxobutyl) acrylamide 36.0 parts by weight,
5.8 parts by weight of n-butyl acrylate, 6.7 parts by weight of 2-ethylhexyl acrylate, 1.5 parts by weight of dimethylaminopropylacrylamide, 2,2'-as a radical polymerization initiator
0.03 parts by weight of azobisisobutyronitrile was charged, and the atmosphere was replaced with nitrogen gas. On the other hand, a mixed solution having the same composition and the same amount as in the reactor was charged in the dropping funnel after the nitrogen substitution was sufficiently performed. Under a nitrogen atmosphere, the mixed solution in the reactor was heated to 80 ° C. with stirring, and the mixed solution in the dropping funnel was gradually added dropwise over 2 hours. Three hours after the completion of the dropping, a solution prepared by dissolving 0.03 parts by weight of 2,2'-azobisisobutyronitrile in 5 parts by weight of methyl ethyl ketone was added and further aged at 80 ° C for 5 hours to obtain a copolymer. The copolymer solution was cooled to room temperature, added with 200 parts by weight of methyl ethyl ketone and diluted, and purified by an ultrafiltration method using a ceramics filtration device manufactured by Toshiba Ceramics Corporation. While stirring, 12.2 parts by weight of 1N hydrochloric acid was added to the purified copolymer solution to partially neutralize the salt-forming groups in the copolymer, and 400 parts by weight of ion-exchanged water was added, and the pressure was reduced. under
Methyl ethyl ketone was completely removed at 70 ° C., and a part of water was distilled off to concentrate to obtain an aqueous dispersion of self-dispersing polymer particles having a polymer solid content concentration of 40% by weight.

Synthesis Example 7 In Synthesis Example 6, as the polymerizable unsaturated monomer, N- (1,1
-Dimethyl-3-oxobutyl) acrylamide 29.1 parts by weight, n-butyl acrylate 18.4 parts by weight, acrylic acid
A copolymer was obtained by using 2.5 parts by weight and otherwise following the formulation shown in Synthesis Example 6. The obtained copolymer was further purified by the ultrafiltration method in exactly the same manner as in Synthesis Example 6. To the purified copolymer solution, 24.4 parts by weight of 1N sodium hydroxide was added with stirring to partially neutralize the salt-forming groups in the copolymer, and then the aqueous system was prepared according to the prescription of Synthesis Example 6. By carrying out phase inversion and concentration, an aqueous dispersion of self-dispersible polymer particles having a polymer solid content concentration of 40% by weight was obtained.

Synthesis Example 8 In Synthesis Example 5, methyl ethyl ketone was used as a polymerization solvent.
50 parts by weight, methyl methacrylate 19.8 parts by weight as polymerizable unsaturated monomer, n-butyl acrylate 12.6 parts by weight, ethyl acrylate 12.3 parts by weight, acrylic acid 5.3 parts by weight, radical polymerization initiator 2,2 ' A copolymer was obtained in the same manner as in Synthesis Example 5, except that 0.05 parts by weight of azobisisobutyronitrile was used. About the obtained copolymer solution, using methyl ethyl ketone as a solvent to be appropriately added, Synthesis Example 5
Purification by the ultrafiltration method was performed according to the prescription. After stirring, 82 parts by weight of 1N sodium hydroxide was added to the purified copolymer solution to partially neutralize the salt-forming groups in the copolymer, and 400 parts by weight of deionized water was added. Completely distilling off methyl ethyl ketone at 70 ° C. under reduced pressure and further distilling off some of the water to concentrate to obtain an aqueous dispersion of self-dispersing polymer particles having a polymer solid content concentration of 40% by weight. ..

Synthesis Example 9 In Synthesis Example 5, 75 parts by weight of acetone as a polymerization solvent, 15.8 parts by weight of ethyl methacrylate as a polymerizable unsaturated monomer, and 1 part of ethyl acrylate were placed in a reactor and a dropping funnel.
7.9 parts by weight, methacrylic acid 7.2 parts by weight, compound represented by the following formula (2) (trade name NK-M230G, manufactured by Shin-Nakamura Chemical Co., Ltd.)
A copolymer was obtained in the same manner as in Synthesis Example 5 except that 9.1 parts by weight, 0.15 parts by weight of 2,2′-azobisisobutyronitrile as a radical polymerization initiator were used. The obtained copolymer solution was purified by the ultrafiltration method according to Synthesis Example 5 using acetone as a solvent to be added as appropriate. After stirring, 8.4 parts by weight of 1N sodium hydroxide was added to the purified copolymer solution to partially neutralize the salt-forming groups in the copolymer, and 400 parts by weight of deionized water was added. 70 ° C under reduced pressure
Then, acetone was completely distilled off, and a part of water was distilled off to concentrate the solution to obtain an aqueous dispersion of self-dispersing polymer particles having a polymer solid content concentration of 40% by weight.

