KR102775900B1 - Amphiphilic thickener for personal care - Google Patents

Abstract

The present invention relates to a thickener that can be used in cosmetics, etc., and more specifically, to a thickener that can provide moisture while being less sticky.
In the present invention, a thickener in the form of homogeneous fine particles coated with a silicone polymer can be manufactured by allowing a polymerization reaction to proceed in a uniform reverse phase emulsion having a small particle size using a PIT (Phase Inversion Temperature) polymerization method. In addition, a thickener can be manufactured using a precipitation polymerization method.
In addition, the thickener in the form of spherical particles manufactured by the present invention has the advantage of high moisture retention capacity due to the silicone polymer coated on the shell while maintaining the particle shape even when swelling in a water phase, and the spherical particles whose surface is coated with the silicone polymer also have high dispersibility in an oil phase, which helps to maintain the durability of the makeup, and the spherical polymer also has the effect of reducing stickiness and smudging.

Description

{Amphiphilic thickener for personal care}

The present invention relates to a thickener that can be used in a composition or product for personal care such as cosmetics, and more specifically, to a thickener that can provide moisture while having little stickiness.

When using makeup or sunscreen, an important attribute is that the makeup lasts long or has high UV protection, so that the makeup effect lasts long without having to touch up or reapply even after one application. However, in order to increase the makeup lasts long, a water-in-oil (W/O) formulation with excellent sweat resistance and sebum resistance is used, so there is a disadvantage in that it feels dry due to a lack of moisture. In addition, because of the volatile oil used for quick setting when applying to the skin, the moldability of the formulation is also reduced during product manufacturing, which lowers productivity.

To solve this problem, if the water-in-oil ratio of the formulation is increased, the stability of the formulation is impaired due to the nature of the water-in-oil type, which makes phase separation easily occur, and if more emulsifiers are used to enhance the stability of the formulation, a vicious cycle of increased stickiness occurs. In addition, if a film former is used to increase the durability of the makeup, stickiness and smudging also increase.

Therefore, there is a need for a technology that can increase the durability of makeup and UV protection while also increasing moisture and improving stickiness and smudging.

To solve this problem, the inventors of the present invention, based on the polymer with a microparticle structure of the previous study, Patent Registration No. 10-2531603, chemically coated the core portion with a polymer that can absorb water and maintain viscosity, and the shell portion with a silicone polymer, thereby suppressing moisture evaporation from the core portion, thereby increasing moisture content and improving the durability of the makeup and stickiness and smudging due to the silicone polymers of the shell portion, thereby completing the present invention.

Republic of Korea Patent No. 10-2531603

An object of the present invention is to provide an amphiphilic thickener for personal care which can increase moisture and improve stickiness and smudging.

Another object of the present invention is to provide a cosmetic having excellent makeup durability and UV protection durability, comprising the amphiphilic thickener of the present invention.

To achieve the above-mentioned purpose, the amphiphilic thickener of the present invention includes a cross-linked polymer obtained by polymerizing a water-soluble monomer represented by the following chemical formula 1, a cross-linkable monomer, and a silicone-containing monomer represented by the following chemical formula 2.

[Chemical Formula 1]

In the above formula,

R ₁ is -H, -CH ₃ or -CH ₂ CH ₃ , -(CH ₂ ) _m CH ₃ , where m = 1 to 3,

R ₂ is -OX, NH ₂ or -NH-R ₃ -SO ₃ Y,

R ₃ is -(CH ₂ )-, -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ) ₂ (CH3) ₂ - or -(CH ₂ ) ₃ CH ₃ -,

X and Y are H ⁺ , Na ⁺ , Li ⁺ , K ^+, or _NH3 ⁺ , and X and Y can be the same.

[Chemical formula 2]

In the above formula,

m is an integer from 1 to 5,

n is an integer between 10 and 5000,

R ₁ is hydrogen or a C _1-3 alkyl group,

R ₂ is a hydroxy group, a C _1-3 alkyl group, or a vinyl group.

In one specific example, the present invention includes a method for producing the amphiphilic thickener, comprising dissolving and heating a water-soluble monomer represented by the chemical formula 1, a crosslinkable monomer, and a silicone-containing monomer represented by the chemical formula 2, and then adding a reaction initiator to polymerize the resulting mixture to produce a crosslinked polymer.

In one specific example, the method for producing an amphiphilic thickener of the present invention may include the steps of: producing an oil-in-water type emulsion composition including an aqueous phase including a water-soluble monomer represented by the chemical formula 1 and a crosslinking monomer, and an oil phase including a silicone-containing monomer represented by the chemical formula 2 and a nonpolar organic solvent; heating to 60° C. or higher to produce a water-in-oil type reversed phase emulsion composition; and adding a reaction initiator to cause a polymerization reaction to produce a crosslinked polymer.

