KR102477498B1 - Oil in water typed silicon elastomer and the Manufacturing method thereof - Google Patents

Abstract

The present invention relates to a silicone elastomer and a method for producing the same, and more specifically, a method for preparing a silicone elastomer used in cosmetics by an emulsion polymerization synthesis method, which has excellent flexibility and can form a soft and refreshing feeling on the skin. It relates to an emulsified silicone elastomer in the form of heavy oil.

Description

Oil in water typed silicon elastomer and the Manufacturing method thereof

The present invention relates to an oil-in-water silicone elastomer that can be used only by simple dispersion when applied to an aqueous phase with even particles used in cosmetics, and a method for manufacturing the same.

Silicone oil is widely used for reasons of fresh feeling of use and excellent safety in the use of cosmetics such as skin care and makeup. Among them, silicone elastomer is used in the form of soft, fresh feeling of use and filling of skin pores. In addition, when basic cosmetics and makeup cosmetics are applied to the skin and time elapses, a phenomenon in which makeup does not last long due to sebum discharged from the skin appears, and the durability of cosmetics due to sebum can be increased by absorbing such sebum.

This silicone elastomer is formed by crushing the elastomer and adding a carrier solvent to it for use in cosmetics. difficult. In addition, the cosmetic silicone elastomer formed in this way is a non-polar material when applied to cosmetics, and if it is to be separately dispersed in the water phase, it must be emulsified by adding an emulsifier. difficult to represent equally.

In addition, silicone elastomer is a relatively non-polar material compared to most water, and it is difficult to contain a polar material capable of exhibiting various effects on the skin inside the elastomer.

Therefore, when forming the elastomer, the particles can be uniformly formed using emulsion polymerization technology, and when applied to the water phase, a silicone elastomer that can be used only by simple dispersion is required.

US registered patent number US 6,936,686 B2 (2005.08.30)

The present invention was made to solve the above problems, and provides a method for preparing a silicone elastomer with improved productivity, dispersibility and particle homogeneity of the silicone elastomer by emulsion polymerization and an oil-in-water silicone elastomer prepared with an optimal composition and composition ratio want to do

The oil-in-water (O/W) silicone elastomer of the present invention for solving the above problems is an emulsion by mixing and reacting an emulsifier, a polysiloxane represented by the following formula (1), a polysiloxane represented by the following formula (2), and a catalyst; and thickeners; preservatives; and a compatibilizer.

[Formula 1]

R ¹ _a R ² _3-a SiO (R ² ₂ SiO) _x SiR ¹ _a R ² _3-a

In Formula 1, R ¹ is an aliphatic unsaturated hydrocarbon group having a vinyl group, allyl group, butadienyl group or hexenyl group at the terminal, R ² is an alkyl group or aryl group having 1 to 8 carbon atoms, x is 30 to 1,000, a is 1 to 3,

[Formula 2]

R ¹ _a R ² _3-a SiO (R ¹ _b R ² _2-b SiO) _x (R ² ₂ SiO) _yx SiR ¹ _a R ² _3-a

In Formula 2, R ¹ is a hydrogen atom or an alkyl group containing -OH, R ² is an alkyl group or aryl group having 1 to 8 carbon atoms, the molar ratio of x and y is 1: 1 to 199, and the sum of x and y is 8 to 500, a is 0 to 3, and b is 1 to 2.

As a preferred embodiment of the present invention, the emulsion contains 0.5 to 10% by weight of an emulsifier, 2.0 to 40.0% by weight of a polysiloxane represented by Formula 1, 0.4 to 20% by weight of a polysiloxane represented by Formula 2, 0.00001 to 0.24000% by weight of a catalyst, and Residual water may be included.

As a preferred embodiment of the present invention, the emulsion may further include 1 to 85% by weight of a carrier solvent.

As a preferred embodiment of the present invention, the carrier solvent may include at least one selected from dimethicone, linear volatile siloxane, cyclic volatile siloxane, branched volatile siloxane, and hydrocarbon oil.

As a preferred embodiment of the present invention, the linear volatile siloxane is one selected from hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetramethylhexasiloxane, and hexadecamethylheptasiloxane. may contain more than

As a preferred embodiment of the present invention, the cyclic volatile siloxane may include at least one selected from hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.

As a preferred embodiment of the present invention, the emulsion may further include at least one selected from polyhydric alcohol ethers having aliphatic unsaturated bonds and polyhydric alcohol esters having aliphatic unsaturated bonds.

As a preferred embodiment of the present invention, the oil-in-water silicone elastomer of the present invention may include 0.1 to 5.0 parts by weight of a thickener, 0.1 to 2 parts by weight of a preservative, and 1 to 400 parts by weight of a compatibilizer based on 100 parts by weight of the emulsion. have.

As a preferred embodiment of the present invention, the thickener may include at least one selected from ionic polymers, salts of ionic polymers, and nonionic polymers.

As a preferred embodiment of the present invention, the preservative may include at least one selected from parabens, salts of parabens, benzoic acid, salts of benzoic acid, phenoxyethanol, and dialkylglycerin.