[0039]

[Chemical 2]

Synthetic Example 10 The copolymer obtained by carrying out the solution polymerization according to Synthetic Example 6 was diluted by adding 200 parts by weight of methyl ethyl ketone and then diluted without further purification by the ultrafiltration method. By performing neutralization, phase inversion to an aqueous system, and concentration according to the formulation of 1., an aqueous dispersion liquid of phase inversion type self-dispersing polymer particles having a polymer solid content concentration of 40% by weight was obtained.

Comparative Synthesis Example 2 50 parts by weight of isopropyl alcohol was used in place of 30 parts by weight of methyl ethyl ketone as a polymerization solvent at the time of solution polymerization and as a diluting solvent after completion of the reaction, and a radical initiator.
0.03 parts by weight of 2,2'-azobisisobutyronitrile to 0.
The amount was changed to 06 parts by weight, and otherwise the same formulation as in Synthesis Example 7 was followed to obtain an aqueous dispersion of self-dispersing polymer particles having a polymer solid content concentration of 40% by weight.

Regarding the water-based resin emulsions obtained in Synthesis Examples 1 to 10 and Comparative Synthesis Examples 1 and 2, the weight average molecular weight of the polymer, the particle size, and the tensile strength of the film obtained by forming the water-based resin emulsion are shown below. It was measured by the method. The results are shown in Table 1. -Measurement method of weight average molecular weight The polymer was dried under reduced pressure at 105 ° C for 2 hours, and measured by gel permeation chromatography using polystyrene as a standard substance and tetrahydrofuran as a solvent. -Measurement method of particle diameter It was measured by a particle size measuring device N4 manufactured by Coulter.

Method for measuring tensile strength A high-performance film manufactured by Orientec Co., Ltd. was used for a film having a thickness of 0.05 ± 0.01 mm obtained by applying an aqueous resin emulsion on release paper and then drying it at room temperature for about 8 hours. It was measured using a universal material testing machine (TENSILON UCT-100).

[0044]

[Table 1]

Examples 1 to 10 and Comparative Examples 1 to 2 Peel-off type pack cosmetics using the water-based resin emulsions obtained in the above Synthetic Examples 1 to 10 and Comparative Synthetic Examples 1 and 2 as film forming agents are described below. It manufactured according to the manufacturing method and compounding recipe example of this, and compared about various performances. The manufacturing method is the polymer aqueous dispersion shown in the formulation example of Table 2, 1,3
-Butylene glycol and components other than Carbopol 940 are stirred with a homomixer while heating to 70 ° C to form a uniform solution. Add to this the Carbopol 94 at 70 ° C with stirring.
0 was added to disperse, and the polymer aqueous dispersion and 1,3
-Butylene glycol was added and mixed well, then cooled to room temperature and deaerated to obtain pack cosmetics of Examples 1-10 and Comparative Examples 1-2.

[0046]

[Table 2]

Note) * 1: Carboxyvinyl polymer * 2: Sorbitan monostearate (nonionic surfactant) * 3: Polyoxyethylene sorbitan monostearate (nonionic surfactant) * 4: Myristic acid- Diglyceride isostearic acid * 5: Polyoxyethylene hydrogenated castor oil (nonionic surfactant) Various physical properties of the pack cosmetics obtained in Examples 1 to 10 and Comparative Examples 1 and 2 were evaluated by the following methods. .. In addition, the physical properties of commercially available pack cosmetics using partially saponified polyvinyl alcohol as a film forming agent were also evaluated. The results are shown in Table 3.

Evaluation Method (1) Drying Property A sample is applied on the skin at room temperature of 25 ° C. and a relative humidity of 60%, and then the time required for forming a peelable film is measured. ○: Within 10 minutes, △: 10 to 20 minutes, ×: 20 minutes or more (2) Stability After allowing the sample to stand for 30 days at room temperature of 35 ° C and relative humidity of 60%, the dispersed state, color, odor, Evaluate changes in pH, etc. and the presence or absence of decomposed products. (3) Peelability A sample formed by applying the sample on the skin at room temperature of 25 ° C and a relative humidity of 60% and then drying for 10 minutes is peeled off from the skin for evaluation. (4) Odorless property Sensory evaluation of the odor of the sample before drying. (5) Applicability When the sample is applied on the skin, the feel (stickiness, body weight,
Sensory evaluation of dripping etc.) With respect to the above evaluation items (2) to (5), the evaluation results were judged as follows.