As a specific example, the phase inversion temperature (PIT) polymerization method can be used as a method for producing the amphiphilic thickener.

In another specific example, the method for producing an amphiphilic thickener of the present invention may include the steps of: dissolving a water-soluble monomer represented by the chemical formula 1, a crosslinkable monomer, and a silicone-containing monomer represented by the chemical formula 2 in an alcohol-based solvent; heating to 60° C. or higher; and adding a reaction initiator to polymerize and produce a crosslinked polymer. A precipitation polymerization method may be used as the method for producing the amphiphilic thickener.

In one specific example, the method for producing the amphiphilic thickener may further include a step of obtaining the thickener as a solid, for example, a precipitation method using a non-solvent of the crosslinked polymer may be used.

The present invention provides a thickener in the form of homogeneous fine particles, wherein the core is composed of a water-soluble polymer cross-linker and the surface is coated with a silicone polymer. Therefore, the thickener in the form of spherical particles of the present invention has an advantage in that the shape of the particles is maintained even when swelling in a water phase, and the moisture retention capacity is enhanced by the coated silicone polymer, which is a shell portion. In addition, the spherical particles whose surface is coated with a silicone polymer have high dispersibility in an oil phase, which helps the makeup to last longer, and the spherical polymer also has the effect of reducing stickiness and smudging.

Figure 1 is an exemplary diagram showing a method for producing an amphiphilic thickener using a reverse emulsification polymerization method in the present invention.
Figure 2 is an exemplary diagram showing a method for producing an amphiphilic thickener using a precipitation polymerization method in the present invention.
Figure 3 is a graph showing the results of confirming the moisture retention capacity of an amphiphilic thickener according to the present invention.
Figure 4 is a photograph showing the results of confirming the smearing of a makeup formulation using an amphiphilic thickener according to the present invention.
Figure 5 is a graph showing the results of confirming the stickiness of a sunscreen formulation using an amphiphilic thickener according to the present invention.

However, the present invention can have various modifications and can have various forms, and the specific examples and descriptions described below are only for helping to understand the present invention, and are not intended to limit the present invention to a specific disclosed form. It should be understood that the scope of the present invention includes all modifications, equivalents, or substitutes included in the spirit and technical scope of the present invention.

Below, the present invention is described in more detail.

In the present invention, the "thickener" means a cross-linked polymer manufactured according to the manufacturing method of the present invention, and may mean a solution in which the cross-linked polymer is dispersed. In particular, the thickener may mean a substance commonly used for the purpose of increasing viscosity in a personal care composition or personal care product.

In one specific example, the amphiphilic thickener of the present invention includes a cross-linked polymer obtained by polymerizing a water-soluble monomer represented by the following chemical formula 1 and a cross-linkable monomer and a silicone-containing monomer represented by the following chemical formula 2.

In one specific example, the water-soluble monomer may be a compound represented by the following chemical formula 1.

[Chemical Formula 1]

In the above formula,

R ₁ is -H, -CH ₃ or -CH ₂ CH ₃ , -(CH ₂ ) _m CH ₃ , where m = 1 to 3,

R ₂ is -OX, NH ₂ or -NH-R ₃ -SO ₃ Y,

R ₃ is -(CH ₂ )-, -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ) ₂ (CH3) ₂ - or -(CH ₂ ) ₃ CH ₃ -,

X and Y are H ⁺ , Na ⁺ , Li ⁺ , K ^+, or _NH3 ⁺ , and X and Y can be the same.

[Chemical formula 2]

In the above formula,

m is an integer from 1 to 5,

n is an integer between 10 and 5000,

R ₁ is hydrogen or a C _1-3 alkyl group,

R ₂ is a hydroxy group, a C _1-3 alkyl group, or a vinyl group.

In one specific example, the method for producing an amphiphilic thickener of the present invention may include a step (step 1-1) of producing an oil-in-water type emulsion composition including an aqueous phase including a water-soluble monomer represented by the chemical formula 1 and a crosslinking monomer; and an oil phase including a silicone-containing monomer represented by the chemical formula 2 and a nonpolar organic solvent; a step (step 1-2) of heating to 60° C. or higher to produce a water-in-oil type reversed phase emulsion composition; and a step (step 1-3) of adding a reaction initiator to cause a polymerization reaction to produce a crosslinked polymer:

In one specific example, the PIT (phase inversion temperature) polymerization method can be used as a method for producing the amphiphilic thickener. The PIT polymerization method forms an oil-in-water type emulsion composition at a low temperature, as in step 1-1, and then, by increasing the temperature through step 1-2, converts it to a water-in-oil type reverse emulsion composition.

In the present invention, step 1-1 is a step of preparing an oil-in-water emulsion composition including an aqueous phase including a water-soluble monomer represented by the chemical formula 1 and a crosslinkable monomer; and an oil phase including a silicone-containing monomer represented by the chemical formula 2 and a non-polar organic solvent.