As a preferred embodiment of the present invention, the compatibilizer may include a polyhydric alcohol having 2 to 20 carbon atoms.

As a preferred embodiment of the present invention, the oil-in-water silicone elastomer of the present invention may have a viscosity of 5,000 to 50,000 cPs at 25 °C.

As a preferred embodiment of the present invention, the water-in-water silicone elastomer of the present invention may satisfy a D ₅₀ value of 2.5 to 5.0 μm upon particle size distribution analysis.

As a preferred embodiment of the present invention, the water-in-water silicone elastomer of the present invention may satisfy Equations 1 and 2 below when analyzing particle size distribution.

[Equation 1]

(D ₅₀ -D ₁₀ ) < 1.50 μm

[Equation 2]

(D ₉₀ -D ₅₀ ) < 2.80 μm

In Equation 1 and / or 2, D ₁₀ , D ₅₀ and D ₉₀ are respectively measured when the particle size distribution of the water-in-water silicone elastomer is 10%, 50% and 90% of the particle size distribution. is the value

Another object of the present invention relates to a method for preparing the oil-in-water silicone elastomer described above by emulsion polymerization, by mixing and emulsion-polymerizing an emulsifier, a polysiloxane represented by Formula 1, a polysiloxane represented by Formula 2, and a catalyst. Step 1 of preparing an emulsion; And a second step of adding and stirring a thickener, a preservative and a compatibilizer to the emulsion; it is prepared by performing a process including.

As a preferred embodiment of the present invention, the first step of emulsion polymerization may be carried out at 40 to 80 °C.

As a preferred embodiment of the present invention, in the second step, the reactant in the first step is cooled to 30 to 40 ° C., a thickener, a preservative and a compatibilizer are added, and the final product can be obtained by sufficiently stirring.

The water-in-water silicone elastomer of the present invention has excellent productivity and excellent dispersibility in water, and the homogeneity of the silicone elastomer particles is very even. Cosmetics with excellent filling effect can be manufactured.

1a to 1c are particle analysis measurement results of silicone elastomer performed in Experimental Example 2.
2 is a water dispersibility measurement result conducted in Experimental Example 3.

Hereinafter, the present invention will be described in more detail through a manufacturing method.

It relates to a method for preparing the oil-in-water silicone elastomer of the present invention by emulsion polymerization, comprising the steps of preparing an emulsion; And a second step of adding and stirring a thickener, a preservative and a compatibilizer to the emulsion; it is prepared by performing a process including.

The emulsion in the first step may be prepared by mixing and emulsion polymerization of an emulsifier, a polysiloxane having an aliphatic unsaturated bond, a polysiloxane having hydrogen-bonded silicon, and a catalyst.

The emulsifier may include at least one selected from anionic emulsifiers, nonionic emulsifiers, and cationic emulsifiers.

Among the emulsifier components, the anionic emulsifier includes an alkaline anionic emulsifier in which a fatty acid having 12 to 20 carbon atoms is saponified with an alkali, a higher alcohol or polyethylene glycol having 10 to 20 carbon atoms in strong acids such as sulfuric acid and phosphoric acid. It may include acidic anionic emulsifiers in the form of esters or amides and neutral and alkaline anionic emulsifiers neutralized with alkali.

In addition, among the emulsifier components, the nonionic emulsifier is a polyhydric alcohol, polyethylene glycol, a polymer of polyhydric alcohol, a polymer in which polyethylene is introduced into a polyhydric alcohol, and a hydrophilic component in which (poly)glycerin is introduced into a polyhydric alcohol has 10 to 10 carbon atoms. It may include an ester compound or an ether compound having 22 alkyl chains, and a preferred example is polyglyceryl-10 laurate, polyglyceryl-10 myristate, It may include at least one selected from polyglyceryl-10 palmitate and polyglyceryl-10 stearate.

In addition, the cationic emulsifier may include a betaine-based cationic emulsifier or a lecithin-based emulsifier.

In addition, the content of the emulsifier may include 0.5 to 10% by weight, preferably 0.8 to 8% by weight, more preferably 1.0 to 6.5% by weight of the total weight of the emulsion, and the emulsifier content is less than 0.5% by weight or Or, if it exceeds 10% by weight, an oil-in-water emulsion may not be formed.

Among the emulsion components, the polysiloxane having an aliphatic unsaturated bond may include polysiloxane represented by Formula 1 below. And, the content of the polysiloxane represented by Formula 1 may include 2.0 to 40.0% by weight, preferably 2.0 to 25% by weight, more preferably 2.0 to 10% by weight, based on the total weight of the emulsion. If the displayed polysiloxane content is less than 2.0% by weight, the form of the elastomer cannot be represented, and if it exceeds 40.0% by weight, there may be a problem in that the oil-in-water emulsion cannot be represented due to the high content in the oil-in-water emulsion.