◎: extremely good, ○: good, △: normal,
×: defective

[0050]

[Table 3]

As is clear from Table 3, the peel-off type pack cosmetic according to the present invention exhibits satisfactory performance in each required physical property.

[0052]

From the aqueous resin emulsion containing the polymerizable unsaturated monomer selected from the group consisting of the hydrogen-bonding monomer and the polymerizable unsaturated monomer having a salt-forming group according to the present invention as a constituent unit. The resulting film is considered to have hydrogen bonds formed between the polymers in the film, and has higher strength than ordinary water-based resin emulsions, and can be used as a film forming agent for film-forming cosmetics such as packs. It is possible. Also, the film of the self-dispersing polymer particles according to the present invention has higher strength than ordinary water-based resin emulsions, and thus can be used as a film-forming agent for film-forming cosmetics such as packs. This is because in general, in an aqueous resin emulsion, fusion between particles is insufficient, but self-dispersion type polymer fine particles do not use an emulsifier or protective colloid, and since the particle size is small, fusion between particles is sufficient. It is considered that this is because the film progresses and a uniform film is formed. Furthermore, from the self-dispersing polymer fine particles containing a hydrogen-bonding monomer as a constituent component, the above two effects are combined, so that a very tough film is obtained. In addition, since self-dispersing polymer particles can be purified by ultrafiltration, it is possible to highly improve substances such as low-boiling substances such as residual monomers, high-boiling substances and ionic substances, or substances that are easily dissolved in polymer fine particles. It can be purified and is advantageous in terms of odor and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Kondo 1-2-27 Sekido, Wakayama City (72) Inventor Hiroshi Yagi 2-8-20 Chuo, Miyashiro-cho, Minamisaitama-gun, Saitama B-203

Claims (9)

[Claims] 1. One or more selected from the group consisting of a polymerizable unsaturated monomer having a group capable of forming a hydrogen bond (excluding a salt-forming group) and a polymerizable unsaturated monomer having a salt-forming group, or Two
30% by weight of one or more polymerizable unsaturated monomers as constitutional units
A film-forming cosmetic, comprising an aqueous resin emulsion containing a resin having a weight-average molecular weight of 30,000 or more as a film-forming agent. 2. The film-forming cosmetic according to claim 1, wherein the polymerizable unsaturated monomer having a group capable of forming a hydrogen bond (excluding a salt-forming group) is a (meth) acrylamide monomer. 3. The (meth) acrylamide monomer is N
The film-forming cosmetic according to claim 2, which is-(1,1-dimethyl-3-oxobutyl) acrylamide. 4. A copolymer having a weight average molecular weight of 30,000 or more obtained by copolymerizing a polymerizable unsaturated monomer mixture containing 0.5 to 70 mol% of at least one polymerizable unsaturated monomer having a salt-forming group. An organic solvent solution of a polymer is purified by adding water, or water is added and then purified, which is obtained by distilling off the organic solvent. An aqueous dispersion of self-dispersing polymer particles is used as a film forming agent. A film-forming cosmetic composition characterized by being blended. 5. A polymerizable unsaturated monomer having 0.5-70 mol% of at least one polymerizable unsaturated monomer having a salt-forming group and a group capable of forming a hydrogen bond (excluding the salt-forming group). Of an organic solvent solution of a copolymer having a weight average molecular weight of 30,000 or more obtained by copolymerizing a polymerizable unsaturated monomer mixture containing 30 to 99% by weight of water, or water is added after purification, or water is added. A film-forming cosmetic composition comprising an aqueous dispersion of self-dispersing polymer particles, obtained by distilling off an organic solvent after purification, as a film-forming agent. 6. The film-forming cosmetic according to claim 5, wherein the polymerizable unsaturated monomer having a group capable of forming a hydrogen bond (excluding a salt-forming group) is a (meth) acrylamide monomer. 7. The (meth) in the polymerizable unsaturated monomer mixture.
The film-forming cosmetic composition according to claim 6, wherein the content of the acrylamide monomer is 30 to 99.5 mol%. 8. A (meth) acrylamide-based monomer,
The film-forming cosmetic according to claim 6, which is N- (1,1-dimethyl-3-oxobutyl) acrylamide. 9. The film-forming cosmetic according to claim 1, wherein the film-forming cosmetic is a pack cosmetic.