In the present invention, the water-soluble monomer and cross-linking monomer represented by the chemical formula 1 are included in the water-soluble monomer and cross-linking monomer represented by the chemical formula 1.

In one specific example, the water-soluble monomer represented by the chemical formula 1 of step 1-1 may be at least one selected from the group consisting of acrylamidopropylmethyl Sulfonic acid (AMPS), acrylic acid, acrylamide, and polyethylene glycol acrylate.

Specifically, the water-soluble monomer represented by the chemical formula 1 may be a compound represented by the following chemical formula 1a.

[Chemical formula 1a]

In the present invention, the content of the water-soluble monomer represented by the chemical formula 1 in the step 1-1 is not particularly limited, but may be included in an amount of, for example, 10 to 99 wt% based on 100 wt% of the total sum of the water-soluble monomer represented by the chemical formula 1, the crosslinking monomer, and the silicone-containing monomer represented by the chemical formula 2, preferably 30 to 95 wt%, and more preferably 50 to 95 wt%. Within the above range, the stability of the composition can be further stabilized and the stickiness improvement effect can be further improved.

In one specific embodiment, the crosslinking monomer of step 1-1 may be a compound having two or more acrylate groups, two or more acrylamide groups, or two or more vinyl groups. As such a crosslinking monomer, for example, at least one selected from the group consisting of trimethylolpropane ethoxylate triacrylate (TMPETA), trimethylolpropane triacrylate (TMPTA), methylene bisacrylamide, divinyl sulfone, divinyl benzene, divinyl ether, divinylacetylene, polyglycol diacrylate, polyglycol triacrylate, and 4-arm-polyglycol tetraacrylate may be used.

In one specific embodiment, the crosslinking monomer of step 1-1 may more preferably be trimethylolpropane ethoxylate triacrylate (TMPETA), trimethylolpropane triacrylate (TMPTA), or a combination thereof. The crosslinking monomer is a compound having three or more crosslinking points and can improve the molecular weight of the crosslinked product, thereby improving the viscosity.

In the present invention, the content of the crosslinking monomer in step 1-1 is not particularly limited, but for example, the content of the crosslinking monomer may be included in an amount of 0.01 to 20 wt% based on 100 wt% of the total sum of the water-soluble monomer represented by the chemical formula 1, the crosslinking monomer, and the silicone-containing monomer represented by the chemical formula 2, preferably 0.1 to 10 wt%, more preferably 0.5 to 5.0 wt%. Within the above range, the stability of the composition may be more excellent or the stickiness improvement effect may be more excellent.

In one specific example, the solvent of the award in step 1-1 may be water (distilled water).

In one specific example, the pH of the water of step 1-1 is not particularly limited, but may be, for example, 5 to 9. The pH can be adjusted using a conventional pH adjuster, for example, ammonia water.

In the present invention, the oil phase of step 1-1 may include a monomer containing silicon represented by the chemical formula 2 and an organic solvent.

In the present invention, the content of the silicone-containing monomer represented by the chemical formula 2 in the step 1-1 is not particularly limited, but may be included in an amount of 1 to 70 wt%, for example, relative to 100 wt% of the total sum of the water-soluble monomer represented by the chemical formula 1, the crosslinkable monomer, and the silicone-containing monomer represented by the chemical formula 2, preferably 5 to 60 wt%, and more preferably 10 to 50 wt%. Within the above range, the stability of the composition may be more excellent or the stickiness-improving effect may be more excellent.

In one specific example, the organic solvent may be a nonpolar organic solvent, and specifically, may be a C _6-17 hydrocarbon oil, and may be a C _6-17 straight-chain saturated hydrocarbon oil. If the carbon number is out of the above range, the production efficiency in the polymerization reaction may be reduced.

In one specific example, heptane can be used as the nonpolar organic solvent. Heptane has a boiling point of 98°C and is not subject to restrictions in the polymerization process according to the present invention compared to other organic solvents. During the process, there is a risk that heat generation occurs due to an explosive reaction during the initiator injection process, and the temperature inside the reactor may rise by about 5-10°C. The method of slowly injecting the initiator to maintain the stability of the reaction temperature has the disadvantage of increasing the process time when applied to a mass production process, which increases the production cost. In addition, since the risk of the reactor exploding due to the reaction product being bumped when heated above the boiling point increases, reaction heat management is a very important factor during mass production. Therefore, in the present invention, by using heptane as the organic solvent, the thickener desired by the present invention can be easily manufactured without any restrictions in the process.

In the present invention, the oil phase of step 1-1 may further include a surfactant.

