KR20150034843A - A composition for producing polymeric beads and a process for preparing polymeric beads using the same - Google Patents

Abstract

The present invention relates to a round-shaped polymeric powder whose specific gravity is light and adhesive property is outstanding, and to a manufacturing method thereof wherein the manufacturing method of the polymeric bead comprises the steps of putting volatile hydrocarbon with strong liquidity in a process of manufacturing polymer powders; selectively removing the hydrocarbon in a polymerization process; and making pores on surfaces or hollowness inside, thereby manufacturing polymeric beads whose specific gravity is light.

Description

TECHNICAL FIELD The present invention relates to a composition for preparing a polymer bead, and a method for producing the polymer bead using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a composition for preparing polymer beads and a process for producing polymer beads using the same.

More specifically, the present invention relates to an aromatic vinyl-based monomer; Acrylic acid or methacrylic acid alkyl ester monomers having 1 to 20 carbon atoms; And at least one monomer selected from the group consisting of acrylic acid or methacrylic acid fluoroalkyl ester monomers having 1 to 20 carbon atoms, a hydrocarbon compound, a phenol derivative compound having 6 to 50 carbon atoms, a crosslinking agent, And a method for preparing polymer beads using the same.

Polymer particles are collectively referred to as spherical particles having a uniform particle size distribution produced by emulsion polymerization or suspension polymerization. Polymer particles are used in a wide variety of applications, and are used not only in light diffusion films, protective films and architectural applications for liquid crystal monitors, but also in soft cosmetic applications due to the difference in refractive index.

Polymer particles used for this purpose such as polystyrene beads and the like are generally produced by methods such as suspension polymerization, dispersion polymerization and emulsion polymerization.

In conventional suspension polymerization, polymer particles are prepared by dispersing monomers present in the aqueous phase by mechanical force. Polymer particles produced by this method have a particle size of at least 100 mu m and tend to have a wide distribution of particles because the particles are dispersed by mechanical force. In this regard, U.S. Pat. Nos. 4,017,670, 4,071,670, 4,085,169 and 4,129,706 disclose techniques for making polystyrene polymer beads by suspension polymerization.

Polymer beads are used as a cosmetic material because they have the effect of giving a SOFT FOCUSS effect when used in a cosmetic formulation and have an effect of improving wrinkles and a volume feel by soft touch when using mascara.

However, when a cosmetic product is formulated, a high specific gravity can cause the product to sink during manufacture, and if the surface is too smooth, it tends to play separately from the formulation.

Therefore, it is required to mix well with various formulations used in cosmetic preparations and do not sink, and to have good adhesion to the skin and to improve the original effect.

Beads in cosmetics have good adhesion to the skin and good flowability. Therefore, unlike existing beads, techniques for increasing the adhesion by changing the surface have recently emerged.

The object of the present invention is to provide a spherical polymer powder suitable for use in cosmetics because it has a spherical shape and sharply disperses it to maximize the spreadability in cosmetics and produces a surface pore, I want to.

The present invention also provides a polymer bead prepared by the above method.

The present invention relates to an aromatic vinyl monomer; Acrylic acid or methacrylic acid alkyl ester monomers having 1 to 20 carbon atoms; And at least one monomer selected from the group consisting of acrylic acid or methacrylic acid fluoroalkyl ester monomers having 1 to 20 carbon atoms, a hydrocarbon compound, a phenol derivative compound having 6 to 50 carbon atoms, a crosslinking agent, Wherein the polymeric bead composition comprises a polymeric bead.

Further, in the method for producing polymer beads,

 At least one monomer selected from the group consisting of aromatic vinyl monomers, acrylic acid or methacrylic acid alkyl ester monomers having 1 to 20 carbon atoms, and acrylic acid or methacrylic acid fluoroalkyl ester monomers having 1 to 20 carbon atoms, a crosslinking agent, Ion exchanged water, and 10 to 30 parts by weight of a hydrocarbone compound,

Wherein the polymer bead is a polymeric bead.

And a polymer bead having a hemispherical shape or a millet shape produced by using the above-described manufacturing method.

