KR102244920B1 - Polymer composition - Google Patents

Abstract

The present application relates to a polymer composition, a film-forming agent, a cosmetic composition, or a method for preparing the polymer composition. The present application is to provide the polymer composition that can form cosmetics, etc. that have excellent oil resistance, do not smear, do not cause powder falling or the like during use, and a film-forming agent, cosmetics or the like prepared by using the same.

Description

Polymer composition {POLYMER COMPOSITION}

The present application relates to a method of manufacturing a polymer composition, a film former, a cosmetic composition, or a polymer composition.

Functional polymers are sometimes required for the manufacture of cosmetics or pharmaceuticals. For example, functional polymers are required in the manufacture of cosmetics such as mascara, or other cosmetics or pharmaceuticals applied to the skin.

These functional polymers are required to have oil resistance, which is resistance to oily components such as sebum, and in some cases, appropriate coating properties or film-forming ability may be required.

In the functional polymer, it may be required that there is no bleeding caused by sebum, tears, sweat, etc. during the use of cosmetics or pharmaceuticals, and that the phenomenon of falling into powder does not occur.

Since cosmetics and medicines are often used in direct contact with the human body, they should not contain harmful substances.

The present application provides a polymer composition, a film forming agent, a cosmetic composition, or a method of manufacturing a polymer composition. The object of the present application is to provide a polymer composition capable of forming cosmetics, etc., which have excellent oil resistance and do not bleed or fall off during use, and a film forming agent or cosmetics prepared using the same.

In the present application, the term polymer composition may include only a polymer to be described later, or may include a polymer and other components to be described later.

The polymer included in the polymer composition includes a polymerized unit of a specific type of monomer, and the ratio of the polymerized unit may be adjusted. Through the control of the type and ratio of these monomers, it is possible to obtain a polymer composition capable of forming a film forming agent, cosmetics, or pharmaceuticals, etc., which prevents the desired physical properties such as oil resistance or bleeding or powder falling off during use.

The ratio (for example, weight% or parts by weight, etc.) to a monomer mentioned in the present specification is the ratio of the monomer applied at the time of manufacture of the polymer, or the ratio of the polymerized units of the monomer included in the polymer. It can mean.

For example, the polymer solubility parameter is 11 (cal / cm ³⁾ a polymerization unit of the solubility parameter of the first monomer 11 or ^1/2 (cal / cm ³⁾ is less than ^one-half comprises polymerized units of second monomer can do.

In the present specification, the polymerization unit of a monomer or compound refers to a form in which the monomer or compound is included as a monomer unit in a polymer through a polymerization reaction.

The term solubility parameter refers to a solubility parameter of a homopolymer prepared by polymerizing a corresponding monomer, and through this, the degree of hydrophilicity and hydrophobicity of the corresponding monomer can be determined. The method of obtaining the solubility parameter is not particularly limited, and a method known in the art may be followed. For example, the solubility parameter can be calculated or determined according to a method known in the art as the so-called Method of Hoftyzer and Van Krevelen of Group contribution.

The first monomer is a monomer having relatively hydrophilicity compared to the second monomer, and this may contribute to securing the desired oil resistance. The solubility parameter of the first monomer is 11.5 (cal/cm ³ ) ^1/2 or more, 12 (cal/cm ³ ) ^1/2 or more, 12.5 (cal/cm ³ ) ^1/2 or more, 13 ( cal/cm ³ ) ^1/2 or more, 13.5 (cal/cm ³ ) ^1/2 or more, or 14 (cal/cm ³ ) ^1/2 or more, or 20 (cal/cm ³ ) ^1/2 or less, 19 (cal /cm ³ ) ^1/2 or less, 18 (cal/cm ³ ) ^1/2 or less, 17 (cal/cm ³ ) ^1/2 or less, 16 (cal/cm ³ ) ^1/2 or less, 15 (cal/cm) ³ ) ^1/2 or less, 14 (cal/cm ³ ) ^1/2 or less, or 13 (cal/cm ³ ) ^1/2 or less.

As the first monomer, a monomer appropriately selected from among monomers known to have the above-described solubility parameter may be used.

For example, as the first monomer, a hydroxy group-containing monomer such as 2-hydroxyalkyl (meth)acrylate; Polymerizable heterocyclic monomers such as vinyl pyrrolidone and the like; (Meth)acrylamide-based monomers such as (meth)acrylamide, N-alkyl (meth)acrylamide or N,N-dialkyl (meth)acrylamide; Acidic monomers such as (meth)acrylic acid, maleic acid or itaconic acid; Glyceryl (meth)acrylate; Alternatively, a monomer including an alkylene oxide unit may be used.

In the present specification, the term (meth)acrylic means acrylic or methacrylic.

In the present specification, the term alkyl or alkyl group, unless otherwise specified, is a straight chain, branched or cyclic alkyl having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, or It means an alkyl group.

In the above, the alkylene oxide unit-containing monomer may be, for example, a monomer represented by Formula 1 or 2 below.

[Formula 1]

In Formula 1, Q is hydrogen or an alkyl group, U is an alkylene group, Z is hydrogen or an alkyl group, and m is an arbitrary number:

[Formula 2]

In Formula 2, Q is hydrogen or an alkyl group, A and U are each independently an alkylene group, X is a hydroxy group or a cyano group, and n is an arbitrary number.

As the alkylene group in Formulas 1 and 2, an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms may be exemplified. The alkylene group may be linear, branched or cyclic. The alkyl group may be optionally substituted with one or more substituents.

As the alkyl group present in Q and Z in Formulas 1 and 2, an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms may be exemplified. The alkyl group may be linear, branched or cyclic. In addition, the alkyl group may be optionally substituted with one or more substituents.

In Formulas 1 and 2, m and n are arbitrary numbers, for example, each independently 1 to 100, 1 to 90, 1 to 80, 1 to 70, 1 to 60, 1 to 50, 1 to 40, 1 It may be a number in the range of to 30, 1 to 20, 1 to 16, or 1 to 12.

In one example, as the first monomer, in Formula 1, Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, U is an alkylene group having 1 to 4 carbon atoms, Z is hydrogen or an alkyl group having 1 to 4 carbon atoms, and m A compound of about 1 to 30 may be used, but is not limited thereto.

In the polymer, the ratio of the polymerized unit of the first monomer as described above may be controlled in consideration of target physical properties, for example, oil resistance, and the like.

For example, the ratio of the polymerized units of the one monomer in the total polymerized units included in the polymer may be about 4 to 40% by weight. In another example, the ratio is 4.5% by weight or more, 5% by weight or more, 5.5% by weight or more, 6% by weight or more, 6.5% by weight or more, 7% by weight or more, 7.5% by weight or more, 8% by weight or more, 8.5% by weight or more , 9% by weight or more, 9.5% by weight or more, 10% by weight or more, 11% by weight or more, 12% by weight or more, 13% by weight or more, 14% by weight or more, or about 14.5% by weight or more, or 39% by weight or less, 38% by weight % Or less, 37% by weight or less, 36% by weight or less, 35% by weight or less, 34% by weight or less, 33% by weight or less, 32% by weight or less, 31% by weight or less, 30% by weight or less, 29% by weight or less, 28% by weight % Or less, 27% by weight or less, 26% by weight or less, 25% by weight or less, 24% by weight or less, 23% by weight or less, 22% by weight or less, 21% by weight or less, 20% by weight or less, 19% by weight or less, 18% by weight % Or less, 17 wt% or less, 16 wt% or less, or 15 wt% or less. It is possible to provide a polymer composition or the like having desired physical properties under such a ratio. For example, as the ratio of the polymerized units of the first monomer increases, it may be advantageous in terms of the aforementioned oil resistance. However, since the first monomer is a relatively hydrophilic monomer, it is not easy to include the first monomer in the polymer at an appropriate level because, for example, it exhibits a thickening effect in the emulsion polymerization process in an aqueous solvent. However, according to the method described later in the present application, a polymer composition including a polymer having a relatively high ratio of the first monomer can be efficiently prepared.