In one specific example, one or more surfactants may be used as the surfactant of the step 1-1. The total HLB value of the surfactants may be 6 to 14, 7 to 10, or 8 to 9. At this time, the total HLB value may mean the HLB value of one surfactant when one surfactant is used, and may mean the sum of the HLB values of two or more surfactants when two or more surfactants are used. When the total HLB value is 6 or less, due to the strong hydrophobicity of the surfactant, the water-in-oil type reversed phase emulsion exists from room temperature and polymerizes without a phase transition process, so the effect of reducing the size of the emulsion may not be sufficient. In addition, when the total HLB value is 14 or more, due to the strong hydrophilicity of the surfactant, the oil-in-water emulsion with the outer phase as the water phase is maintained, so that spherical particles are not formed, and there is a concern that the amorphous state of the manufactured thickener may increase.

In one specific example, two types of surfactants can be used as the surfactants of step 1-1. In this case, a surfactant having an HLB value of 3 to 8 and a surfactant having an HLB value of 8 to 16 can be used in combination, or a surfactant having an HLB value of 5 to 7 and a surfactant having an HLB value of 9 to 11 can be used in combination.

In one specific example, polyoxyethylene (3) oleyl ether (HLB = 6.6) and polyoxyethylene (6) oleyl ether (HLB = 9.6) may be used in combination as the surfactant of step 1-1. Specifically, polyoxyethylene (3) oleyl ether (HLB = 6.6) and polyoxyethylene (6) oleyl ether (HLB = 9.6) may be used in combination at a weight ratio of 1:1, and at this time, the HLB value may be 8.1.

Specifically, by appropriately combining a surfactant having an HLB value of 3 to 8 and two surfactants having an HLB value of 8 to 16, or a surfactant having an HLB value of 5 to 7 and two surfactants having an HLB value of 9 to 11, a PIT (phase inversion temperature) polymerization method in which the polymerization is converted into an oil-in-water (o/w) emulsion phase at room temperature or a water-in-oil (w/o) emulsion phase above a certain temperature can be used to cause a polymerization reaction to proceed in a uniform reverse emulsion phase having a small particle size. Through this, the present invention can produce a thickener in the form of homogeneous spherical fine particles.

The thickener in the form of spherical fine particles polymerized in the above manner has the advantage of not only maintaining the shape of the particles even when swelling in a water phase, but also having a transparent appearance and high stability due to uniform particle dispersion.

In one specific example, the content of the surfactant in step 1-1 is not particularly limited, but may vary depending on the type of the organic solvent. Specifically, the content of the surfactant may be 5 to 30 wt% with respect to 100 wt%, which is the total sum of purified water, the organic solvent, the surfactant, the water-soluble monomer represented by the chemical formula 1, the crosslinking monomer, and the silicone-containing monomer represented by the chemical formula 2. In the above content range, phase inversion of the emulsion is possible, and PIT polymerization can be easily performed.

In one specific example, the weight ratio of the water phase and the oil phase in step 1-1 may be 30:70 to 70:30. Within this range, the composition may be more stabilized or have a better stickiness improvement effect.

In the present invention, the step 1-2 is a step of preparing a water-in-oil type reverse phase emulsion composition by heating to 60°C or higher. The heating in the step 1-2 can be performed at 50°C to 80°C, preferably 55°C to 75°C, and if heated to less than 50°C, there is a problem that it is difficult for the phase transition phenomenon of the emulsion to occur.

In one specific example, the emulsion prepared in step 1-1 of the present invention has an oil-in-water type at room temperature, but can be transformed into a water-in-oil type emulsion by step 1-2. The emulsion produced by the transformation can have the effect of reducing the size of the emulsion, and can have the effect of reducing the particle size of the polymer prepared in the step described below.

In one specific example, the reaction temperature of step 1-2 may be, for example, 62°C or higher, 65°C or higher, 70°C or higher, or 75°C or higher, and its upper limit may be 100°C. A thickener can be manufactured more stably in the above temperature range.

In the present invention, steps 1-3 are steps for producing a cross-linked polymer by adding a reaction initiator and performing a polymerization reaction.

In one specific embodiment, the type of the reaction initiator of steps 1-3 is not particularly limited to a typical radical polymerization initiator, but may be selected from the group consisting of, for example, peroxides and azo compounds. As the peroxide initiator, benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, cumyl hydroperoxide, hydrogen peroxide, or potassium persulfate may be used, and as the azo compound initiator, azo nitrile, azo ester, azo amide, azo imidazolin, azo amidine, Macro Azo initiator, or the like may be used. In the present invention, it may be advantageous in terms of polymerization efficiency to use an azo compound initiator, more preferably 4,4'-Azobis(4-cyanovaleric acid).

In the present invention, after preparing a reverse emulsion, an initiator is added and reacted to obtain a crosslinked polymer having the viscosity desired by the present invention, i.e., a thickener, and the yield of the thickener can be increased.

