KR101313069B1 - Composition for preparing crosslinked polymer particles and preparation method for crosslinked polymer particles using the same - Google Patents

Abstract

The present invention relates to a composition for producing monodisperse crosslinked polymer particles and a method for producing monodisperse crosslinked polymer particles using the same. The composition for producing monodisperse crosslinked polymer particles according to the present invention comprises a vinyl monomer capable of radical polymerization; 200 to 2,000 parts by weight of the solvent based on 100 parts by weight of the vinyl monomer; 0.1 to 10 parts by weight of a dispersion stabilizer based on 100 parts by weight of the solvent; And a second crosslinking agent having a high degree of crosslinking in the composition for preparing the seed polymer particles, including 0.1 to 10 parts by weight of a radical polymerization initiator with respect to 100 parts by weight of the vinyl monomer. According to the present invention, monodisperse crosslinked polymer particles having a crosslinking degree of 5% by weight or more may be prepared through seed dispersion polymerization, and particles having excellent stability to an organic solvent may be prepared due to the use of a crosslinking agent having a high crosslinking degree.

Seed, dispersion, polymerization, crosslinking agent, monodispersion, radical, dispersion stabilizer

Description

Composition for preparing monodisperse crosslinked polymer particles and method for producing monodisperse crosslinked polymer particles using the same {Composition for preparing crosslinked polymer particles and preparation method for crosslinked polymer particles using the same}

The present invention relates to a composition for producing monodisperse crosslinked polymer particles and a method for preparing monodisperse crosslinked polymer particles using the same, and more particularly, to seed particles crosslinked by a non-crosslinking or a predetermined fraction or less (by a second crosslinking agent) through dispersion polymerization. After preparing the first crosslinking agent (first crosslinking agent) having a high degree of crosslinking by the radical crosslinking polymerization reaction, the composition for producing monodisperse crosslinked polymer particles having a high degree of crosslinking and stable in an organic solvent and a method for producing monodisperse crosslinked polymer particles using the same It is about.

Monodisperse crosslinked polymer particles are used in spacers, optical acid fillers, anti-glare coating fillers, fillers for anisotropic conductive films, heat resistant particles, and porous particles in LCD devices. .

Such monodisperse crosslinked polymer particles are generally produced through emulsion polymerization, suspension polymerization, dispersion polymerization, seed polymerization.

In the case of emulsion polymerization, a method of preparing particles by adding a monomer and an emulsifier to an aqueous solution and using an initiator that is dissolved in the aqueous solution. Generally, the particle size is 1 micron or less, and in order to prepare more than one particle, Seed polymerization of is required. This process requires a lot of time in the process and requires an increase in manufacturing cost. In addition, due to the agglomeration phenomenon due to the crosslinking agent, it is possible to prepare only particles having a crosslinking degree of typically less than 5% by weight.

In the case of suspension polymerization, a method of preparing particles through mechanical stirring by adding monomers and surfactants to an aqueous solution and using an initiator dissolved in the monomers, generally, the size of the particles produced is from several microns to several hundred microns. However, there is a disadvantage in that the particle size distribution is very wide due to the combination of monomer droplets during mechanical stirring.

In the case of dispersion polymerization, the monomer is dissolved but the resulting polymer is not dissolved, and the monomer, a dispersion stabilizer, and an initiator are added to polymerize the particles. Hundreds of nanometers to several tens of microns of monodisperse particles can be obtained. In the case of the non-crosslinked linear polymer, the monodispersed spherical particles can be obtained as described above. However, when the crosslinking agent is added to prepare the crosslinked particles, the crosslinking agent dissolved in the solvent causes the aggregation of particles to occur. Since the surface of the nucleus is formed in the glass phase having a high degree of crosslinking, it is difficult to absorb the monomer from the solvent and swelling is difficult, so that it is difficult to obtain spherical particles. In general, spherical crosslinked monodisperse particles do not exceed 3% by weight of crosslinking, and US Patent No. 5216096 reported that polydispersion and aggregation occur even with 0.5% by weight of crosslinking agent.

In order to solve the shortcomings of the conventional manufacturing techniques, a dispersion polymerization method using improved solvent and crosslinking agent properties is used, or monodisperse polymer particles are prepared using emulsion and dispersion polymerization and used as seeds to swell and polymerize the crosslinking agent. Seed polymerization methods have been proposed. Dispersion polymerization method with improved properties of solvent and crosslinking agent can produce polymer particles with high degree of crosslinking, but there is a disadvantage of low yield due to agglomeration, or organic compounds due to the use of long chain flexible crosslinking agent. Swelling to the solvent has a severe disadvantage. The seed polymerization process is in most cases a seed emulsion polymerization or seed suspension polymerization which is divided into the steps of redispersing the resulting seeds in an aqueous solution, swelling the seeds with a crosslinking agent or a mixture of crosslinking agents and monomers, and a polymerization step. By preparing particles having a crosslinking degree of 5% by weight or more through seeded suspension polymerization, the process time is very long, which increases the manufacturing cost.