The second monomer is a monomer having relatively hydrophobicity compared to the first monomer. The solubility parameter of the second monomer is 10.5 (cal/cm ³ ) ^1/2 or less or 10 (cal/cm ³ ) ^1/2 or less, or 4 (cal/cm ³ ) ^1/2 or more, 5 (cal/cm ³ ) ^1/2 or more, 6 (cal/cm ³ ) ^1/2 or more, 7 (cal/cm ³ ) ^1/2 or more, 8 (cal/cm ³ ) ^1/2 or more, 8.5 (cal /cm ³ ) ^1/2 or more, 9 (cal/cm ³ ) ^1/2 or more, or 9.5 (cal/cm ³ ) ^1/2 or more.

As the second monomer, a monomer appropriately selected from among monomers known to have the above-described solubility parameter may be used. These second monomers are included in the polymer together with the first monomer, and may contribute to forming a film forming agent, cosmetics, or pharmaceuticals without powder dropping or bleeding while securing oil resistance.

As a monomer that can be used as the second monomer, an alkyl (meth)acrylate or an aromatic (meth)acrylate may be exemplified. In the present application, the term (meth)acrylate may mean acrylate or methacrylate.

As the alkyl group contained in the alkyl (meth)acrylate, a straight, branched or cyclic alkyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, or 2 to 8 carbon atoms may be exemplified, and the The alkyl group may be optionally substituted with one or more substituents. As such monomers, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (Meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isobornyl (meth)acrylate , Isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and the like may be exemplified, but are not limited thereto.

As the aromatic (meth)acrylate, an aryl (meth)acrylate or an arylalkyl (meth)acrylate may be exemplified. In the above, the aryl group of the aryl or arylalkyl may be, for example, an aryl group having 6 to 24 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. In addition, the alkyl group of the arylalkyl may be, for example, an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. In the above, the alkyl group may be linear, branched or cyclic, and the alkyl group or aryl group may be optionally substituted with one or more substituents.

Examples of the aryl group or arylalkyl group include a phenyl group, a phenylethyl group, a phenylpropyl group, or a naphthyl group, but are not limited thereto.

As the second monomer, for example, a monomer represented by Formula 3 below may be used.

[Formula 3]

In Formula 3, Q may be hydrogen or an alkyl group, and B may be a C2 or more linear or branched alkyl group or an alicyclic hydrocarbon group, or an aromatic substituent such as the aryl group or an arylalkyl group.

As the alkyl group present in Q in Formula 3, an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms may be exemplified. The alkyl group may be linear, branched or cyclic. The alkyl group may be optionally substituted with one or more substituents.

In Formula 3, B may be a linear or branched alkyl group having 2 or more carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, or 2 to 10 carbon atoms.

In another example, B in Formula 3 may be an alicyclic hydrocarbon group, for example, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, or 6 to 12 carbon atoms, and examples of such a hydrocarbon group include a cyclohexyl group or An alicyclic alkyl group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, or 6 to 12 carbon atoms such as an isobornyl group may be exemplified. Compounds having an alicyclic hydrocarbon group as described above are also known as relatively hydrophobic compounds.

In order to secure the desired physical properties, a mixture of at least two or more types of monomers may be used as the second monomer.

For example, as the second monomer, a monomer (A) having a relatively high glass transition temperature (hereinafter, Tg) and a monomer (B) having a relatively low Tg may be used. Thus, for example, the polymer may include, as the second monomer polymerization unit, a monomer (A) polymerization unit having a Tg of 20°C or higher and a monomer (B) polymerization unit having a Tg of less than 20°C.

The Tg of a monomer referred to in the present specification is a known Tg for a homopolymer made of the monomer.

In another example, the Tg of the monomer (A) is 25°C or more, 30°C or more, 35°C or more, 40°C or more, 45°C or more, 50°C or more, 55°C or more, or 60°C or more, or 150°C or less, 145°C Or less, 140°C or less, 135°C or less, 130°C or less, 125°C or less, 120°C or less, 115°C or less, 110°C or less, 105°C or less, 100°C or less, 95°C or less, 90°C or less, 85°C or less, It may be about 80°C or less, 75°C or less, or 70°C or less, and the Tg of the monomer (B) is 15°C or less, 10°C or less, 5°C or less, 0°C or less, -5°C or less, -10°C or less in other examples. , -15℃ or less, -20℃ or less, -25℃ or less, -30℃ or less, -35℃ or less, -40℃ or less or -45℃ or less, -150℃ or more, -145℃ or more, -140℃ -135℃ or more, -130℃ or more, -125℃ or more, -120℃ or more, -115℃ or more, -110℃ or more, -105℃ or more, -100℃ or more, -95℃ or more, -90℃ It may be above, -85°C or higher, -80°C or higher, -75°C or higher, -70°C or higher, -65°C or higher, -60°C or higher, or -55°C or higher.

As the second monomer, when a mixture of two types of monomers is applied as described above, the Tg of the overall polymer can be maintained at an appropriate level, and other desired properties along with oil resistance (e.g., prevention of bleeding or powder falling off) It is advantageous to form a polymer having both.

As the monomer (A) and the monomer (B), an appropriate type may be selected in consideration of the Tg of the corresponding monomer from among the above-described monomers mentioned as the second monomer.

For example, as the monomer (A), in Formula 3, Q is an alkyl group, for example, an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, or , A methyl group, and B may be a straight-chain or branched alkyl group having 2 or more carbon atoms. In this case, the alkyl group of B may be a linear or branched alkyl group having 2 to 4 carbon atoms.

For example, as the monomer (B), in Formula 3, Q is hydrogen, and B may be a compound having 2 or more carbon atoms, 4 or more carbon atoms, or a straight or branched chain alkyl group having 6 or more carbon atoms. In this case, the upper limit of the number of carbon atoms of the alkyl group of B is not particularly limited, and may be, for example, about 20, 18, 16, 14, 12 or 10.

The ratio of the second monomeric polymerization unit in the polymer may be in the range of 150 to 2400 parts by weight based on 100 parts by weight of the first monomeric polymerization unit. In another example, the ratio is about 200 parts by weight or more, 250 parts by weight or more, 300 parts by weight or more, 350 parts by weight or more, 400 parts by weight or more, 450 parts by weight or more, 500 parts by weight or more, or 550 parts by weight or more, or 2350 parts by weight. It may be about parts by weight or less, 2300 parts by weight or less, 2250 parts by weight or less, 2200 parts by weight or less, 2150 parts by weight or less, 2100 parts by weight or less, 2050 parts by weight or less, 2000 parts by weight or less, or 1950 parts by weight or less.

On the other hand, as the polymerization unit of the second monomer, when the monomer (A) and the monomer (B) are applied, the weight ratio (A/B) of the polymerization unit of the monomer (A) and the polymerization unit of the monomer (B) is 0.25 It may be in the range of to 3. The weight ratio (A/B) is, in another example, about 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, 0.5 or more, 0.55 or more, 0.6 or more, 0.65 or more, 0.7 or more, 0.75 or more, 0.8 or more, 0.85 or more, It may be 0.9 or more, 0.95 or more, 1.0 or more, 1.5 or more, or 2 or more, 2.5 or less, 2 or less, 1.5 or less, 1 or less, 0.95 or less, 0.9 or less, 0.85 or less, 0.8 or less, 0.75 or less, or 0.7 or less.

In addition to the above-described first and second monomers, the polymer may appropriately contain known additional monomers within a range that does not impair desired physical properties.