In one specific example, the steps 1-3 may be at a reaction temperature of 62°C or higher, 65°C or higher, 70°C or higher, or 75°C, and the upper limit thereof may be 100°C. A thickener can be manufactured more stably within the above temperature range.

In one specific embodiment, steps 1-3 may be performed for a reaction time of 1 to 12 hours, preferably 2 to 6 hours.

In another specific embodiment of the present invention, the method for producing an amphiphilic thickener of the present invention comprises the steps of dissolving a water-soluble monomer represented by the chemical formula 1, a crosslinkable monomer, and a silicone-containing monomer represented by the chemical formula 2 in an alcohol-based solvent (step 2-1);

Step of heating to 60℃ or higher (Step 2-2); and

A step (step 2-3) of producing a cross-linked polymer by adding a reaction initiator and performing a polymerization reaction may be included.

In one specific example, the method for producing the amphiphilic thickener may be, in particular, a precipitation polymerization method. The water-soluble monomer of chemical formula 1, the silicone-containing monomer of chemical formula 2, the crosslinking monomer, and the reaction initiator used in the precipitation polymerization method may be the same as those used in the PIT polymerization method.

In one specific example, the alcohol solvent used as the solvent may be a C _2-8 alcohol. The reaction yield can be further increased within the above range.

In the present invention, the solution itself in which the cross-linked polymer is formed by the above-described manufacturing method can be used as a thickener. In addition, the solution can be precipitated with a precipitating agent to finally manufacture a thickener in a solid form such as a powder. At this time, a precipitating agent non-solvent can be used, and in particular, acetone can be used.

In addition, the present invention provides a thickener manufactured by the method for manufacturing a thickener described above.

Figure 1 is an exemplary diagram illustrating a method for manufacturing a polymer thickener according to the present invention (steps 1-1 to 1-3).

The thickener according to the present invention may be in the form of a spherical thickener manufactured by the same method as in Fig. 1.

The thickener according to the present invention may be in the form of a spherical thickener manufactured by the method as shown in Fig. 2.

The thickener according to the present invention has a spherical fine particle form and can swell in water, ethanol or a water-ethanol mixed solution to provide a high viscosity solution that is visually uniform in appearance.

The thickener manufactured by the present invention may have an average particle diameter of 10 to 300 um.

Additionally, the thickener manufactured in the present invention may have a viscosity of 500 to 150,000 cPs, or 5,000 to 100,000 cPs at 25°C in a 1% (w/v) aqueous dispersion.

Hereinafter, the present invention will be described in more detail through implementation/comparative examples. These examples are intended only to illustrate the present invention, and the scope of the present invention is not limited by these examples.

[Example]

Comparative example 1.

Solution: Dissolve 17 g of acrylamidomethylpropanesulfonic acid and 0.5 g of trimethylolpropane ethoxylate triacrylate in 63 g of distilled water, then neutralize to pH 7-9 with ammonia water.

Yusang: Add 10g each of polyoxyethylene (3) oleyl ether and polyoxyethylene (6) oleyl ether to 80g of heptane and mix well.

The water and oil phases were placed in a reactor and heated to 70°C. 0.1 g of the initiator 4,4′-Azobis (4-cyanovaleric acid) was added and reacted for 3 hours. The thickener was precipitated with acetone and dried to obtain the product.

Comparative Example 2

Solution: Dissolve 17 g of acrylamidomethylpropanesulfonic acid and 0.5 g of trimethylolpropane ethoxylate triacrylate in 63 g of distilled water, then neutralize to pH 7-9 with ammonia water.

Yusang: Add a certain amount of silicone methacrylate (molecular weight: 5,000) to 80g of heptane and mix well.

The water and oil phases were placed in a reactor and heated to 70°C. 0.1 g of the initiator 4,4′-Azobis (4-cyanovaleric acid) was added and reacted for 3 hours. The thickener was precipitated with acetone and dried to obtain the product.

In this case, it appears that emulsion polymerization using an emulsifier is necessary because the reaction that proceeded without an emulsifier did not result in a uniform reaction and a gel of a form that was difficult to use for testing was formed.

Examples 1 to 3.

Solution: Dissolve 17 g of acrylamidomethylpropanesulfonic acid and 0.5 g of trimethylolpropane ethoxylate triacrylate in 63 g of distilled water, then neutralize to pH 7-9 with ammonia water.

Yusang: Add a certain amount of silicone methacrylate (molecular weight: 1,000 / 5,000 / 10,000) to 80g of heptane, add 10g each of polyoxyethylene (3) oleyl ether and polyoxyethylene (6) oleyl ether, and mix well.

The water and oil phases were placed in a reactor and heated to 70°C. 0.1 g of the initiator 4,4′-Azobis (4-cyanovaleric acid) was added and reacted for 3 hours. The thickener was precipitated with acetone and dried to obtain the product.