The present invention relates to a polymer bead having enhanced adhesion and a method for producing the polymer bead. More specifically, the present invention relates to a method for producing a polymer powder having a small specific gravity as compared with conventional polymer beads, The present invention relates to a spherical polyurethane powder.

The present invention can make a polymer bead having good adhesion and uniform wetting property by using a composition for preparing a polymer bead containing a predetermined amount of a monomer, a crosslinking agent, an initiator, ion exchanged water and a hydrocarbon compound.

According to the method for producing a polymer powder having excellent spherical adhesion of the present invention, by adding a hydrocarbon compound during polymerization and polymerizing an emulsion obtained through emulsification, pores are formed on the surface of the emulsion and the weight of the polymer is reduced to make cosmetic formulations The surface of the polymer powder does not sink, and the polymer powder having excellent adhesion can be produced.

Further, the polymer powder produced in accordance with the present invention has a spherical shape and is excellent in physical properties such as optical properties, powder flowability, workability, and strength, and is thus suitably used for cosmetics as well as for optical applications.

According to the present invention, it is possible to observe that the specific gravity is smaller than that of the conventional three-dimensional structure due to the structure in which the irregularities are formed mainly on the surface while the spherical shape of the uniform size is formed.

1 is an electron micrograph of a polymer powder according to Example 1 of the present invention.
Fig. 2 is an electron micrograph of the polymer powder of Example 2. Fig.
3 is an electron micrograph of the polymer powder of Example 3 of the present invention.
Fig. 4 is an electron micrograph of the polymer powder of Comparative Example 2. Fig.
5 is an electron micrograph of the polymer powder of Comparative Example 3. Fig.
6 shows the hydrocarbon structure and property table.
7 is an electron micrograph of the polymer powder of Comparative Example 1. Fig.

The present invention relates to a resin composition comprising at least one monomer selected from the group consisting of aromatic vinyl monomers, acrylic acid or methacrylic acid alkyl ester monomers having 1 to 20 carbon atoms, and acrylic acid or fluoroalkyl methacrylate monomers having 1 to 20 carbon atoms; Hydrocarbon compounds; A crosslinking agent; Initiator; And ion-exchanged water.

The hydrocarbone compound is selected from the group consisting of ISOPAR C, ISOPAR E, ISOPAR G, ISOPAR M, ISOPAR H, ISOPAR J, ISOPAR K, ISOPAR L, ISOPAR M, ISOPAR N, ISOPAR P and isoparaffinic hydrocarbon as a paraffinic compound It may be more than one kind.

   The difference between these solvents is volatile, boiling. Evaporation rate, refractivity of flash point, etc., and the hydrocarbons derivative compound may be contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the monomer.

The composition for preparing a polymer bead may further comprise a dispersion stabilizer.

The present invention also relates to a process for producing an acrylic resin composition, which comprises the steps of: a) preparing an acrylic resin composition comprising a monomer mixture of a) an aromatic vinyl monomer, an acrylic acid or methacrylic acid alkyl ester monomer having 1 to 20 carbon atoms and an acrylic acid or a methacrylic acid fluoroalkyl ester monomer having 1 to 20 carbon atoms Monomers; Crosslinking agents, initiators; And ion exchanged water to prepare a suspension, and polymerizing the suspension to proceed an exothermic reaction of the initiator.

The present invention also provides a polymer bead prepared using the composition for preparing a polymer bead, wherein the polymer bead has an average particle diameter of 1 to 50 μm and a coefficient of variation (CV) of 5% to 30%.

The present invention also provides a polymer bead produced by the above method, wherein the average particle diameter is 1 to 50 μm and the coefficient of variation (CV) is 5% to 30%.

Hereinafter, the present invention will be described in more detail.

The inventors of the present invention found that when polymer beads were mixed with cosmetic formulations, they were difficult to use in cosmetics due to lack of adherence of the surface and time after they were submerged.

 However, it was confirmed that when the powder was prepared by forming the surface cavity by the method used in the present invention, the specific gravity was lowered and the flowability and adhesion were improved.

The polymer beads of the present invention basically include beads made of polymethylmethacrylate beads, polystyrene beads, polyurethane beads, etc. Among them, polymethacrylate beads and the like are more preferable examples in terms of optical properties .