[Formula 1]

R ¹ _a R ² _3-a SiO (R ² ₂ SiO) _x SiR ¹ _a R ² _3-a

In Formula 1, R ¹ is an aliphatic unsaturated hydrocarbon group having a vinyl group, an allyl group, a butadienyl group, or a hexenyl group at the terminal, preferably C containing a vinyl group, an allyl group, a butadienyl group, or a hexenyl group at the terminal. It is an alkylene group of ₂ to C ₅ . R ² in Formula 1 is a C ₁ to C ₈ alkyl or aryl group, preferably a C ₁ to C ₃ alkyl or phenyl group. In Formula 1, x is 30 to 1,000, preferably x is 70 to 500, and a is 1 to 3.

Next, among the emulsion components, the polysiloxane having hydrogen-bonded silicon may include polysiloxane represented by Formula 2 below. The content of the polysiloxane represented by Formula 2 may include 0.4 to 25.0% by weight, preferably 0.4 to 10.0% by weight, more preferably 0.45 to 2.00% by weight, based on the total weight of the emulsion. If the polysiloxane content is less than 0.4% by weight, the form of the elastomer cannot be exhibited, and if it exceeds 25% by weight, there may be a problem in that hydrogen gas is generated due to the high hydrogen content.

[Formula 2]

R ¹ _a R ² _3-a SiO (R ¹ _b R ² _2-b SiO) _x (R ² ₂ SiO) _y SiR ¹ _a R ² _3-a

In Formula 2, R ¹ is a hydrogen atom or an alkyl group containing -OH, preferably a hydrogen atom. R ² in Formula 2 is a C ₁ to C ₈ alkyl or aryl group, preferably a C ₁ to C ₃ alkyl or phenyl group. The molar ratio of x and y in Formula 2 is 1:1 to 199, preferably the molar ratio of x and y is 1:1 to 10, and the sum of x and y is 8 to 500. In Formula 2, a is 0 to 3, b is 1 to 2, preferably a is 1 to 3, and b is 1 to 2.

Next, the catalyst of the emulsion component may be a silicidation catalyst that is hydrated with a platinum group metal including at least one selected from ruthenium, rhodium, palladium, osmium, iridium, and platinum, which are platinum group. , Karstedt's catalyst (US Pat. No. 3,715,334A and 3,814,730A) containing chloroplatinic acid and polysiloxane having terminal aliphatic unsaturation, or siloxane containing unsaturated hydrocarbons, platinum containing acetylenic alcohol can be a catalyst. The catalyst content may contain 0.00001 to 0.24000% by weight of the catalyst, preferably 0.00001 to 0.10000% by weight, based on the total weight of the emulsion as the content of undiluted pure catalyst. In addition, at 0.24000% by weight or more, it is difficult to form an oil-in-water emulsion due to a too fast reaction rate, and browning occurs over time, which may cause a problem of deterioration in quality as a cosmetic.

When the emulsion of the first step is used as a cosmetic, the elastomer may further include a carrier solvent to deliver effective ingredients to the skin, such as improving the feeling of use on the skin, whitening, wrinkle improvement, sunscreen, etc. to the skin. The carrier solvent may include at least one selected from dimethicone, linear volatile siloxane, cyclic volatile siloxane, branched volatile siloxane and hydrocarbon oil, preferably dimethicone, linear volatile siloxane and cyclic volatile siloxane One or more selected species may be used, and more preferably, dimethicone having a weight average molecular weight of 550 to 1350 may be used.

The linear volatile siloxane may include at least one selected from hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetramethylhexasiloxane, and hexadecamethylheptasiloxane, and the cyclic Volatile siloxane may include at least one selected from hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. In addition, as the hydrocarbon oil, linear or branched hydrocarbon oil having 8 to 24 carbon atoms may be used, and preferably, at least one selected from isododecane and isohexadecane may be included. Whether or not to use the carrier solvent is optional, and when using the carrier solvent, it is recommended to use 1 to 85% by weight, preferably 60 to 85% by weight, more preferably 70 to 85% by weight, based on the total weight of the emulsion. It is good, and if the carrier solvent content exceeds 85% by weight in the emulsion, it may be difficult to form a silicone elastomer.

In addition, the carrier solvent may contain an effective material such as an organic/inorganic sunscreen, niacinamide, adenosine, arbutin, and/or bisabolol.

In addition, the emulsion in the first step may further include at least one selected from ethers of polyhydric alcohols having aliphatic unsaturated bonds and esters of polyhydric alcohols having aliphatic unsaturated bonds for the effect of including a hydrophilic component in the silicone elastomer, Preferably, sucrose-linked alkyl esters are suitable.

In step 1, the emulsion composition described above is mixed by a general mixing method used in the art, preferably a homomixer or an azimixer, and then mixed at 40 to 80 ° C, preferably 45 to 70 ° C, more preferably 45 to 60 ° C. An emulsion may be prepared by carrying out an emulsion polymerization reaction at °C. If the reaction temperature is less than 45 ℃ during the emulsion polymerization reaction, there may be a problem that the reaction cannot be performed, and if the reaction temperature exceeds 80 ℃ during the emulsion polymerization reaction, the reaction is accelerated or the emulsion droplets are coalesced, resulting in non-uniform particle size. Since there may be, it is preferable to carry out the emulsion polymerization reaction in the above temperature range.