Tg of the polymer of the present application as described above, for example, may be in the range of about -30 ℃ to 30 ℃. In another example, the Tg of the polymer is about -25°C or more, -20°C or more, -15°C or more, or -10°C or more, or about 25°C or less, 20°C or less, 15°C or less, 10°C or less, 5°C Hereinafter, it may be about 0°C or less or -5°C or less. The Tg is a theoretical value obtained from the monomer composition of the polymer through a so-called Fox equation. The Tg is a theoretical value obtained from the monomer composition of the polymer through a so-called Fox equation. Tg as described above may be useful, for example, when the polymer is applied as a film forming agent for cosmetics or pharmaceuticals. By using the polymer in the range of the Tg, it may be possible to efficiently form a film having excellent oil resistance without stickiness, bleeding or cracking.

In the present application, the polymer may have a weight average molecular weight (Mw) in the range of 100,000 to 2 million. In the present application, the weight average molecular weight may be, for example, a value converted to standard polystyrene measured using GPC (Gel Permeation Chromatograph), and unless otherwise specified, the term molecular weight may refer to the weight average molecular weight. have. The molecular weight (Mw) as described above may be useful, for example, when the polymer is applied as a film forming agent. By using the polymer within the range of the molecular weight (Mw), it may be possible to efficiently form a film having excellent oil resistance without stickiness, bleeding or cracking.

In another example, the molecular weight (Mw) is 150,000 or more, 200,000 or more, 250,000 or more, 300,000 or more, 350,000 or more, 400,000 or more, 450,000 or more or 500,000 or more, 1.9 million or less, 1.8 million or less, It may be 1.7 million or less, 1.6 million or less, 1.5 million or less, 1.4 million or less, 1.3 million or less, 1.2 million or less, 1.1 million or less, 1 million or less, 900,000 or less, 800,000 or less, or 700,000 or less.

The polymer composition of the present application including the polymer as described above does not contain methanol or may contain a minimum amount of methanol. For example, the methanol content of the polymer composition is about 30 ppm or less, 25 ppm or less, 20 ppm or less, 15 ppm or less, 10 ppm or less, 5 ppm or less, 4 ppm or less, 3 ppm or less, 2 ppm or less, 1 ppm It may be less than or about 0.5 ppm or less. That is, in polymers known for producing film forming agents, etc., the type or ratio of monomers is controlled in order to control Tg, etc., and among monomers known as such monomers, methanol is produced by hydrolysis or the like. For example, methyl (meth)acrylate is very frequently applied to control Tg in the production of a polymer forming a film-forming agent, but it generates methanol by hydrolysis or the like. Fished methanol produces formaldehyde, which is a typical harmful substance in polymer compositions or film-forming agents, or in cosmetics and pharmaceuticals. However, in the case of the present application, a monomer that generates methanol among the monomers forming a polymer is not used, or the ratio thereof is minimized so that methanol is not included, or a polymer composition, film-forming agent, cosmetics, or pharmaceuticals containing the monomer is minimized. Can provide. However, since the monomer that generates methanol is a monomer that is known to be very effective in controlling physical properties such as Tg of a polymer, it is not easy to meet the target physical properties without applying such a monomer. However, in the present application, it is possible to provide a polymer composition that does not contain or contains a small amount of methanol and has desired physical properties through the use of the above-described types of first and second monomers, monomers (A) and monomers (B). have. Since it is most appropriate that methanol is not included in the polymer composition, the lower limit of the methanol ratio may be about 0 ppm.

Since the polymer composition of the present application does not contain methanol or contains a minimum amount of methanol, formaldehyde, which is a harmful substance produced thereby, also does not contain or contains minimally. For example, the formaldehyde content of the polymer composition is about 30 ppm or less, 25 ppm or less, 20 ppm or less, 15 ppm or less, 10 ppm or less, 5 ppm or less, 4 ppm or less, 3 ppm or less, 2 ppm or less, 1 It may be less than or equal to ppm or less than or equal to 0.5 ppm. Since it is most appropriate that formaldehyde is not included in the polymer composition, the lower limit of the formaldehyde ratio may be about 0 ppm.

The ratio of methanol and formaldehyde as described above is measured in the manner described in Examples to be described later.

In order to form the polymer composition having the above ratio of methanol and formaldehyde, the polymer may not contain a polymerized unit of a methanol-generating monomer. As a monomer that generates methanol by hydrolysis or the like, a monomer widely used in the production of a film forming agent includes methyl methacrylate or metal acrylate.

As applied to a polymer forming a film forming agent, etc., a monomer having a relatively hydrophobicity (for example, the second monomer of the present application) or a monomer having a relatively high Tg (for example, the monomer of the present application (A )), a monomer having a methyl group such as methyl methacrylate is often used. However, in the present application, the type of monomer mentioned as the second monomer does not produce methanol, or even if it is produced, only a very small amount of methanol is formed. Accordingly, in the present application, it is appropriate to apply only the above-mentioned types of monomers as the second monomer, in particular, the monomer (A) of at least the second monomer.

Accordingly, in one example, the polymer may include only the polymerized unit of the monomer represented by the following formula (3) as the polymerized unit of the second monomer or the monomer (A).

For example, the polymer is at least a polymerized unit of the monomer (A), and in Formula 3, Q is an alkyl group, for example, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or Only a polymerization unit of a compound having 1 to 4 carbon atoms or a methyl group, and B is a linear or branched alkyl group having 2 or more carbon atoms may be applied.In this case, the alkyl group of B is a linear or branched chain having 2 to 4 carbon atoms. It may be an alkyl group of.

The polymer composition of the present application may include only the polymer, or may include other necessary components in addition to the polymer.

As such a necessary component, a formaldehyde removing agent can be illustrated, for example. As an applicable formaldehyde removing agent, ammonia, urea, sodium hydrogen sulfite and/or sodium metabisulfite may be exemplified, but are not limited thereto. The proportion of the formaldehyde removing agent in the polymer composition may be at an appropriate level, for example, about 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight based on 100 parts by weight of the polymer. It may be about 5 parts by weight or less, 4 parts by weight or less, or 3 parts by weight or less. The formaldehyde removing agent may be about 0 parts by weight or more, about 0 parts by weight, 0.5 parts by weight or more, 1 part by weight or more, 1.5 parts by weight or more, or about 2.5 parts by weight or more based on 100 parts by weight of the polymer.

The polymer composition may appropriately further include additives required in addition to the polymer and/or formaldehyde removing agent.

Such additives include oils, surfactants, purified water, polyhydric alcohols (eg, glycerin, propylene glycol, butylene glycol, etc.), organic powders, inorganic powders, ultraviolet absorbers, preservatives, antifoaming agents, antibacterial agents, antioxidants, cosmetic Ingredients, fragrances, thickeners, gelling agents, metal soaps, water-soluble polymers, oil-soluble polymers, fibers (nylon, rayon, etc.), pigments and/or pearl agents may be exemplified, but are not limited thereto.

The polymer composition as described above can be prepared by various known methods, but it is effective to apply an emulsion polymerization method in consideration of the formation efficiency and application efficiency of the polymer. For example, an aqueous solvent such as water An emulsion polymerization method using as a continuous phase may be applied.

In particular, it is effective to apply a seed emulsion polymerization method among the above emulsion polymerization methods when it is desired to form a polymer containing the above-described first monomer as a polymer, and further, a high proportion of the polymerized units of the first monomer. . Seed emulsion polymerization is a polymerization method in which particles are grown by polymerizing homogeneous or heterogeneous monomers in a seed using an emulsion polymer of relatively small particles previously polymerized as a seed. It is possible to effectively produce the polymer of interest in the present application.

The seed emulsion polymerization method may include, for example, a seed polymerization step and a seed growth step.

In one example, the polymerization method includes a first step of seed emulsion polymerization of a reaction solution containing a monomer mixture, an aqueous solvent, and a surfactant; And a second step of growing the seed generated in the first step by performing emulsion polymerization while adding a reaction solution containing a monomer mixture to the seed emulsion polymerized product of the first step.