According to one embodiment of the present invention, there is provided an acrylic resin composition comprising an aromatic vinyl monomer, an acrylic acid or methacrylic acid alkyl ester monomer having 1 to 20 carbon atoms, and 1 to 20 carbon atoms selected from the group consisting of acrylic acid or methacrylic acid fluoroalkyl ester monomer Monomer or higher; A phenol derivative compound having 6 to 50 carbon atoms; A crosslinking agent; Initiator; And ion-exchanged water.

The monomer may be selected from the group consisting of methylmethacrylate, styrene, divinylbenzene, butylmethacrylate, trimethylolmethane tetraacrylate, trimethylolmethane triacrylate trimethylolmethane triacrylate, trimethylolbutane triacrylate, ethylene glycol dimethacrylate, and the like can be used.

 Of these monomers, methyl methacrylate, styrene, divinylbenzene, and butyl methacrylate are preferred from the viewpoint of securing excellent optical properties of the polymer beads.

The content of the monomer may be used as a basis of each component for producing the polymer bead.

In this case, when the total polymer bead composition is used as a standard, the monomer is included in an amount of 10 to 50 parts by weight, preferably 20 to 40 parts by weight, more preferably 30 parts by weight, based on 100 parts by weight of the total polymer bead composition .

 The monomer content is preferably 10 parts by weight or more from the viewpoint of controlling the particle size, and 50 parts by weight or less from the viewpoint of increasing the degree of crosslinking.

  Therefore, there is a problem that the particle diameter and the degree of crosslinking of the polymer bead can not be obtained at a desired level when the content of the monomer is too small or too large.

Hydrocarbons are compounds of the parafine type, which are included in the polymerization process from the beginning and can be located inside the polymer bead while polymerizing.

 However, as the paraffin oil is highly volatile and has excellent flow ability, the reaction proceeds to the surface, resulting in surface cavities or large cavities inside.

Isopar C, ISOPAR E, ISOPAR G, ISOPAR M, ISOPAR H, ISOPAR J, ISOPAR K, ISOPAR L, ISOPAR M, and Isopar C are used as the hydrocarbon compounds used in the present invention. ISOPAR N, ISOPAR P, and the like.

The above-mentioned paraffinic oils have a higher carbon number as they go toward the ISOPAR P side, and products using heavy formulations that are too heavy can not come out to the surface as the reaction progresses and the polymerization stability can not be secured and the shape of the spherical shape can not be achieved. G or ISORPA E is more preferable.

The content of the hydrocarbon compound may be 1 to 50 parts by weight, preferably 3 to 50 parts by weight, more preferably 5 to 15 parts by weight based on 100 parts by weight of the monomer.

If the hydrocarbon compound is added in an amount exceeding 25 parts by weight, the spherical shape may not be formed during the final polymerization and may not be uniformly arranged in the secondary processing.

   As a result, it may be difficult to produce a polymer bead having good adhesion and uniform wettability.

  Further, there is a problem that the effect of generating the surface PORE is weak.

  Accordingly, it is preferable that the content of the hydrocarbon compound is maintained within the above-mentioned range so that the polymer bead having excellent adhesion from the monomer can be produced.

  That is, the content of the hydrocarbon compound is preferably 10 parts by weight or more from the viewpoints of improvement in adhesion and spreadability, and is preferably 25 parts by weight or less in view of polymerization stability.

Also, the crosslinking agent may be at least one selected from the group consisting of 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, Acrylate, 1,6-hexanediol diacrylate, divinylbenzene, ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, poly Propylene glycol diacrylate, propylene glycol diacrylate, polybutylene glycol diacrylate, allyl acrylate, 1,2-ethanediol dimethacrylate, 1,3-propanediol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol di Meta Polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, triethylene glycol methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, At least one selected from the group consisting of glycol dimethacrylate, polybutylene glycol dimethacrylate, allyl methacrylate, diallyl maleate, and trimethylolpropane triacrylate (TMPTA) can be used .

 Of these, 1,2-ethanediol diacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate and the like are more preferable from the viewpoint of polymerization stability.