In the emulsion containing the oil-in-water silicone emulsion polymer prepared in step 1, the specific gravity of the dispersion is lower than that of the continuous phase. If contained, microbial growth may occur. Therefore, a thickening agent, a preservative and/or a compatibilizing agent are included to ensure stability.

The thickening agent may include at least one selected from among ionic polymers, ionic polymer salts, nonionic polymers and nonionic polymer salts, preferably at least one selected from ionic polymers and ionic polymer salts. can do.

Ionic polymers and ionic polymer salts include all polymer forms or cross-linked forms of acrylic acid, acrylamide, acryloyl dimethyltaurate, and esters of acrylic acid, and are combined with the ionic polymer to form an ionic polymer salt As a salt, it may be a cationic counter ion such as sodium, potassium, triethanolamine, arginine, and ammonium.

In addition, the ionic polymer may be used by mixing an anionic polymer and a cationic polymer as a counterion. A preferred example is carbomer as an anionic polymer and guarhydroxypropyltrimonium chloride as a cationic polymer. (Guar Hydroxypropyltrimonium Chloride) can be mixed and used. In addition, a preferable example of an ionic polymer salt constituting a thickener by using the anionic polymer and a cationic polymer as a counter ion is sodium alginate.

The nonionic polymer may be a natural polymer or a nonionic polymer obtained by processing a natural polymer, including a polymer form of a polyhydric alcohol ester of acrylic acid or a crosslinked form.

The amount of thickener is preferably 0.1 to 5.0 parts by weight, preferably 0.1 to 4.0 parts by weight, based on 100 parts by weight of the emulsion in the first step. There may be a problem in that it is impossible to produce an underwater type silicone elastomer because it is not secured.

Next, the preservative is used to prevent contamination from bacteria, microorganisms, etc., and the preservative is at least one selected from parabens, salts of parabens, benzoic acid, salts of benzoic acid, phenoxyethanol, and dialkylglycerin. can include In addition, the amount of preservative used is 0.1 to 2 parts by weight, preferably 0.1 to 1 part by weight, more preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of the emulsion. At this time, if the amount of the preservative used is less than 0.1 part by weight, the water-in-water silicone elastomer may not be resistant to bacteria and microorganisms, and if it is used in excess of 2 parts by weight, it may cause skin trouble when applying the water-in-water silicone elastomer as a cosmetic. Therefore, it is recommended to use it within the above range.

Next, the compatibilizer is for improving the feeling of use as a cosmetic and improving the compatibility of preservatives and water, and a polyhydric alcohol having 2 to 20 carbon atoms (C ₂ to C ₂₀₎ can be used, preferably C ₂ to It is preferable to use C ₁₀ alkylene glycol. In addition, the amount of the compatibilizing agent is preferably 1 to 400 parts by weight, preferably 4 to 300 parts by weight, more preferably 4 to 260 parts by weight, based on 100 parts by weight of the emulsion. The compatibilizer does not need to be added, but when used in excess of 400 parts by weight, it may be difficult to form an oil-in-water emulsion by lowering the interfacial tension between water and a non-polar material.

The oil-in-water silicone elastomer of the present invention thus prepared may have a viscosity at 25° C. of 5,000 to 50,000 cPs, preferably 7,000 to 45,000 cPs, and more preferably 7,500 to 40,000 cPs. If the viscosity exceeds 50,000 cPs, the viscosity is too high, and miscibility with other cosmetics is poor when used as a raw material for cosmetics, making it unsuitable for use as a cosmetic.

In addition, the water-in-water silicone elastomer of the present invention satisfies the D ₅₀ value of 2.5 to 5.0 μm, preferably 2.7 to 4.8 μm, and more preferably 3.20 to 4.50 μm when analyzing the particle size distribution of the particles, and the particle size distribution is according to the following formula 1 and Equation 2 can be satisfied.

[Equation 1]

(D ₅₀ -D ₁₀ ) < 1.50 μm, preferably (D ₅₀ -D ₁₀ ) < 1.40 μm, more preferably (D ₅₀ -D ₁₀ ) < 1.35 μm

[Equation 2]

(D ₉₀ -D ₅₀ ) < 2.80 μm, preferably (D ₉₀ -D ₅₀ ) < 2.65 μm, more preferably (D ₉₀ -D ₅₀ ) < 2.50 μm

In Equation 1 and / or 2, D ₁₀ , D ₅₀ and D ₉₀ are respectively measured when the particle size distribution of the water-in-water silicone elastomer is 10%, 50% and 90% of the particle size distribution. is the value

The water-in-water silicone elastomer of the present invention has excellent dispersibility in water and has uniform particles, so it can be applied as a cosmetic for various cosmetics.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are not intended to limit the scope of the present invention, which should be interpreted to aid understanding of the present invention.

[Example]

Example 1: Preparation of oil-in-water silicone elastomer

After dissolving purified water and polyglyceryl-10 myristate, a nonionic emulsifier, in a beaker, polysiloxane represented by the following formula 1-1, polysiloxane represented by the following formula 2-1, and Karsted catalyst were added. After that, it was stirred. Next, after raising the temperature to about 50 ° C., emulsion polymerization was performed for 8 hours while slowly stirring to prepare an emulsion containing an emulsion polymerization product.