The monomer mixture applied in the first and second steps may include the above-described first and second monomers, and as the second monomer, the aforementioned monomers (A) and (B) may be included. have. In this case, the ratio of each of the monomers in the monomer mixture may be adjusted to form a polymerized unit of the aforementioned ratio, and may be approximately similar to the ratio of the polymerized units mentioned above in one example.

For example, in the monomer mixture, the first monomer may be included in a ratio within the range of about 4 to 40% by weight, and the ratio may be 4.5% by weight or more, 5% by weight or more, 5.5% by weight or more, 6 Wt% or more, 6.5 wt% or more, 7 wt% or more, 7.5 wt% or more, 8 wt% or more, 8.5 wt% or more, 9 wt% or more, 9.5 wt% or more, 10 wt% or more, 11 wt% or more, 12 Wt.% or more, 13 wt% or more, 14 wt% or more, or 14.5 wt% or more, or 39 wt% or less, 38 wt% or less, 37 wt% or less, 36 wt% or less, 35 wt% or less, 34 wt% or less , 33% or less, 32% or less, 31% or less, 30% or less, 29% or less, 28% or less, 27% or less, 26% or less, 25% or less, 24% or less , 23 wt% or less, 22 wt% or less, 21 wt% or less, 20 wt% or less, 19 wt% or less, 18 wt% or less, 17 wt% or less, 16 wt% or less, or 15 wt% or less.

In addition, in the monomer mixture, the second monomer may be included in a ratio within the range of 150 to 2400 parts by weight with respect to 100 parts by weight of the first monomer, and the ratio is about 200 parts by weight or more, 250 parts by weight or more, 300 Parts by weight or more, 350 parts by weight or more, 400 parts by weight or more, 450 parts by weight or more, 500 parts by weight or more, or 550 parts by weight or more, or 2350 parts by weight or less, 2300 parts by weight or less, 2250 parts by weight or less, 2200 parts by weight or less, It may be about 2150 parts by weight or less, 2100 parts by weight or less, 2050 parts by weight or less, 2000 parts by weight or less, or about 1950 parts by weight or less.

In addition, as the second monomer, when the monomer (A) and the monomer (B) are applied, the weight ratio (A/B) of the monomer (A) and the monomer (B) may be in the range of 0.25 to 3, and , The weight ratio (A/B) is about 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, 0.5 or more, 0.55 or more, 0.6 or more, 0.65 or more, 0.7 or more, 0.75 or more, 0.8 or more, 0.85 or more , 0.9 or more, 0.95 or more, 1.0 or more, 1.5 or more, or 2 or more, 2.5 or less, 2 or less, 1.5 or less, 1 or less, 0.95 or less, 0.9 or less, 0.85 or less, 0.8 or less, 0.75 or less, or about 0.7 or less.

The ratio of the first and second monomers and the monomers (A) and (B) in the above-mentioned monomer mixture may be a ratio determined based on the sum of all monomer mixtures applied in the first and second steps. . That is, as described later, in the polymerization method of the present application, components such as monomers and surfactants are first dispersed in a solvent (aqueous solvent such as water) to prepare a reaction solution, and then a part of the reaction solution is divided into the first step. After performing seed emulsion polymerization, the remaining part may be added to the reaction solution in the second step, and thus the ratio of the monomers may be based on the sum of the monomer mixtures applied in the first and second monomers.

For the emulsion polymerization, a surfactant is applied together with the monomer mixture. As the surfactant, a known surfactant applied in emulsion polymerization can be used. As such surfactants, anionic or nonionic surfactants may be exemplified, and specifically, sodium lauryl sulfate (SLS), sodium dodecyl benzene sulfate (SDBS), and ammonium Anionic surfactants such as ammonium lauryl sulfate (ALS), sodium cetyl stearyl sulfate or sodium lauryl ether sulfate (SLES), or known by names such as Triton or Tween. Nonionic surfactants may be exemplified, and one or a mixture of two or more of the above may be applied.

The ratio of the surfactant may be appropriately adjusted according to the purpose, for example, about 0.5 to 20 parts by weight of a surfactant based on 100 parts by weight of the monomer mixture may be included in the reaction solution. In another example, the ratio is about 1 part by weight or more, 1.5 parts by weight or more, 2 parts by weight or more, 2.5 parts by weight or more, 3 parts by weight or more, 3.5 parts by weight or more, 4 parts by weight or more, or 18 parts by weight or less, 16 parts by weight. It may be about parts by weight or less, 14 parts by weight or less, 12 parts by weight or less, 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, or 6 parts by weight or less.

The ratio of the surfactant is a ratio in the reaction solution in the first step, or if a surfactant is present in the second step, as in the case of a monomer mixture, of the reaction solution in the first and second steps. It can be a ratio based on the sum.

The reaction solution may be prepared by dispersing the monomer mixture and/or surfactant in a solvent (eg, an aqueous solvent such as water). Therefore, the reaction solution may further contain the solvent. There is no particular limitation on the proportion of the solvent, and in one example, the concentration of the monomer mixture in the solvent may be controlled to be in the range of about 5 to 90% by weight.

There is no particular limitation on a method of initiating polymerization of the reaction solution as described above and performing the first step. For example, a known polymerization initiator may be added to the reaction solution, and the first step may be performed by controlling conditions so that the polymerization reaction by the initiator proceeds.

As such an initiator, a known initiator, for example, a known water-soluble initiator may be used, and the kind includes potassium persulfate (KPS), ammonium persulfate (APS), sodium persulfate and/ Or hydrogen peroxide may be exemplified, but is not limited thereto.

The ratio of the initiator is also not particularly limited, and an appropriate ratio may be applied depending on the purpose. The method of initiating polymerization by the initiator is also not particularly limited, for example, if the initiator is a thermal initiator, a method of applying appropriate heat may be applied, and if the initiator is a photoinitiator, a method of irradiating appropriate light may be applied.

As described above, in the method, a reaction solution is prepared by dispersing the monomer mixture and a surfactant in a solvent, some of which are subjected to the seed polymerization reaction of the first step, and then the remaining part is The second step may be performed by adding it to the seed polymer of the first step. In this case, the method includes the step of dispersing the monomer mixture and surfactant in a solvent before the first step to prepare a total reaction solution, and then separating a part of the reaction solution as the reaction solution of the first step. can do. The ratio of the reaction solution separated from the above and applied to the first step is not particularly limited, and, for example, about 1 to 10% by weight of the total reaction solution may be applied as the reaction solution in the first step.

In the method of the present application, the reaction solution introduced in the second step may further include an aqueous solvent and a surfactant together with the monomer mixture. For example, when the first step is performed by dividing the entire reaction solution mentioned above, and the remaining reaction solution is applied to the second step, the reaction solution of the second step is also interfaced as in the case of the reaction solution of the first step. Even when an activator is included, and a separate reaction solution is added in the second step without applying the above method, the surfactant or the like may be included in the reaction solution of the second step.

The rate of the reaction liquid introduced in the second step can be controlled. By controlling the rate of the reaction solution, a polymer having a desired monomer composition and physical properties can be formed more effectively.

For example, the rate at which the reaction solution is added in the second step may be adjusted to be slower than that of the monomer.

The method of performing the second step by initiating polymerization while adding the reaction solution as described above is not particularly limited, for example, as in the case of the first step, a known polymerization initiator is added together with the reaction solution, and the initiator The second step can be performed by controlling the conditions so that the polymerization reaction can proceed. In this case, the type or ratio of the initiator that can be applied, and the method of initiating polymerization by the initiator are the same as those of the first step.

In the method for preparing the polymer composition of the present application, a step of mixing the polymer formed subsequent to the first and second steps and other necessary components such as the formaldehyde removing agent may be additionally performed.