The content of the crosslinking agent may be 1 to 98 parts by weight, preferably 5 to 50 parts by weight, more preferably 8 to 30 parts by weight based on 100 parts by weight of the monomer.

 The content of the crosslinking agent may be 1 part by weight or more in view of enhancing the solvent resistance, and may be 98 parts by weight or less in terms of polymerization yield.

Wherein the initiator is selected from the group consisting of benzoyl peroxide, azobisisobutyronitrile, azobismethylbutyronitrile, azobiscyclohexanecarbonitrile, potassium persulfate, sodium persulfate, ammonium persulfate and azo based water soluble initiators. More than species can be used.

The initiator may be selected from at least one peroxide compound such as benzoyl peroxide, lauryl peroxide, octanoyl peroxide, and dicumyl peroxide.

 Of these, benzoyl peroxide, azobisisobutyronitrile, azobismethylbutyronitrile and the like are more preferable in terms of polymerization stability.

The initiator is preferably used in an amount of 1 to 5 parts by weight based on 100 parts by weight of the monomer. If the content is less than 1 part by weight, unreacted monomers may be excessively produced. If the content is more than 5 parts by weight, there is a problem that the polymerization stability is deteriorated due to rapid heat generation.

In addition, the composition for preparing a polymer bead of the present invention may further comprise a dispersion stabilizer for suspension stabilization.

 Examples of the dispersion stabilizer include polyvinyl alcohol, polyvinyl pyrrolidone, methylcellulose, ethylcellulose, sodium carboxymethylcellulose, polyacrylic acid, polymethacrylic acid, sodium polyacrylate, sodium polymethacrylate, gelatin, A mixture of at least one member selected from the group consisting of polyacrylamide, polyethylene oxide, polyvinyl methyl ether, polyethyleneimide, vinyl acetate copolymer, hydroxypropyl cellulose, silica and siloxane can be used. Particularly, from the viewpoint of polymerization stability, polyvinyl alcohol, polyvinyl methyl ether, vinyl acetate copolymer and the like are more preferable.

The content of the dispersion stabilizer may be 1 to 50 parts by weight, preferably 1 to 10 parts by weight based on 100 parts by weight of the monomer.

 If the content of the dispersion stabilizer is less than 1 part by weight, the stability of emulsification tends to be poor, resulting in a large amount of polymer aggregates. When the content of the dispersion stabilizer is more than 50 parts by weight, the removal of the dispersion stabilizer is difficult.

In addition, the composition for preparing polymer beads of the present invention includes ion-exchanged water together with monomers, content of hydrocarbon compounds, crosslinking agents, initiators, and the like.

 The ion-exchanged water used in the present invention preferably has a smaller cation number, and more preferably has a resistance value of at least 5 M OMEGA under a nitrogen stream generated through an ion exchanger.

 At this time, the content of the ion-exchanged water can be appropriately added to the level included in the conventional suspension polymerization, and the content thereof is not limited, and can be appropriately adjusted within a range well known in the art.

For example, the ion exchange water may be contained in an amount of 50 to 1000 parts by weight, preferably 50 to 500 parts by weight, based on 100 parts by weight of the monomer.

The present invention provides a spherical polymer powder produced by the above method, wherein the spherical polymer powder produced by the present invention has a CV value (Coefficient of Variation) of 40% or less and a product yield of 90% or more .

Also, the average particle size of the polymer powder is in the range of about 2 to 200 μm, preferably about 5 to 100 μm. As a result of the specific gravity measurement, the density of the beads without using the hydrocarbon compound is about 1.0 to 1.3, ~ 40% of the weight, and it is understood that the test result of the adhesion test is excellent as the surface porre.

   More preferably, the polymer powder has a density of 0.8 to 1, and it can be seen that the adhesion power test result is excellent.

Therefore, the polymer powder prepared according to the present invention is spherical and has a variation coefficient, a product yield, and an average particle size, which are equal to or higher than those of the conventional polymer powder, and are relatively light in density, so that the sedimentation rate is much slower than that according to the STOKE law Able to know. Vs is the descending velocity, μ is the viscosity of the fluid, ρs is the density of the sediment particles, ρ is the density of the fluid, D is the diameter of the sediment particle, and g is the gravitational acceleration.