Next, with respect to 100 parts by weight of the emulsion, 0.16 parts by weight of carbomer, an anionic polymer, and 0.16 parts by weight of guarhydroxypropyltrimonium chloride, a cationic polymer, thickener containing 0.16 parts by weight of ethylhexylglycerin, a preservative, commercially available An oil-in-water silicone elastomer was prepared by mixing and stirring 4.79 parts by weight of zein butylene glycol. The specific composition ratio of the composition used for preparing the emulsion is as shown in Table 1 below.

[Formula 1-1]

R ¹ _a R ² _3-a SiO (R ² ₂ SiO) _x SiR ¹ _a R ² _3-a

In Formula 1-1, R ¹ is a butylene group having a vinyl group at the end, R ² is a methyl group, x is 100 to 110, and a is 1.

[Formula 2-1]

R ¹ _a R ² _3-a SiO (R ¹ _b R ² _2-b SiO) _x (R ² ₂ SiO) _y SiR ¹ _a R ² _3-a

In Formula 2-1, R ¹ is a hydrogen atom, R ² is a methyl group, the molar ratio of x and y is 1: 9 to 10, the sum of x and y is 50 to 70, a is 3, b is is 1

Examples 2 to 5 and Comparative Examples 1 to 6

An emulsion polymerization reaction was performed under the same conditions as in Example 1 to prepare an oil-in-water silicone elastomer, but the oil-in-water silicone elastomer was prepared by varying the composition and composition ratio as shown in Tables 1 and 2 below, and Examples 2 to 6 and Comparative Examples 1 to 5 were carried out.

division Example 1 Example 2 Example 3 Example 4 Example 5 emulsion
(weight%) emulsifier nonionic emulsifier 1.06 1.06 1.09 3.45 1.14 Formula 1-1 polysiloxane 2.66 2.65 2.71 8.82 2.84 Formula 2-1 polysiloxane 0.53 0.53 0.54 1.72 0.57 catalyst 0.0002 0.0002 0.0002 0.00069 0.0002 carrier solvent dimethicone
(Mw=828) - 84.93 - - - purified water (water) remaining amount thickener cationic polymer Guar Hydroxy
Propyltrimonium
chloride 0.53 - - 1.72 3.64 anionic polymer carbomer 0.53 - - 1.72 3.64 ionic salt sodium alginate - - 3.26 - - preservative Ethylhexylglycerin 0.16 0.16 0.16 0.52 0.17 compatibilizer Butylene Glycol 5.16 6.00 5.27 24.00 6.19 synthesis 100% by weight (100 parts by weight)

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 emulsion
(weight%) emulsifier nonionic emulsifier 5.25 5.26 5.26 1.04 5.25 5.26 Formula 1-1 polysiloxane 42 52.63 54.74 2.61 41.97 13.16 Formula 2-1 polysiloxane 21 31.58 31.58 0.21 20.99 2.63 catalyst 0.0002 0.0002 0.0002 0.00002 0.31 0.0001 carrier solvent dimethicone
(Mw=828) - - - 85.68 - - purified water (water) remaining balance thickener cationic polymer Guar Hydroxy
Propyltrimonium
chloride 0.16 0.05 0.16 - 0.05 2.63 anionic polymer carbomer 0.16 0.05 0.16 - 0.05 2.63 ionic salt sodium alginate - - - - - - preservative Ethylhexylglycerin 0.16 0.16 0.16 0.16 0.16 0.79 compatibilizer Butylene Glycol 4.79 5.00 4.79 4.49 4.67 42 synthesis 100% by weight (100 parts by weight)

Experimental Example 1: Emulsion formation of water-in-water silicone elastomer, elastomer formation and viscosity measurement

The oil-in-water silicone elastomer prepared in the above Examples and Comparative Examples was measured for emulsion formation, elastomer formation, and viscosity (cPs) at 25° C., and the results are shown in Table 3 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 - emulsion formation formed formed formed formed formed - formation of elastomers formed formed formed formed formed - Viscosity (cPs) 12,870 16,820 35,610 8,700 not measurable - division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 emulsion formation formed formed not formed not formed
not not formed
not not formed
not formation of elastomers formed formed formed not formed formed formed Viscosity (cPs) 9,500 23,300 not measurable not measurable not measurable not measurable

Looking at the physical property measurement results in Table 3, in the case of Examples 1 to 5 and Comparative Examples 1 to 2, emulsion formation and elastomer formation were successful, whereas Comparative Examples 3 to 6 did not form emulsion, and Comparative Example 4 In the case of , the elastomer formation was also not well performed. In addition, in the case of Example 5 and Comparative Examples 3 to 5, there was a problem in which the viscosity could not be measured. It was impossible to measure with a viscometer because it greatly exceeded, and when applied as a cosmetic, a large amount of loss of ingredients occurred, resulting in poor compatibility with other cosmetics, so there was no marketability.