Each composition is shown in Table 1 below.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 premier
(unit g) Distilled water 63 63 63 63 63 Acrylamidomethylpropanesulfonic acid 17 17 17 17 17 Trimethylolpropane oxylate triacrylate 0.5 0.5 0.5 0.5 0.5 ammonia Chinese Chinese Chinese Chinese Chinese Paid
(unit g) Heptane 80 80 80 80 80 Silicone methacrylate (molecular weight 1,000) - - 3.4 - - Silicone methacrylate (molecular weight 5,000) - 3.4 - 3.4 - Silicone methacrylate (molecular weight 10,000) - - - - 3.4 Polyoxyethylene (3) oleyl ether 10 - 10 10 10 Polyoxyethylene (6) oleyl ether 10 - 10 10 10 4,4′-Azobis(4-cyanovaleric acid) 0.1 0.1 0.1 0.1

Comparative example 3.

20 g of acrylamidomethylpropanesulfonic acid and 1 g of trimethylolpropane ethoxylate triacrylate were added to 100 g of t-butanol, then 6.4 g of ammonia water was added and stirred for 30 minutes to completely dissolve.

After heating to 70℃, 0.3 g of the initiator 4,4′-Azobis (4-cyanovaleric acid) was added and reacted for 3 hours, and the thickener was precipitated with ethanol and acetone and dried to obtain the product.

Example 4

To 100 g of t-butanol, 20 g of acrylamidomethylpropanesulfonic acid and 1 g of trimethylolpropane ethoxylate triacrylate were added, then 6.4 g of ammonia water was added and stirred for 30 minutes to completely dissolve. Then, a certain amount of silicone methacrylate (molecular weight: 5,000) was added and mixed well.

After heating to 70℃, 0.3 g of the initiator 4,4′-Azobis (4-cyanovaleric acid) was added and reacted for 3 hours, and the thickener was precipitated with ethanol and acetone and dried to obtain the product.

The compositions are shown in Table 2 below (unit: g).

Comparative Example 2 Example 4 t-butanol 100 100 Acrylamidomethylpropanesulfonic acid 20 20 Trimethylolpropane oxylate triacrylate 1 1 ammonia 6.4 6.4 Silicone methacrylate (molecular weight 5,000) - 6 4,4′-Azobis(4-cyanovaleric acid) 0.3 0.3

Experimental Example 1. Comparison of moisture retention capacity (Figure 3)

Dissolve 1 g of each thickener prepared according to the compositions of Comparative Examples 1 and 3 and Examples 1 to 4 in 99 g of distilled water. Then, transfer 10 g of the polymer solution at 55°C to a petri dish and place it in an oven. The weight of the sample was measured over time to check the amount of moisture evaporation. The results are shown in Fig. 3.

As a result, as shown in Fig. 3, the thickeners of Examples 1 to 4 showed a significantly increased moisture retention time compared to Comparative Examples 1 and 3. This means that when silicone is coated, moisture evaporation is suppressed in the core portion of the polymer that retains moisture, thereby increasing the moisturizing power.

Experimental Example 2. Comparison of smudging when applying colored cosmetics

First, a color cosmetic formulation was prepared as shown in Table 3 below.

The raw materials corresponding to the oil phase were first mixed and melted by heating to 80℃. In the meantime, the water phase was added and melted, and then the water phase was added to the oil phase and homomixed at 5000 rpm for 10 minutes to prepare a formulation.

The manufactured formulation was dropped 30 μl at a time on a marble floor, spread thinly to a thickness of 25 μm, and dried for 4 hours. 10 μl of artificial sebum was dropped on the dried formulation, left at room temperature for 10 minutes, and then artificial leather was covered and a 200 g weight was applied by reciprocating 10 times. The covered artificial leather was removed, and the amount of colored cosmetics on the leather was visually compared. The results are shown in Fig. 4.

Ingredient name (unit g) Color tone 1 Color tone 2 Color tone 3 Color tone 4 Color tone 5 Color tone 6 premier Purified water 24.5 22.5 22.5 22.5 22.5 22.5 Sodium polystyrene sulfonate 1 1 1 1 1 1 1,2-Hexanediol 1.5 1.5 1.5 1.5 1.5 1.5 Comparative Example 1 - 2 - - - - Example 1 - - 2 - - - Example 2 - - - 2 - - Example 3 - - - - 2 - Example 4 - - - - - 2 Paid Cyclopentasiloxane 30 30 30 30 30 30 Caprylic/Capric Triglyceride 6 6 6 6 6 6 Silicone acrylate 0.5 0.5 0.5 0.5 0.5 0.5 Diphenylsiloxyphenyl trimethicone 2 2 2 2 2 2 Trimethylsiloxysilicate 5 5 5 5 5 5 Lauryl PEG-9 polydimethylsiloxy decyl dimethicone 3 3 3 3 3 3 Cetyl PEG/PPG-10/1 Dimethicone 1 1 1 1 1 1 Dimethicone/Phynyldimethicone crosspolymer 5 5 5 5 5 5 Quaternium-18 hectorite 0.5 0.5 0.5 0.5 0.5 0.5 Pigment No. 21 20 20 20 20 20 20 Total 100 100 100 100 100 100