The present application also relates to a film forming agent, a cosmetic composition, or a cosmetic comprising the polymer. If the above-described polymer is used, it is possible to form a uniform film (film) by application, etc., it can exhibit high stability even when applied to the skin, etc., it is excellent in oil resistance, anti-smear property, and powder fall prevention property. It is possible to provide a film forming agent and the like in which the ratio is also minimized.

Accordingly, the polymer may be used in the manufacture of a variety of cosmetics, including beauty packs, makeup such as mascara applied to the lips or eyes, nail polish, lipstick, eye shadow, hair styling agents or eyeliners that may be applied to nails or toenails. It can be applied to the manufacture of a film forming agent or cosmetic composition. In addition, the polymer or film forming agent may be applied for pharmaceutical use due to the above-described properties, and a band-aid or transdermal absorption agent may be exemplified as a pharmaceutical use.

The ratio of the polymer in the film forming agent, cosmetic composition, or cosmetic product is not particularly limited, and may be selected in consideration of application purposes, and the like. For example, if the polymer is applied to a cosmetic composition, the concentration of the polymer in the composition may be in the range of 1% by weight to 20% by weight, but is not limited thereto.

The film forming agent, the cosmetic composition, or the cosmetic may further contain other active ingredients depending on the use. As the additional active ingredient, not only cosmetic ingredients such as whitening or UV protection, but also medicinal ingredients, physiologically active ingredients, or pharmacologically active ingredients may be exemplified. As such active ingredients, local anesthetic ingredients (lidocaine, dibucaine hydrochloride, dibucaine, ethyl aminobenzoate, etc.), analgesic ingredients (salicylic acid derivatives such as methyl salicylate, indomethacin, piroxicam, ketoprofen, perbinac Etc.), anti-inflammatory ingredients (glycyrrhizinic acid salts such as glycyrrhizinic acid, dipotassium glycyrrhizinate, glycyrrhetinic acid, stearyl glycyrrhetinic acid, bpekisamac, benzyl nicotinic acid, hydrocortisone, hydrocortisone butyrate, Hydrocortisone Acetate, Prednisone Acetate Gilacetic Acid, Prezonizone Acetate, Presonizone, Dexamethasone, Dexamethasone Acetate, Dimethyl Isopropyl Azlen Ibprofen Piconore, Alnica Extract, Golden Extract, Toad Ear Extract, Camomile Extract, Kara Min, Licorice extract, Guaiazulene, Gardenia extract, Gentiana extract, Black tea extract, Tocopherol, Tocopherol acetate, Jasper root extract, Perilla extract, Peony extract, Sage extract, Bitter grass extract, Camellia extract, Pyridoxine hydrochloride, Peach leaf Extract, cornflower extract, rock odor extract, mugwort extract, Roman chamomile extract, etc.), anti-histamine ingredients (chlorpheniramine maleate, diphenhydramine, diphenhydramine hydrochloride, diphenhydramine salicylate, ISO penyl hydrochloride, etc.), local irritation Ingredients (ammonia, l-menthol dl-can paste, mentha oil, benzyl nicotinic acid, wanirylamide, etc.), antiseptic ingredients (crotamiton, etc.), antiseptic or antiseptic ingredients (aclinol, chlorhexidine gluconate, chlorhexidine hydrochloride, Benzalkonium chloride, bencenium chloride, povidone-iodine, iodine form, iodine, potassium iodide, merbromin, oxider, cresol, tricrosan, phenol, isopropyl methylphenol, thymol, sodium salicylate, undecylenic acid, photosensitizer, Hinokitiol, phenoxy ethanol, chlorobutanol, quatanium 73, ginpyritione, paraoxybenzoic acid esters, eucalyptus extract, resolsin rosemary extract, etc.), antifungal ingredients (crotrimazor, acetic acid crotrimazor, etc.) , Miconazole acetate, Econazole acetate, Biponazor, Oxyconazole acetate, Srconazor acetate, Nechikonazor hydrochloride, Biponazor and Imidazole antifungal agents such as thioconazole and omoconazor acetate, allylamine antifungal agents such as terbinafine, terbinafine hydrochloride and naphthypine, benzylamine antifungal agents such as butenapine, amorphine hydrochloride, etc. Allylamine-based antifungal agents, thiocarbamine acid-based antifungal agents such as trnaftate, trsicrat, pyrrolnitrin, echisarmid, cyclopyroxoramine, etc.)Tissue repair ingredients (allatoin, heparin-like substances, vitamin A, etc.) Palmitate, vitamin D2, retinol acetate, retinol, vitamin A oil, bread tenor, etc.), astringent ingredients (zinc oxide, gasiogapi extract, aluminum chloride, sulfur extract, its salt, citric acid, shirakaba extract, che extract, hop Extract, maronier extract, etc.), keratin softening ingredients (urea, glycerin, concentrated glycerin, potassium hydroxide, salicylic acid, sulfur, colloidal sulfur, resolsin, gluconic acid, lactic acid, sodium sulfate, etc.), moisturizing ingredients (butylene glycol, blood Sodium Rolidone Carboxylate, Propylene Glycol, Sodium Ribonucleic Acid, Momidium Leaf Extract, Asraginic Acid, Alanine, Arginine Sodium Alginate, Artea Extract, Aloe Vera Extract, Oyster-Extract, Hydrolyzed Keratin, Hydrolyzed Collagen, Hydrolyzed Hi Kyrion, hydrolyzed egg shell membrane, hydrolyzed egg white, hydrolyzed silk, brown algae extract, quince extract, kiichigo extract, xylitol, chitosan, cucumber extract, quince seed extract, glycine, glycerin, glucose, cape aloe extract, cystin , Cysteine, Xenia cucumber extract, serine, sorbitol, trehalulose, sodium lactate, sodium hyaluronate, placenta extract, loofah extract, multi-use, mannitol, lily extract, lactoferrin, lysine, apple extract, royal jelly extract, etc.) Emollient ingredients (almond oil, avocado oil, olive oil, oleic acid, orange rape oil, cacao butter), carrot akis, squalene, ceramide, evening primrose oil, grape seed oil, jojoba oil, macadamia nut oil, mineral oil, mink oil, eucalyptus Oil, rosehip oil, warerin, etc.), whitening ingredients (ascorbic acid, ascorbic acid derivatives, arbutin, resinor, etc.) Lagic acid, glutathione, kojic acid, age stick kiss, kiwi extract, etc.), UV protection ingredients (paraaminobenzoic acid, ethyl ester of paraaminobenzoic acid, glycerin ester of paraaminobenzoic acid, amyl alcohol ester of paradimethylaminobenzoic acid, paradimethylamino 2-ethylhexyl alcohol ester of benzoic acid, t-butylmethoxydibenzoyl methane, oxybenzone, octyl triazone, octyl salicylate, ethyl diisopropyl cinnamic acid, diisopropyl methyl cinnamic acid, synokisate, dimethoxy cinnamic acid octanoic acid glycerol Reel, dimethoxy benzylidene dioxoimidazolidine propionate octyl, body leaf extract, dromethrizor, paramethoxy isopropyl acid, homosarate, methoxy cinnamic acid octyl, etc.), herbal extract ingredients, vitamins, Amino acids or minerals may be exemplified, but are not limited thereto.

The film forming agent, the cosmetic composition, or the cosmetic may contain other solvents, solvents, or additives depending on the use.

In the above, as the solvent or solvent component, depending on the purpose of the composition and the form of use, for example, alcohol (e.g., polyethylene glycol, etc.), ether (diethyl ether, etc., glycol ethers (methyl cellosolve, etc.) Cellosolve types; diethylene glycol, dialkylene glycol alkyl ethers such as ethyl ether, etc.), nitriles (acetonitrile, etc.), ketones (acetone, etc.) or esters (carboxylic acid alkyl esters such as ethyl acetate, etc.) And the like can be exemplified.