Experimental Example 2: Particle size analysis and measurement of water-in-water silicone elastomer

Particle size analysis was performed to confirm the emulsified particle uniformity of the silicone elastomers of Examples 1 to 5 and Comparative Examples 1 to 2, and the results are shown in FIGS. 1A to 1C.

Looking at the particle size analysis results of Figure 1 and Table 4, in the case of Comparative Examples 1 and 2, although emulsified particles were formed, the size of the particles was not uniform due to the excessive use of polysiloxane represented by Formula 1 and / or Formula 2 I was able to check the results.

And, in the case of Examples 1 to 5, when forming the emulsion and measuring the particle size distribution of the emulsified particles, the D ₅₀ value is about 2.5 to 5.0 μm, preferably 2.7 to 4.8 μm, more preferably 3.20 to 4.50 μm. While having, it was confirmed that the particle size distribution measurement value satisfied Equations 1 and 2 below, so that the particle size was very uniform. In particular, in the case of Example 4, it was confirmed that the particle distribution graph was relatively dense compared to other examples, so that very uniform emulsified particles were formed.

[Equation 1]

(D ₅₀ -D ₁₀ ) < 1.50 μm

[Equation 2]

(D ₉₀ -D ₅₀ ) < 2.80 μm

division D ₁₀ (μm) D ₅₀ (μm) D ₉₀ (㎛) D ₅₀ -D ₁₀ , μm D ₉₀ - D ₅₀ , μm Comparative Example 1 0.60 1.32 5.39 0.72 4.07 Comparative Example 2 0.60 1.32 5.18 0.72 3.86 Example 1 2.37 3.66 5.89 1.29 2.23 Example 2 2.37 3.65 5.89 1.28 2.24 Example 3 2.33 3.67 6.04 1.34 2.37 Example 4 2.00 2.78 3.93 0.78 1.15 Example 5 2.29 3.63 6.00 1.34 2.37

Experimental Example 3: Measurement of dispersibility of water-in-water silicone elastomer in water

In Experimental Example 1, the dispersibility and dispersion stability in water of Examples 1 to 5 and Comparative Examples 1 to 2, in which the emulsification of the silicone elastomer was well formed, were measured. After mixing and stirring water, the dispersibility was measured by leaving it for 24 hours, and the results are shown in FIG. 2 .

Looking at the dispersibility measurement results of FIG. 2, in the case of Examples 1 to 5, the initial dispersibility was excellent, but in the case of Comparative Examples 1 and 2, after 2 hours, the dispersibility increased and phase separation occurred. I was able to confirm.

And, looking at the results measured after 24 hours, in the case of Examples 1 and 4, it was confirmed that there was no phase separation phenomenon and had excellent dispersibility and dispersion stability. In the case of Example 5, compared to Examples 1 and 4, the dispersibility was somewhat insufficient, but compared to Examples 2 to 3, it showed excellent dispersibility. However, in the case of Example 5, as confirmed in Experimental Example 1, there is a problem in that the viscosity is too high.

And, in the case of Examples 2 and 3, compared to Examples 1 and 4, the dispersibility was somewhat poor.

Example 6

An oil-in-water silicone elastomer was prepared in the same manner as in Example 1, but polysiloxane represented by Chemical Formula 1-2 was used instead of polysiloxane represented by Chemical Formula 1-1, and polysiloxane represented by Chemical Formula 2-1 was replaced by the following chemical formula. After preparing an emulsion having a composition ratio as shown in Table 5 using polysiloxane represented by 2-2, an oil-in-water silicone elastomer was prepared.

[Formula 1-2]

R ¹ _a R ² _3-a SiO (R ² ₂ SiO) _x SiR ¹ _a R ² _3-a

In Formula 1-2, R ¹ is a propylene group including a vinyl group at the end, R ² is an ethyl group, x is 110 to 115, and a is 1.

[Formula 2-2]

R ¹ _a R ² _3-a SiO (R ¹ _b R ² _2-b SiO) _x (R ² ₂ SiO) _y SiR ¹ _a R ² _3-a

In Formula 2-2, R ¹ is a hydrogen atom, R ² is an ethyl group, the molar ratio of x and y is 1:7, the sum of x and y is 80, a is 3, and b is 1.

Example 7

An oil-in-water silicone elastomer was prepared in the same manner as in Example 1, but instead of polysiloxane represented by Chemical Formula 1-1, polysiloxane represented by Chemical Formula 1-3 was used instead of polysiloxane represented by Chemical Formula 2-1. After preparing an emulsion having a composition ratio as shown in Table 5 using the polysiloxane represented by 2-3, an oil-in-water silicone elastomer was prepared.

[Formula 1-3]

R ¹ _a R ² _3-a SiO (R ² ₂ SiO) _x SiR ¹ _a R ² _3-a

In Formula 1-3, R ¹ is a propylene group having a vinyl group at the end, R ² is a propyl group, x is 120 to 124, and a is 1.

[Formula 2-3]

R ¹ _a R ² _3-a SiO (R ¹ _b R ² _2-b SiO) _x (R ² ₂ SiO) _y SiR ¹ _a R ² _3-a

In Formula 2-3, R ¹ is a hydrogen atom, R ² is a phenyl group, the molar ratio of x and y is 1:3, the sum of x and y is 80, a is 3, and b is 1.