As shown in Fig. 4, it was confirmed that the higher the molecular weight of silicone methacrylate, the less the color cosmetics were smudged. When no polymer was used, the color cosmetics had almost no sebum resistance, and in the case of the polymer that was not coated with silicone methacrylate, the color cosmetics were smudged at a high level. It is believed that this is because the silicone coated on the spherical polymer surface adheres to each other and forms a film when the formulation is set, thereby exhibiting sebum resistance and water resistance.

Experimental Example 3. Comparison of stickiness when applying color cosmetics

Each color cosmetic of Experimental Example 2 was dropped at 10 μl on artificial leather and spread to 2 X 2 (cm), and the stickiness according to the drying time was measured. A cylindrical applicator was used as a texture analyzer device, and the measurement parameters were set to a measurement speed of 1 mm/s and a measurement force of 1.0 g, and the stickiness was calculated as the negative energy at the point when the applicator first touched the dried formulation. The results are shown in Table 4 below.

Color tone 1 Color tone 2 Color tone 3 Color tone 4 Color tone 5 Color tone 6 Stickiness (gf·s) 14.4 16.5 12.1 8.6 6.5 6.7

As shown in Table 4, when a general water-dispersing polymer was used, the stickiness was very strong, but when silicone methacrylate was used, the stickiness was less. This is because when a water-dispersing polymer is used to solve the dryness of a color product, the dryness is reduced, but the stickiness increases. Therefore, in order to reduce the stickiness while maintaining the moisture, a spherical polymer coated with silicone methacrylate can be used to solve the problem.

Experimental Example 4. Comparison of stickiness when applying UV-blocking cosmetics

First, a UV-blocking cosmetic formulation was prepared as shown in Table 5 below.

First, mix the raw materials corresponding to the oil phase and heat to 80℃ to melt. In the meantime, add the water phase and melt it. Then, add the water phase to the oil phase and homomix at 4000 rpm for 10 minutes to prepare the formulation.

After dropping 3 μl of UV-blocking cosmetics (sunscreen) on artificial leather, the stickiness was measured according to the number of times the applicator touched it. A ball-shaped applicator was used as a texture analyzer device, and the measurement parameters were set to a measurement speed of 1 mm/s and a measurement force of 1.0 g, and the experiment was repeated 200 times. The stickiness was calculated as the negative energy at the point where the applicator touched the formulation. The results are shown in Fig. 5.

Paid Ingredient name Sunscreen 1 Sunscreen 2 Cetyl ethylhexanoate 2.00 2.00 Ethylhexyl salicylate 20.00 20.00 Sorbitan Olivate 0.50 0.50 Hydrogenated polyisobutene 2.00 2.00 Cetearyl alcohol 2.00 2.00 Glyceryl stearate 0.50 0.50 Cyclopentasiloxane 10.00 10.00 premier Purified water 53.68 54.08 Example 2 - 0.30 Tromethamine 0.30 0.15 Dipropylene glycol 5.00 5.00 1,2-Hexanediol 1.00 1.00 Cetyl phosphate 2.5 2.5 Carbomer 0.50 0.25 Trisodium EDTA 0.02 0.02 Total 100.0 100.0

As shown in Fig. 5, when a general polymer was used, the stickiness was very strong, but when silicone methacrylate was used, the stickiness was confirmed to be less. This can be solved by using a spherical polymer coated with silicone methacrylate to reduce stickiness while maintaining moisture in UV-blocking products, as in color products.

Experimental Example 5. Comparison of UV protection performance duration when applying UV protection cosmetics

In Experimental Example 4, 33.5 μg of the sunscreen was spread thinly on a 5 X 5 (cm) UV protection factor measuring PMMA plate (Helioplate, Helioscreen, France). After 15 minutes, the initial UV protection factor (SPF) was measured using an in vitro measuring device, and after 4 hours, 10 μg of artificial sebum was dropped and spread on the PMMA plate to which the sunscreen had been applied, and the SPF value was measured again after 10 minutes to confirm the change in SPF. The results are shown in Table 6 below.