In addition, additives include plasticizers, wetting agents, antifoaming agents, coloring agents, preservatives, fragrances, flavoring agents, pigments or thickeners, as well as conventional components used in quasi-drugs, pharmaceuticals or cosmetics, for example, powdered bases or carriers ( Binders, disintegrants, excipients or lubricants, etc.), oily bases or carriers (animal and vegetable oils, waxes, petrolatum, paraffin oils, silicone oils, higher fatty acid esters or higher fatty acids, etc.), aqueous bases or carriers (gel bases such as xanthan gum, etc.) Etc.), preservatives, chelating agents, antioxidants, refreshing agents, stabilizers, fluidizing agents, emulsifying agents, thickening agents, buffering agents, dispersing agents, adsorbents, moisturizing agents, wetting agents, desiccants, antistatic agents, or other resins (addition of polyamide resin hydrogen Olefin-based resins such as polybutene, etc.) may be exemplified, but are not limited thereto.

A method of preparing the film forming agent, a cosmetic composition, or cosmetics using the above ingredients or, if necessary, other known ingredients is not particularly limited, and a known method may be applied.

The object of the present application is to provide a polymer composition capable of forming cosmetics, etc., which have excellent oil resistance and do not bleed or fall off during use, and a film forming agent or cosmetics prepared using the same.

1 is a photograph of the polymer prepared in Example 3.

Hereinafter, the polymer of the present application will be described in detail through Examples and Comparative Examples, but the scope of the polymer and the like is not limited to the following Examples. In the following Examples and Comparative Examples, each physical property was evaluated in the following manner.

1.Measurement of methanol and formaldehyde ratio

The ratio of methanol was confirmed by GC-FID (Gas Chromatography Flame Ionization Detector) method. As a measuring device, Agilent Technologies' 7890B GC System product was used, and the sample was diluted in ACN (Acetonitrile) to check the methanol ratio. Measurement conditions at the time of checking the methanol ratio are as follows.

<Measurement conditions>

Meter: 7890B GC System (Agilent Technologies)

Column: HP-FFAP (19091F-115) (50m*320㎛ *0.5㎛)

Injector templerautre: 220℃

Oven temperature: 60℃/10min-25℃/min-220℃/13min

Flow rate: 1.5 mL/min

Injection volume: 1.5 μL injection

The proportion of formaldehyde was confirmed by LC-UV (Liquid Chromatography-UV) method. A 1260 Infinity II LC product of Agilent Technologies was used as a measuring instrument. The sample was expressed with water and obtained by ultrasonic extraction for 1 hour, and then the formaldehyde ratio was checked. Measurement conditions at the time of confirming the formaldehyde ratio are as follows.

<Measurement conditions>

Column: C18 (5 μm, 4.6 * 250 mm)

Mobile phase: ACN: Water = 60: 40

Oven temperature: 30℃

Injection volume: 10 μL

Detection: 360nm

2. Molecular weight measurement

The weight average molecular weight (Mw) and molecular weight distribution (PDI) were measured using GPC under the following conditions, and the measurement results were converted using standard polystyrene of Agilent system to prepare a calibration curve.

<Measurement conditions>

Measuring instrument: Agilent GPC (Agilent 1200 series, U.S.)

Column: Connect 2 PL Mixed B

Column temperature: 40°C

Eluent: Tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

Concentration: ~1 mg/mL (100 μL injection)

3. Calculation of glass transition temperature

The glass transition temperature (Tg) was calculated by the following equation according to the monomer composition.

<Equation>

1/Tg = ΣWn/Tn

In the above formula, Wn is the weight fraction of each monomer of the polymer, Tn is the glass transition temperature that appears when the monomer forms a homopolymer, and the right side of the formula is the weight fraction of the monomer used, and the monomer forms a homopolymer. This is the result of summing all the calculated values after calculating the value divided by the glass transition degree (Wn/Tn) for each monomer.

4. Spreading Assessment

The bleeding evaluation was performed in the following manner. First, a sample (mascara formulation) was applied to a thickness of about 100 μm on a glass plate, and then dried at 25° C. for 24 hours. ^{After that, drop 0.1 g of artificial sebum on an area of about 4 cm 2} of the dried sample, perform wetting for 10 minutes, place the paper on it, and perform horizontal reciprocation 20 times with a 500 g weight on the paper. Image analysis was performed to determine the extent to which artificial sebum was deposited.

The artificial sebum contains 40% by weight of triglyceride, 2.2% by weight of diglyceride, 16.4% by weight of free fatty acid, 12% by weight of squalene, 25% by weight of wax ester, 1.4% by weight of cholesterol, and 2% by weight of cholesterol ester. Was used.

Through image analysis, the measured value of the color difference meter of the paper in the above case where the sample was applied and dried, and the artificial sebum was dropped and buried on the paper, was measured without applying the formulation, and the measured value of the color difference meter of the paper dropped on the artificial sebum was The divided value was confirmed, and the higher this value, the better the anti-bleeding property.

5. Evaluation of powder dropping

The powder dropping evaluation was performed in the following manner. First, the mascara formulation was applied to the human hair glass strands 10 times, and after drying, the dried human hair sample was immersed in distilled water at 25° C. for 5 seconds, and then taken out. After drying the human hair for 3 minutes, using a nylon brush, the amplitude was compared through image analysis of falling powder by applying friction 20 times within 2 cm. The powder dropping value is a measure of the number of powders dropped by applying friction after applying the formulation to the human hair strands, drying them, and then immersing them in water and taking them out.

6. Panel evaluation

A mascara test was conducted by 20 professional evaluation panels (ages 25 to 50). After 6 hours after applying mascara to the panels, the degree of bleeding (the degree of smearing on sebum) and the degree of powdering were evaluated in 5 steps according to the following criteria, and the average was judged.

<Evaluation criteria for smearing and powdering off>

A: Average score of 4.5 or higher

B: Average 3.5 or more, less than 4.5

C: average 2.5 points or more, less than 3.5 points

D: average less than 2.5 points

<Score evaluation criteria>

<Evaluation of smearing>

5 points: no smearing

4 points: slightly bleeding

3 points: Moderate

2 points: severe bleeding

1 point: Very severe bleeding

<Evaluation of powder dropping>

5 points: no powder fall off

4 points: less powder fall off

3 points: Moderate

2 points: a lot of powder fall off

1 point: Very much powder fall off

Example 1.

200 g of purified water and 5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were added to a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer, and a stirrer, and uniformly mixed, and the temperature was raised to 70°C.

In reactor 2 equipped with a separate stirrer, 100 g of purified water, acrylic acid (solubility parameter: 13.6 (cal/cm ³ ) ^1/2 , Tg 105°C) 10 g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal/ cm ³ ) ^1/2 , Tg: -50°C) 110 g, ethyl methacrylate (solubility parameter: 9.7 (cal/cm ³ ) ^1/2 , Tg: 65°C) 80 g, sodium lauryl sulfate 4 g and 4 g of Triton X-405 was added and emulsified. In the emulsion of reactor 2, 5% by weight of the emulsion was separated, put into the reactor 1, 0.5 g of an initiator (ammonium persulfate) was added, and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When introducing the emulsion remaining in the reactor 2, 0.5 g of an initiator (ammonium persulfate) dissolved in purified water was added together and polymerization was performed for 24 hours. In this process, the rate of introduction of the emulsion was controlled to about 85 mL/min. Through the above process, a polymer polymerization solution having excellent phase stability could be obtained without an increase in viscosity. The molecular weight (Mw) of the prepared polymerization solution was about 500,000 to 650,000, and the Tg was about -8.6°C. Subsequently, 5 g of an aqueous ammonia solution (28% by weight), which is a formaldehyde removing agent, was mixed with the polymerization solution to prepare a polymer composition. Subsequently, the polymer composition was mixed with other ingredients as shown in Table 1 below to obtain a mascara formulation. The numbers in Table 1 below are weight ratios.