Comparative Example 7

An oil-in-water silicone elastomer was prepared in the same manner as in Example 1, but using the polysiloxane represented by the following Chemical Formula 1-4 instead of the polysiloxane represented by the Chemical Formula 1-1, and replacing the polysiloxane represented by the Chemical Formula 2-1 by the following formula. After preparing an emulsion having a composition ratio as shown in Table 5 using the polysiloxane represented by 2-4, an oil-in-water silicone elastomer was prepared.

[Formula 1-4]

R ¹ _a R ² _3-a SiO (R ² ₂ SiO) _x SiR ¹ _a R ² _3-a

In Formula 1-2, R ¹ is a heptyl group having a vinyl group at the end, R ² is an ethyl group, x is 110 to 115, and a is 1.

[Formula 2-4]

R ¹ _a R ² _3-a SiO (R ¹ _b R ² _2-b SiO) _x (R ² ₂ SiO) _y SiR ¹ _a R ² _3-a

In Formula 2-4, R ¹ is a hydrogen atom, R ² is a nonyl group, the molar ratio of x and y is 1:7, the sum of x and y is 80, a is 3, and b is 1.

division Example 6 Example 7 Comparative Example 7 emulsion
(weight%) emulsifier nonionic emulsifier 1.06 1.06 1.06 Formula 1-2 polysiloxane 2.66 - - Formula 2-2 polysiloxane 0.53 - - Formula 1-3 polysiloxane - 2.65 - Formula 2-3 polysiloxane - 0.53 - Formula 1-4 polysiloxane - - 2.65 Formula 2-4 polysiloxane - - 0.53 catalyst 0.0002 0.0002 0.0002 purified water (water) remaining amount thickener cationic polymer Guar Hydroxy
Propyltrimonium
chloride 0.53 0.53 0.53 anionic polymer carbomer 0.53 0.53 0.53 preservative Ethylhexylglycerin 0.16 0.16 0.16 compatibilizer Butylene Glycol 0.16 0.16 0.16 synthesis 100% by weight (100 parts by weight)

Experimental Example 4: Particle size analysis and measurement of water-in-water silicone elastomer 2

The particle size analysis of the water-in-water silicone elastomer prepared in Examples 6 to 7 and Comparative Example 7 was measured in the same manner as in Experimental Example 2, and the results are shown in Table 6 below.

division D ₁₀ (μm) D ₅₀ (μm) D ₉₀ (㎛) D ₅₀ -D ₁₀ , μm D ₉₀ - D ₅₀ , μm Example 6 2.93 3.87 6.18 0.94 2.31 Example 7 3.10 4.43 6.92 1.33 2.49 Comparative Example 6 3.02 5.31 8.65 2.29 3.34

Looking at the particle size analysis measurement results in Table 6, it was confirmed that Examples 6 and 7 had uniform particle sizes by showing results satisfying Equations 1 and 2. On the other hand, in the case of the elastomer prepared using polysiloxane outside the range suggested by the present invention, it was confirmed that the particle size was generally large and the particle size was uneven.

Claims (10)