According to Stokes' law, sedimentation velocity increases as the density of sediments increases, as the density of fluid decreases, as the viscosity of fluid decreases, and as the diameter of sediment particles increases. When all conditions are equal, the sedimentation rate decreases as the density of sediments decreases.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Example  One

As shown in the following Table 1, 100 parts by weight (386.6 g) of methylmethacrylate (MMA), 10 parts by weight (42 g) of ISORPAR G,

12 weight parts (46.4 g) of ethylene glycol dimethacrylate (EGDMMA), 1 weight part (3.8 g) of azobisisobutyronitrile (ABIBN) and ion-exchanged water (918.13 g) After the preparation, the mixture was placed in a reactor and stirred at a speed of 700 rpm for 30 minutes.

  The suspension was discharged from the reactor and repeated twice at 7,000 rpm in a homomixer to perform intensive stirring.

  The suspension prepared by the strong stirring was put into a 2L reactor and heated at an internal temperature of 60 ° C under stirring in a nitrogen stream at 250 rpm.

 After about 2 hours or more after the heating, an initiator is expressed and the internal temperature rises to 80 to cause an exothermic reaction.

After the exothermic reaction, when the time elapsed from 30 minutes to 1 hour, the internal temperature dropped again to 60 ° C., the exothermic reaction was terminated, and the stirring was further continued for 2 hours at a temperature of 90 ° C. After completion of the polymerization, , Followed by washing, dewatering and drying in a usual manner to prepare 386 g of polymer beads.

Example  2 to 3

382 g, 380 g and 379 g of polymer beads were obtained by carrying out the same procedure as in Example 1, except that the content of ISORPAR G was increased to 5 parts by weight and 15 parts by weight, respectively, as shown in the following Table 1 .

Example  4 to 5

As shown in the following Table 1, 280 g of a polymer bead was prepared in the same manner as in Example 1, except that ISORPAR M and ISORPAR E were used in place of ISORPAR G, respectively.

Example  6

As shown in the following Table 1, 300 g of a polymer bead was prepared in the same manner as in Example 1, except that trimethylolpropane triacrylate (TMPTA) was used as a crosslinking agent.

Example  7

Except that benzoyl peroxide (BZPO) was used as an initiator as shown in the following Table 1, to thereby prepare 300 g of a polymer bead.

Example  8

As shown in the following Table 1, 300 g of a polymer bead was prepared in the same manner as in Example 1, except that styrene was used as the monomer.

Example  9

As shown in the following Table 1, in the same manner as in Example 1 except that polyvinyl alcohol (hereinafter referred to as PVA) as a dispersion stabilizer was further added in an amount of 6 parts by weight based on 100 parts by weight of the monomer and mixed to prepare a suspension To prepare 354 g of polymer beads.

Comparative Example  One

As shown in the following Table 1, 380 g of a polymer bead was prepared in the same manner as in Example 1, except that no hydrocarbon compound was added.

Comparative Example  2 to 3

As shown in the following Table 1, 380 g of a polymer bead was prepared by carrying out the same procedure as in Example 1, except that 25 parts by weight of ISOPAR G, which is a hydrocarbon compound, and 25 parts by weight of ISORPAR M were added, respectively Respectively.

The compositions of the polymer bead compositions of Examples 1 to 9 and Comparative Examples 1 to 3 are shown in Table 1 below. Each content unit is parts by weight.