Example 2.

200 g of purified water and 5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were added to a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer, and a stirrer, and uniformly mixed, and the temperature was raised to 70°C.

In reactor 2 equipped with a separate stirrer, 100 g of purified water, methacrylic acid (solubility parameter: 12.3 (cal/cm ³ ) ^1/2 , Tg: 225°C) 10 g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal/cm ³ ) ^1/2 , Tg: -50°C) 115 g, ethyl methacrylate (solubility parameter: 9.7 (cal/cm ³ ) ^1/2 , Tg: 65°C) 75 g, sodium lauryl sulfate 4 g and 4 g of Triton X-405 were added and emulsified. In the emulsion of reactor 2, 5% by weight of the emulsion was separated, put into the reactor 1, 0.5 g of an initiator (ammonium persulfate) was added, and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When introducing the emulsion remaining in the reactor 2, 0.5 g of an initiator (ammonium persulfate) dissolved in purified water was added together and polymerization was performed for 24 hours. In this process, the rate of introduction of the emulsion was controlled to about 85 mL/min. Through the above process, a polymer polymerization solution having excellent phase stability could be obtained without an increase in viscosity. The molecular weight (Mw) of the prepared polymerization solution was about 500,000 to 650,000, and the Tg was about -9.0°C. Subsequently, 5 g of an aqueous ammonia solution (28% by weight), which is a formaldehyde removing agent, was mixed with the polymerization solution to prepare a polymer composition. Subsequently, the polymer composition was mixed with other ingredients as shown in Table 1 below to obtain a mascara formulation.

Example 3.

200 g of purified water and 2.5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were added to a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer, and a stirrer, and uniformly mixed, and the temperature was raised to 70°C.

Purified water 100 g, 2-hydroxyethyl acrylate (solubility parameter: 14.1 (cal/cm ³ ) ^1/2 ,Tg: -15°C) 30 g, 2-ethylhexyl acrylate in reactor 2 equipped with a separate stirrer (Solubility parameter: 8.8 (cal/cm ³ ) ^1/2 , Tg: -50°C) 90 g, ethyl methacrylate (solubility parameter: 9.7 (cal/cm ³ ) ^1/2 , Tg: 65°C) 80 g , 4 g of sodium lauryl sulfate and 4 g of Triton X-405 were added and emulsified. In the emulsion of reactor 2, 5% by weight of the emulsion was separated, put into the reactor 1, 0.5 g of an initiator (ammonium persulfate) was added, and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When introducing the emulsion remaining in the reactor 2, 0.5 g of an initiator (ammonium persulfate) dissolved in purified water was added together and polymerization was performed for 24 hours. In this process, the rate of introduction of the emulsion was controlled to about 85 mL/min. 1 is a photograph of a polymer polymerization solution obtained through the above process. Through the above process, a polymer polymerization solution having excellent phase stability could be obtained without an increase in viscosity. The molecular weight (Mw) of the prepared polymerization solution was about 500,000 to 650,000, and Tg was about -9°C. Subsequently, 4 g of an aqueous ammonia solution (28% by weight), which is a formaldehyde removing agent, was mixed with the polymerization solution to prepare a polymer composition. Subsequently, the polymer composition was mixed with other ingredients as shown in Table 1 below to obtain a mascara formulation.

Example 4.

200 g of purified water and 2.5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were added to a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer, and a stirrer, and uniformly mixed, and the temperature was raised to 70°C.

Purified water 100 g, 2-hydroxyethyl acrylate (solubility parameter: 14.1 (cal/cm ³ ) ^1/2 , Tg: -15°C) 30 g, 2-ethylhexyl acrylate in reactor 2 equipped with a separate stirrer (Solubility parameter: 8.8 (cal/cm ³ ) ^1/2 , Tg: -50°C) 55 g, methyl methacrylate (solubility parameter: 10.1 (cal/cm ³ ) ^1/2 , Tg: 105°C) 115 g , 4 g of sodium lauryl sulfate and 4 g of Triton X-405 were added and emulsified. In the emulsion of reactor 2, 5% by weight of the emulsion was separated, put into the reactor 1, 0.5 g of an initiator (ammonium persulfate) was added, and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When introducing the emulsion remaining in the reactor 2, 0.5 g of an initiator (ammonium persulfate) dissolved in purified water was added together and polymerization was performed for 24 hours. In this process, the rate of introduction of the emulsion was controlled to about 85 mL/min. Through the above process, a polymer polymerization solution having excellent phase stability could be obtained without an increase in viscosity. The molecular weight (Mw) of the prepared polymerization solution (polymer composition) was about 500,000 to 650,000, and the Tg was about 26.5°C. Subsequently, the polymer composition was mixed with other ingredients as shown in Table 1 below to obtain a mascara formulation.

Comparative Example 1.

200 g of purified water and 5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were added to a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer, and a stirrer, and uniformly mixed, and the temperature was raised to 70°C.

In reactor 2 equipped with a separate stirrer, 100 g of purified water, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal/cm ³ ) ^1/2 , Tg: -50°C) 120 g, methyl methacrylate (solubility parameter : 10.1 (cal/cm ³ ) ^1/2 , Tg: 105°C) 80 g, sodium lauryl sulfate 4 g and Triton X-405 4 g were added and emulsified. In the emulsion of reactor 2, 5% by weight of the emulsion was separated, put into the reactor 1, 0.5 g of an initiator (ammonium persulfate) was added, and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When introducing the emulsion remaining in the reactor 2, 0.5 g of an initiator (ammonium persulfate) dissolved in purified water was added together and polymerization was performed for 24 hours. In this process, the rate of introduction of the emulsion was controlled to about 85 mL/min. The molecular weight (Mw) of the prepared polymerization solution (polymer composition) was about 500,000 to 650,000, and the Tg was about -6.2°C. Subsequently, the polymer composition was mixed with other ingredients as shown in Table 1 below to obtain a mascara formulation.

Example Comparative example One 2 3 4 One Polymer composition 30 30 30 30 30 Water 44.4 44.4 44.4 44.4 44.4 Disodium EDTA 0.1 0.1 0.1 0.1 0.1 Butylene glycol 5 5 5 5 5 Triethanolamine One One One One One Phenoxy ethanol 0.5 0.5 0.5 0.5 0.5 hydroxyethylcellulose 0.5 0.5 0.5 0.5 0.5 Iron oxides (CI77499) 5 5 5 5 5 Stearic acid 5 5 5 5 5 Beeswax 6 6 6 6 6 Copernicia cerifera(carnauba) wax 2 2 2 2 2 Polyglyceryl-3 beewax 0.5 0.5 0.5 0.5 0.5

The physical property evaluation results for each of the Examples and Comparative Examples are summarized in Table 2 below (in Table 2, the methanol ratio and formaldehyde ratio are for the polymer composition, and the unit is ppm).

Example Comparative example One 2 3 4 One Methanol ratio Not detected Not detected Not detected 21 23 Formaldehyde ratio 2.3 3.5 3.3 37.5 36.5 Smear test 94.3 93.9 97.3 96.6 51.6 Powder drop test 4 3 4 11 3 Smear (panel evaluation) A B A A D Falling off powder (Panel evaluation) B A B D A

Reference Example 1

200 g of purified water and 5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were added to a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer, and a stirrer, and uniformly mixed, and the temperature was raised to 70°C.