emulsion; preservatives; and a compatibilizer; or an emulsion; thickeners; preservatives; and a compatibilizer;
When a carrier solvent is included during the emulsion polymerization reaction of the emulsion, the water-in-water silicone elastomer does not contain a thickener,
The emulsion is mixed and emulsified with 0.5 to 10% by weight of an emulsifier, 2.0 to 40.0% by weight of a polysiloxane represented by the following formula (1), 0.4 to 25.0% by weight of a polysiloxane represented by the following formula (2), 0.00001 to 0.24000% by weight of a catalyst, and the remaining amount of water. containing emulsions subjected to polymerization; or or
The emulsion includes an emulsion obtained by further mixing and emulsion polymerization of the emulsifier, the polysiloxane represented by Formula 1, the polysiloxane represented by Formula 2, the catalyst, and the water with a carrier solvent;
The emulsifier includes at least one selected from anionic emulsifiers, nonionic emulsifiers, and cationic emulsifiers,
The catalyst includes a silylation catalyst hybridized with a platinum group metal containing at least one selected from ruthenium, rhodium, palladium, osmium, iridium, and platinum,
The carrier solvent includes at least one selected from dimethicone, linear volatile siloxane, cyclic volatile siloxane, branched volatile siloxane, and hydrocarbon oil,
The preservative includes at least one selected from parabens, salts of parabens, benzoic acid, salts of benzoic acid, phenoxyethanol, and dialkyl glycerin,
Based on 100 parts by weight of the emulsion, including 0.1 to 5.0 parts by weight of a thickener,
When measuring the particle size distribution of silicone elastomer particles, D ₅₀ satisfies 2.5 to 5.0 μm, and oil-in water silicone elastomer, characterized in that it satisfies the following formulas 1 and 2.
[Formula 1]
R ¹ _a R ² _3-a SiO (R ² ₂ SiO) _x SiR ¹ _a R ² _3-a
In Formula 1, R ¹ is a C ₂ to C ₅ alkylene group including a vinyl, allyl, butadienyl or hexenyl group at the end, R ² is an alkyl or aryl group having 1 to 8 carbon atoms, and x is 30 to 1,000, a is 1 to 3,
[Formula 2]
R ¹ _a R ² _3-a SiO (R ¹ _b R ² _2-b SiO) _x (R ² ₂ SiO) _y SiR ¹ _a R ² _3-a
In Formula 2, R ¹ is a hydrogen atom or an alkyl group containing -OH, R ² is an alkyl group having 1 to 3 carbon atoms or a phenyl group, the molar ratio of x and y is 1: 1 to 199, and the sum of x and y is 8 to 500, a is 0 to 3, b is 1 to 2,
[Equation 1]
(D ₅₀ -D ₁₀ ) < 1.50 μm
[Equation 2]
(D ₉₀ -D ₅₀ ) < 2.80 μm
In Equation 1 and / or 2, D ₁₀ , D ₅₀ and D ₉₀ are respectively measured when the particle size distribution of the water-in-water silicone elastomer is 10%, 50% and 90% of the particle size distribution. is the value
delete The oil-in-water silicone elastomer according to claim 1, wherein the emulsion further comprises 1 to 85% by weight of a carrier solvent based on the total weight.
The method of claim 1, wherein the linear volatile siloxane includes at least one selected from hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetramethylhexasiloxane, and hexadecamethylheptasiloxane. and
The cyclic volatile siloxane is an oil-in-water silicone elastomer, characterized in that it comprises at least one selected from hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.
The oil-in-water silicone elastomer according to claim 1, wherein the emulsion further comprises at least one selected from ethers of polyhydric alcohols having aliphatic unsaturated bonds and esters of polyhydric alcohols having aliphatic unsaturated bonds.
The oil-in-water silicone elastomer according to claim 1, which comprises 0.1 to 2 parts by weight of a preservative and 1 to 40 parts by weight of a compatibilizer based on 100 parts by weight of the emulsion.
The method of claim 1, wherein the thickener includes at least one selected from ionic polymers, salts of ionic polymers, and nonionic polymers,
The compatibilizer is an oil-in-water silicone elastomer, characterized in that it comprises a polyhydric alcohol having 2 to 20 carbon atoms.
The oil-in-water silicone elastomer according to any one of claims 1 and 3 to 7, which has a viscosity of 5,000 to 50,000 cPs at 25°C.
0.5 to 10% by weight of an emulsifier, 2.0 to 40.0% by weight of a polysiloxane represented by the following formula (1), 0.4 to 25.0% by weight of a polysiloxane represented by the following formula (2), 0.00001 to 0.24000% by weight of a catalyst, and the remaining amount of water were mixed and emulsion-polymerized. Step 1 of preparing an emulsion; and
A second step of adding and stirring a thickener, a preservative and a compatibilizer to the emulsion;
The emulsifier includes at least one selected from anionic emulsifiers, nonionic emulsifiers, and cationic emulsifiers,
The catalyst includes a silylation catalyst hybridized with a platinum group metal containing at least one selected from ruthenium, rhodium, palladium, osmium, iridium, and platinum,
The preservative includes at least one selected from parabens, salts of parabens, benzoic acid, salts of benzoic acid, phenoxyethanol, and dialkyl glycerin,
The thickener of the second step is added in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the emulsion,
The silicone elastomer particles prepared by performing step 2 satisfy D ₅₀ of 2.5 to 5.0 μm when measuring the particle size distribution and satisfy the following formulas 1 and 2. Of the oil-in-water silicone elastomer, manufacturing method;
[Formula 1]
R ¹ _a R ² _3-a SiO (R ² ₂ SiO) _x SiR ¹ _a R ² _3-a
In Formula 1, R ¹ is a C ₂ to C ₅ alkylene group including a vinyl, allyl, butadienyl or hexenyl group at the end, R ² is an alkyl or aryl group having 1 to 8 carbon atoms, and x is 30 to 1,000, a is 1 to 3,
[Formula 2]
R ¹ _a R ² _3-a SiO (R ¹ _b R ² _2-b SiO) _x (R ² ₂ SiO) _y SiR ¹ _a R ² _3-a
In Formula 2, R ¹ is a hydrogen atom or an alkyl group containing -OH, R ² is an alkyl group having 1 to 3 carbon atoms or a phenyl group, the molar ratio of x and y is 1: 1 to 199, and the sum of x and y is 8 to 500, a is 0 to 3, b is 1 to 2,
[Equation 1]
(D ₅₀ -D ₁₀ ) < 1.50 μm
[Equation 2]
(D ₉₀ -D ₅₀ ) < 2.80 μm
In Equation 1 and / or 2, D ₁₀ , D ₅₀ and D ₉₀ are respectively measured when the particle size distribution of the water-in-water silicone elastomer is 10%, 50% and 90% of the particle size distribution. is the value
[Claim 10] The method for preparing an oil-in-water silicone elastomer according to claim 9, wherein the first step of the emulsion polymerization reaction is performed at 40 to 80 °C.

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