Table 1. Composition content of the Examples and Comparative Examples division Monomer Hydrocarbon
compound Cross-linking agent Initiator Dispersion stabilizer ingredient content ingredient content ingredient content ingredient content ingredient content Example 1 MMA 100 ISOPAR G 10 EGDMMA 12 ABIBN One - - Example 2 MMA 100 ISOPAR G 5 EGDMMA 12 ABIBN One - - Example 3 MMA 100 ISOPAR G 15 EGDMMA 12 ABIBN One - - Example 4 MMA 100 ISOPAR M 10 EGDMMA 12 ABIBN One - - Example 5 MMA 100 ISOPAR E 10 EGDMMA 12 ABIBN One - - Example 6 MMA 100 ISOPAR G 10 TMPTA 12 ABIBN One - - Example 7 MMA 100 ISOPAR G 10 EGDMMA 12 BZPO One - - Example 8 Styrene 100 ISOPAR G 10 EGDMMA 12 ABIBN One - - Example 9 MMA 100 ISOPAR G 10 EGDMMA 12 ABIBN One PVA 6 Comparative Example 1 MMA 100 - - EGDMMA 12 ABIBN One - - Comparative Example 2 MMA 100 ISOPAR M 25 EGDMMA 12 ABIBN One - - Comparative Example 3 MMA 100 ISOPAR GM 25 EGDMMA 12 ABIBN One - -

< Experimental Example >

The properties of the polymer beads prepared according to Examples 1 to 9 and Comparative Examples 1 to 3 were measured by the following methods. The measured properties are summarized in Table 2 below.

 [comparison analysis]

In order to compare the spherical polyurethane powders prepared in Examples 1-2 and 1-5, SEM measurement, product yield, average particle size, compressive modulus, recovery rate, sedimentation rate Speed, adhesion test coefficient of variation, etc. were measured. The results of comparative analysis are shown in Table 1.

  1 and 2 show electron micrographs (SEM) photographs of the polyurethane powder of Example 1 and Comparative Example 1.

- SEM measurement: Hitachi S-4300

- Measuring product yield: Measuring the yield after filtering

- Average particle size: Measured using Coulter Multisizer M3

- Settling velocity: measured by the following equation 1 (Stoch law)

- Coefficient of variation (CV): Measured by the following formula 2

- Adhesion: 0.5% of each polymer powder is mixed with foundation cosmetic formulation and tested directly on the skin. Measure the extent to which it is applied to the back of the hand and then buried. When adhesion is good, it does not come out easily. It is indicated by 1 ~ 5 depending on the degree of adhesion.

5: Almost never appears

4: The amount of sticking out is less than the amount used

3: The amount of burying is about half of the used amount.

2: A small amount but a larger amount than the used amount

1: Almost does not come close, and most of it is buried.

-Oil Absorbtion: expressed in g of oil per 100 g of pigment (Table 3)

[Equation 1]

In the above formula, each definition is as described above.

[Equation 2]

CV (%) = (standard deviation of particle diameter / average particle diameter of particle) x 100

Table 2. Measurement of physical properties of examples and comparative examples division
Average particle diameter
(탆) CV
(%) importance
Settling velocity Adhesion Example 1 rectangle 15 18 0.9452 0.00402 5 Example 2 rectangle 15 17 1.1025 0.00912 4 Example 3 rectangle 15 19 0.9372 0.00436 5 Example 4 rectangle 14 16 1.0021 0.0920 4 Example 5 rectangle 15 18 0.9958 0.00821 4 Example 6 rectangle 15 17 1.0221 0.01021 4 Example 7 rectangle 15 30 1.1524 0.01073 3 Example 8 rectangle 15 16 0.9800 0.00501 4 Example 9 rectangle 14 18 0.9550 0.00412 5 Comparative Example 1 rectangle 15 20 1.1856 0.01073 3 Comparative Example 2 Hemispherical 30 30 0.8954 0.00400 5 Comparative Example 3 Rugby ball shape 30 35 0.8764 0.00390 5

division Liquid parafins Propylen Glycol Example 1 1.82 1.87 Example 2 0.80 0.78 Example 3 1.90 1.90 Example 4 1.68 1.67 Example 5 1.60 1.69 Example 6 0.86 0.81 Example 7 0.74 0.72 Example 8 1.80 1.77 Example 9 1.68 1.72 Comparative Example 1 0.56 0.57 Comparative Example 2 2.01 2.07 Comparative Example 3 3.21 3.31

As shown in Table 2, the polymer beads of Examples 1 to 9 prepared using the hydrocarbon compound of C8 to C20 according to the present invention had an average particle diameter of 15 to 14 mu m and a variation coefficient of 16% to 19% As shown in Fig.