SPF beginning Later Decrease rate (%) Sunscreen 1 53.3 26.0 51.3 Sunscreen 2 51.5 36.8 28.6

As shown in the above results, it was confirmed that when a spherical thickener coated with silicone methacrylate was used, the SPF reduction rate was lower than that of sunscreens made using general polymers. This shows that, similar to Experimental Example 2 above, the anti-sebum properties observed in colored cosmetics are also applied to UV-blocking cosmetics, thereby increasing the durability of UV-blocking performance.

Experimental Example 6. Real-use test on stickiness and moisture when applying skin formulation

First, a skin formulation for exfoliation was prepared as shown in Table 7 below.

The skin formulation was applied to the face once a day for 3 days to 20 women aged 25 to 50. After application, a questionnaire was conducted on the feeling of use. Each feeling of use was evaluated using the criteria of “◎: 16 or more out of 20 subjects said it was not sticky or had a high moisture content, ○: 12 to 15 out of 20 subjects said it was not sticky or had a high moisture content, △: 8 to 11 out of 20 subjects said it was not sticky or had a high moisture content.” The results are shown in Table 7 below.

Ingredient name (unit weight%) Skin 1 Skin 2 Skin 3 Skin 4 Skin 5 Purified water To 100 To 100 To 100 To 100 To 100 Dexpanthenol 0.500 0.500 0.500 0.500 0.500 1,2-Hexanediol 4.000 1.000 1.000 1.000 1.000 Dipropylene glycol 8.000 8.000 8.000 8.000 8.000 Xanthan gum 0.400 0.400 0.400 0.400 0.400 Example 2 - 0.25 0.5 - - Example 4 - - - 0.25 0.5 Gluconolactone 3.000 3.000 3.000 3.000 3.000 Lactic acid 3.000 3.000 3.000 3.000 3.000 Total 100.000 100.000 100.000 100.000 100.000 Less sticky △ ○ ◎ ○ ◎ Moisture ○ ○ ◎ ○ ◎

As can be seen from the results shown in Table 7, the exfoliating ingredient in the formulation for exfoliating has high stickiness, but when the polymer provided by the present invention is used, the stickiness is reduced and the moisture content is increased.

Claims (17)

A step for preparing an oil-in-water emulsion composition comprising an aqueous phase comprising a water-soluble monomer and a crosslinking monomer, and an oil phase comprising a silicone-containing monomer represented by the following chemical formula 2 and a non-polar organic solvent;
A step of preparing a water-in-oil type reverse phase emulsion composition by heating to 60℃ or higher; and
A method for producing an amphiphilic thickener, comprising: a step of adding a reaction initiator to cause a polymerization reaction to produce a cross-linked polymer, wherein the water-soluble monomer comprises at least one selected from the group consisting of acrylamidomethylpropanesulfonic acid (AMPS), acrylic acid, acrylamide, and polyethylene glycol acrylate, and the cross-linked polymer is formed in a core-shell structure:
[Chemical formula 2]

In the above formula,
m is an integer from 1 to 5,
n is an integer between 10 and 5000,
R ₁ is hydrogen or a C _1-3 alkyl group,
R ₂ is a hydroxy group, a C _1-3 alkyl group, or a vinyl group.
In the first paragraph,
A method for producing an amphiphilic thickener, wherein the amphiphilic thickener is contained in an amount of 50 to 95 wt% based on 100 wt% of the total sum of the water-soluble monomer, the crosslinking monomer, and the silicone-containing monomer represented by the chemical formula 2.
In the first paragraph,
A method for producing an amphiphilic thickener, wherein the crosslinking monomer is a compound having two or more acrylate groups, two or more acrylamide groups, or two or more vinyl groups.
In the first paragraph,
A method for producing an amphiphilic thickener, wherein the above nonpolar organic solvent is a C _6-17 hydrocarbon oil.
In the first paragraph,
A method for producing an amphiphilic thickener, wherein the silicone-containing monomer represented by the chemical formula 2 is included in an amount of 5 to 50 wt% based on 100 wt% of the total sum of the water-soluble monomer represented by the chemical formula 1, the crosslinkable monomer, and the silicone-containing monomer represented by the chemical formula 2.
In the first paragraph,
A method for producing an amphiphilic thickener, wherein the oil further comprises one or more surfactants, and the total HLB value of the combination of said surfactants is from 6 to 14.
In paragraph 6,
A method for producing an amphiphilic thickener, wherein the above surfactant uses two types of surfactants: a surfactant having an HLB value of 3 to 8 and a surfactant having an HLB value of 8 to 16.
In the first paragraph,
A method for producing an amphiphilic thickener, wherein the above reaction initiator is at least one selected from the group consisting of peroxides and azo compounds.
In the first paragraph,
A method for producing an amphiphilic thickener, wherein the above polymerization reaction is performed at 60°C or higher for 2 to 6 hours.
In paragraph 1,
A method for producing an amphiphilic thickener, further comprising the step of obtaining the thickener in a solid form by precipitating it with a precipitating agent.
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