In reactor 2 equipped with a separate stirrer, 100 g of purified water, acrylic acid (solubility parameter: 13.6 (cal/cm ³ ) ^1/2 , Tg 105°C) 10 g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal/ cm ³ ) ^1/2 , Tg: -50°C) 110 g, ethyl methacrylate (solubility parameter: 9.7 (cal/cm ³ ) ^1/2 , Tg: 65°C) 80 g, sodium lauryl sulfate 4 g and 4 g of Triton X-405 was added and emulsified. In the emulsion of reactor 2, 5% by weight of the emulsion was separated, put into the reactor 1, 0.5 g of an initiator (ammonium persulfate) was added, and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When introducing the emulsion remaining in the reactor 2, 0.5 g of an initiator (ammonium persulfate) dissolved in purified water was added together and polymerization was performed for 24 hours. In this process, the rate of introduction of the emulsion was controlled to about 85 mL/min. The Tg of the prepared polymerization solution (polymer composition) is about -8.6°C. As a result of confirming the polymer composition in the same manner as in Examples and Comparative Examples, methanol was not detected, and the proportion of formaldehyde was about 20.8 ppm.

Reference Example 2

200 g of purified water and 5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were added to a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer, and a stirrer, and uniformly mixed, and the temperature was raised to 70°C.

In reactor 2 equipped with a separate stirrer, 100 g of purified water, acrylic acid (solubility parameter: 13.6 (cal/cm ³ ) ^1/2 , Tg 105°C) 10 g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal/ cm ³ ) ^1/2 , Tg: -50°C) 60 g, ethyl methacrylate (solubility parameter: 9.7 (cal/cm ³ ) ^1/2 , Tg: 65°C) 130 g, sodium lauryl sulfate 4 g and 4 g of Triton X-405 was added and emulsified. In the emulsion of reactor 2, 5% by weight of the emulsion was separated, put into the reactor 1, 0.5 g of an initiator (ammonium persulfate) was added, and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When introducing the emulsion remaining in the reactor 2, 0.5 g of an initiator (ammonium persulfate) dissolved in purified water was added together and polymerization was performed for 24 hours. In this process, the rate of introduction of the emulsion was controlled to about 85 mL/min. The Tg of the prepared polymerization solution (polymer composition) is about 21.1°C. As a result of measuring the ratio of methanol and formaldehyde with respect to the polymer composition in the same manner as in Examples and Comparative Examples, methanol was not detected, and the ratio of formaldehyde was 21.6 ppm. In addition, the results of the smearing test, powder dropping test, smearing test (panel evaluation) and powder dropping test (panel evaluation) for the mascara formulation obtained in the same formulation as Example 1 except for using the polymer composition were 93.4 and 10, respectively. , B and D.

Reference Example 3

200 g of purified water and 5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were added to a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer, and a stirrer, and uniformly mixed, and the temperature was raised to 70°C.

In reactor 2 equipped with a separate stirrer, 100 g of purified water, acrylic acid (solubility parameter: 13.6 (cal/cm ³ ) ^1/2 , Tg 105°C) 10 g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal/ cm ³ ) ^1/2 , Tg: -50°C) 85 g, methyl methacrylate (solubility parameter: 10.1 (cal/cm ³ ) ^1/2 , Tg: 105°C) 105 g, sodium lauryl sulfate 4 g and 4 g of Triton X-405 was added and emulsified. In the emulsion of reactor 2, 5% by weight of the emulsion was separated, put into the reactor 1, 0.5 g of an initiator (ammonium persulfate) was added, and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When introducing the emulsion remaining in the reactor 2, 0.5 g of an initiator (ammonium persulfate) dissolved in purified water was added together and polymerization was performed for 24 hours. In this process, the rate of introduction of the emulsion was controlled to about 85 mL/min. The Tg of the prepared polymerization solution (polymer composition) is about 18.8°C. As a result of measuring the ratio of methanol and formaldehyde with respect to the polymer composition in the same manner as in Examples and Comparative Examples, the ratio of methanol and formaldehyde was 19 ppm and 38.1 ppm, respectively. In addition, the smearing test, powder dropping test, smearing test (panel evaluation), and powder dropping test (panel evaluation) of the mascara formulation obtained in the same formulation as Example 1 except that the polymer composition was used were 95.5 and 14, respectively. , A and D.

Reference Example 4

Purified water 300g, 2-hydroxyethyl acrylate (solubility parameter: 14.1 (cal/cm ³ ) ^1/2 ,Tg: -15℃) 30g, 2-ethylhexyl in a reactor equipped with a cooler, nitrogen injector, thermometer and stirrer Acrylate (solubility parameter: 8.8 (cal/cm ³ ) ^1/2 , Tg: -50°C) 90 g, ethyl methacrylate (solubility parameter: 9.7 (cal/cm ³ ) ^1/2 , Tg: 65°C) 80 g, 4 g of sodium lauryl sulfate, 4 g of Triton X-405, and 2.5 g of sodium hydrogen carbonate saturated with a neutralizing agent were added thereto, followed by emulsification, and the temperature was raised to 70°C. Then, 1 g of an initiator (ammonium persulfate) was added, and polymerization was performed for 24 hours. The Tg of the prepared polymerization solution is about -9°C.

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Reference Example 5

Purified water 300g, 2-hydroxyethyl acrylate (solubility parameter: 14.1 (cal/cm ³ ) ^1/2 ,Tg: -15℃) 30g, 2-ethylhexyl in a reactor equipped with a cooler, nitrogen injector, thermometer and stirrer acrylate (solubility ^{parameter: 8.8 (cal / cm 3)} 1/2, Tg: -50 ℃) 55 g, methyl methacrylate (solubility ^{parameter: 10.1 (cal / cm 3)} 1/2, Tg: 105 ℃) 115 g, 4 g of sodium lauryl sulfate, 4 g of Triton X-405, and 2.5 g of sodium hydrogen carbonate saturated with a neutralizing agent were added thereto, followed by emulsification, and the temperature was raised to 70°C. Then, 1 g of an initiator (ammonium persulfate) was added, and polymerization was performed for 24 hours. The Tg of the prepared polymerization solution is about 26.5°C.

Claims (13)

A polymer comprising a first monomeric polymerization unit having a solubility parameter of a single polymer of 11.0 (cal/cm ³ ) ^1/2 or more and a second monomeric polymerization unit having a solubility parameter of a single polymer of less than ^{11.0 (cal/cm 3} ) ^1/2 Including,
The ratio of the first monomeric polymerization unit in the polymer is in the range of 4 to 40% by weight, the second monomeric polymerization unit is included in the polymer in 150 to 2400 parts by weight based on 100 parts by weight of the first monomeric polymerization unit,
The second monomeric polymerization unit includes a monomer (A) polymerization unit having a glass transition temperature of 20°C or higher and a monomer (B) polymerization unit having a glass transition temperature of less than 20°C, and the monomer (A) polymerization unit and the monomer ( B) the weight ratio (A/B) of the polymerized unit is in the range of 0.25 to 1.5,
The first monomer polymerized unit is a hydroxy group-containing monomer; Polymerizable heterocyclic monomers; (Meth)acrylamide-based monomer; Acidic monomers; Or glyceryl (meth)acrylate,
The polymer composition in which the glass transition temperature of the polymer is in the range of -30°C to 5°C. The polymer composition according to claim 1, wherein the methanol ratio is 30 ppm or less. The polymer composition according to claim 1, wherein the formaldehyde ratio is 30 ppm or less. The polymer composition according to claim 1, wherein the polymer does not contain a polymerized unit of a methanol-generating monomer. The polymer composition according to claim 4, wherein the methanol-generating monomer is methyl (meth)acrylate. The polymer composition of claim 1, wherein the second monomer is represented by the following formula (3):
[Formula 3]

In Formula 3, Q is hydrogen or an alkyl group, and B is a C2 or more linear or branched alkyl group, an alicyclic hydrocarbon group, or an aromatic substituent. delete delete delete The polymer composition according to claim 1, wherein the polymer has a weight average molecular weight in the range of 100,000 to 2 million. The polymer composition according to claim 1, further comprising a formaldehyde removing agent. A film forming agent comprising the polymer composition of claim 1. A cosmetic composition comprising the polymer composition of claim 1 or the film forming agent of claim 12.

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