However, in the case of Example 7, since the initiator BZO is a reactive initiator having a high reactivity, the reaction proceeds before the hydrocarbon compound is placed and the CV value is not excellent.

In the first-bead system of the present invention, the specific gravity of Examples 1-9 was reduced to 20% as compared with the polymer powders prepared without the hydrocarbon of Comparative Example 1, and the adhesion test was also excellent.

  In addition, the polymer powder according to the present invention was normally polymerized without abnormal polymerization during the polymerization process, and there was no significant difference in particle size as compared with Comparative Example 1.

Also, in the case of beads prepared according to the present invention, the sedimentation rate is slowed down due to the decrease of the specific gravity, and thus the beads can be positioned without sinking in the cosmetic formulations.

On the other hand, the polymer beads of Comparative Example 1 prepared without a separate hydrocarbon derivative compound had similar physical properties such as average particle diameter and coefficient of variation, but the oil absorption was small as shown in Table 3, The adhesion may not be more excellent.

Therefore, the polymer bead of Comparative Example 1 may be less adherent than Examples 1 to 9 when used for beads for cosmetics.

   Further, even when the hydrocarbon compound was added as in Example 1, if the content was too small beyond the range of the present invention, no pore could be provided on the surface, so that it was not effective.

 In the case of Example 3, when 15% was added, the pore size was increased, but stability was poor in polymerization, and a small amount of small particles were produced.

 In addition, when the content is too large as in Comparative Examples 2 and 3, there is a large void in the inside, and the adhesion can be excellent.

 However, in the case of Comparative Example 3, as seen from a microscopic photograph (FIG. 3), the inside is empty, and the oil absorption is large in the future.

As shown in Table 3, according to the present invention, the polymer beads of the examples prepared using the hydrocarbon compounds of C8 to C20 according to the present invention have oil absorbtion (the amount of the solvent is mixed with the beads, In general, if the surface is smooth, the solvent is absorbed a little more.

It can be seen that the solvent is mainly used for the cosmetic, and the solvent is used for the cosmetic, and the adhesion is also improved. The porosity and the joints result in a smaller specific gravity and do not settle in cosmetic formulations.

As described above, the spherical polymer powder of Examples 1-9 of the present invention exhibits an average particle size, a variation coefficient, and the like equal to or more than those of Comparative Examples 1 to 3, and the adhesion test is also excellent without any coarse particles.

Therefore, the polysaccharide powder of the present invention can be usefully used as an additive which can be used in the production of cosmetics.

Claims (20)

Aromatic vinyl monomers; Acrylic acid or methacrylic acid alkyl ester monomers having 1 to 20 carbon atoms; And at least one monomer selected from the group consisting of acrylic acid or methacrylic acid fluoroalkyl ester monomers having 1 to 20 carbon atoms, a hydrocarbon compound, a phenol derivative compound having 6 to 50 carbon atoms, a crosslinking agent, &Lt; / RTI &gt; wherein the polymeric bead comprises a polymeric bead. The composition of claim 1, wherein the monomer is selected from the group consisting of methyl methacrylate, styrene, divinyl benzene, butyl methacrylate, trimethylol methane tetraacrylate, trimethylol methane triacrylate, trimethylol butane triacrylate, Wherein the polymer bead is at least one selected from the group consisting of polyvinylpyrrolidone and methacrylate. The composition of claim 1, wherein the hydrocarbone compound is selected from the group consisting of ISOPAR C, ISOPAR E, ISOPAR G, ISOPAR M, ISOPAR H, ISOPAR J, ISOPAR K, ISOPAR L, ISOPAR M and ISOPAR N By weight based on the total weight of the polymer beads. The composition for preparing polymer beads according to claim 1, wherein the hydrocarbone compound is contained in an amount of 10 to 30 parts by weight based on 100 parts by weight of the monomer. The method according to claim 1,
The crosslinking agent is selected from the group consisting of 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, , 1,6-hexanediol diacrylate, divinylbenzene, ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol Diacrylate, diacrylate, polybutylene glycol diacrylate, allyl acrylate, 1,2-ethanediol dimethacrylate, 1,3-propanediol dimethacrylate, 1,3-butanediol dimethacrylate, Butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol dimethacrylate re Diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, triethylene glycol methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol Wherein the polymer bead is at least one selected from the group consisting of dimethacrylate, polybutylene glycol dimethacrylate, allyl methacrylate, diallyl maleate, and trimethylpropane triacrylate. The method according to claim 1,
The initiator may be selected from the group consisting of benzoyl peroxide, azobisisobutyronitrile, azobismethylbutyronitrile, azobiscyclohexanecarbonitrile, potassium persulfate, sodium persulfate, ammonium persulfate, azo based water soluble initiator, benzoyl peroxide Wherein the polymer bead is at least one selected from the group consisting of lauryl peroxide, octanoyl peroxide, and dicumyl peroxide. The method according to claim 1,
Based on 100 parts by weight of at least one monomer selected from the group consisting of an aromatic vinyl monomer, an acrylic acid or methacrylic acid alkyl ester monomer having 1 to 20 carbon atoms, and an acrylic acid or a methacrylic acid fluoroalkyl ester monomer having 1 to 20 carbon atoms ,
10 to 30 parts by weight of the hydrocarbon compound having 8 to 30 carbon atoms,
1 to 98 parts by weight of a crosslinking agent,
1 to 5 parts by weight of initiator, and
Ion exchanged water 50 to 1000 parts by weight
&Lt; / RTI &gt; wherein the polymeric bead comprises a polymeric bead. The composition for preparing a polymer bead according to claim 1, further comprising a dispersion stabilizer in the composition. 9. The composition of claim 8, wherein the dispersion stabilizer is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, methylcellulose, ethylcellulose, sodium carboxymethylcellulose, polyacrylic acid, polymethacrylic acid, sodium polyacrylate, sodium polymethacrylate Wherein the polymer bead is at least one selected from the group consisting of gelatin, polyacrylamide, polyethylene oxide, polyvinyl methyl ether, polyethyleneimide, vinyl acetate copolymer, hydroxypropyl cellulose, silica and siloxane. The polymer bead composition according to claim 8, wherein the dispersion stabilizer is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the monomer. In the method for producing polymer beads,
At least one monomer selected from the group consisting of aromatic vinyl monomers, acrylic acid or methacrylic acid alkyl ester monomers having 1 to 20 carbon atoms, and acrylic acid or methacrylic acid fluoroalkyl ester monomers having 1 to 20 carbon atoms, a crosslinking agent, Ion exchanged water, and 10 to 30 parts by weight of a hydrocarbone compound,
&Lt; / RTI &gt; 12. The method of claim 11, wherein the suspension is prepared by mixing monomers, a crosslinking agent, an initiator and ion-exchanged water, followed by stirring at a stirring speed of 100 to 600 rpm. 12. The method of claim 11, wherein the suspension is prepared by mixing monomers, a crosslinking agent, an initiator, and ion-exchanged water, stirring at a stirring speed of 100 to 600 rpm, and stirring at 1,000 to 6,000 rpm in a homomixer &Lt; / RTI &gt; 12. The method according to claim 11, wherein the exothermic reaction is carried out at a reaction temperature of 70 to 80 DEG C for 30 minutes to 2 hours By weight based on the total weight of the polymer beads. 12. The method according to claim 11, wherein the exothermic reaction is carried out at a reaction temperature of 60 to 90 DEG C for 2 to 4 hours, Of the polymer beads. The method for producing a polymer bead according to claim 11, wherein the polymerizing step is carried out at a stirring speed of 100 to 600 rpm. A polymer bead produced using the composition according to any one of claims 1 to 10 and having an average particle diameter of 1 to 50 μm and a coefficient of variation (CV) of 5% to 30%. A polymer bead produced by the process according to any one of claims 11 to 16, characterized by an average particle diameter of 1 to 50 μm and a coefficient of variation (CV) of 5% to 30%. A compound prepared by using the composition according to any one of claims 1 to 10 or having a hemispherical shape in the shape of a bead prepared by the process according to any one of claims 11 to 16. A compound produced by using the composition according to any one of claims 1 to 10 or having a shape of a bead in which the shape of the bead is narrowed by the method according to any one of claims 11 to 16

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