As the prior art related to the present invention, Korean Patent Publication Nos. 2001-0095368, 10-2005-0034165, 2003-0056100, 10-2004-0016624, 10-2004-0054986, and 10-2004- 0071431, 10-2005-0043416, 10-2006-0052566, etc., but it is not easy to produce monodisperse crosslinked polymer particles having a high degree of crosslinking of 5% by weight or more, and even if such preparation is possible, inefficiency in the manufacturing process, There is a need for new economics because of non-economics, and the present invention has been devised under such technical background.

The present invention is not capable of producing monodisperse polymer particles having a crosslinking degree of 5% by weight or more by conventional dispersion polymerization techniques, and producing, drying or filtering seed particles through conventional seed emulsion and suspension polymerization methods, and redispersing seeds. There is a problem in solving the problem that the necessity of an increase in the manufacturing cost is necessary because the high-crosslinked polymer particles can be manufactured only through a multi-step manufacturing method such as swelling and polymerization of seeds. The present invention provides a composition for preparing crosslinked polymer particles having a crosslinking degree of 5% by weight or more by introducing a crosslinking agent having a high degree of crosslinking into seed dispersion polymerization and a method for preparing monodisperse crosslinked polymer particles using the same. It aims to do it.

The composition for producing monodisperse crosslinked polymer particles provided as a problem solving means for achieving the problem to be solved by the present invention, a vinyl monomer capable of radical polymerization; 200 to 2,000 parts by weight of the solvent based on 100 parts by weight of the vinyl monomer; 0.1 to 10 parts by weight of a dispersion stabilizer based on 100 parts by weight of the solvent; And 0.1 to 10 parts by weight of a radical polymerization initiator with respect to 100 parts by weight of the vinyl monomer; and having a crosslinking degree of 5 to 50 parts by weight or more based on 5 to 50 parts by weight relative to 100 parts by weight of the vinyl monomer. A first crosslinking agent is further included.

It is preferable that the composition for preparing the seed polymer particles further comprises a second crosslinking agent having a content of more than 0 and less than 5 parts by weight with respect to 100 parts by weight of the vinyl monomer.

Monodisperse crosslinked polymer particle manufacturing method provided as a problem solving means for achieving the problem to be solved by the present invention, (S1) 200 to 2,000 parts by weight of the vinyl monomer capable of radical polymerization, 100 parts by weight of the vinyl monomer Preparing a composition comprising a solvent, 0.1 to 10 parts by weight of a dispersion stabilizer based on 100 parts by weight of the solvent, and 0.1 to 10 parts by weight of a radical polymerization initiator based on 100 parts by weight of the vinyl monomer; (S2) adding the prepared composition to a reactor, and reacting for 5 to 72 hours at a temperature condition of 50 to 80 ℃ to prepare a seed polymer particles; (S3) adding 5 to 50 parts by weight of the first crosslinking agent based on 100 parts by weight of the vinyl monomers, based on 100 parts by weight of the vinyl monomers, to the prepared seed polymer particle solution; And (S4) cross-polymerizing the seed polymer particle solution to which the first crosslinking agent is added by a radical polymerization reaction at a temperature of 50 to 80 ° C. for 3 to 48 hours to prepare cross-linked polymer particles. It features.

The addition of the first crosslinking agent in the step (S3) is preferably performed after the seed particle conversion prepared in the step (S1) is saturated. When the first crosslinking agent is added before the conversion rate of the seed particles is saturated, it is preferable to add the crosslinking agent after the conversion rate is saturated because unreacted monomers present in the solvent and the introduced crosslinking agent may react with each other.

The first crosslinking agent is used to crosslink uncrosslinked or crosslinked seed polymer particles to less than 5% by weight to 5% by weight or more to increase mechanical properties and stability to organic solvents. The first crosslinking agent is preferably included in an amount of 5 to 50 parts by weight based on 100 parts by weight of the vinyl monomer. In relation to the numerical range for the first crosslinking agent content, when the lower limit is reached, the degree of crosslinking is not sufficiently secured, so that the stability of the organic solvent is lowered. When the upper limit is exceeded, the crosslinking agents present in the solvent react with each other to cause aggregation. It is not desirable because it occurs.

The first crosslinking agent is preferably a substance belonging to one selected from vinylbenzene, a polyfunctional monomer crosslinking agent, and an oligomer crosslinking agent. The polyfunctional acrylate crosslinking agent is pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, trimethylpropane ethoxy triacrylate, propoxylated glycerol triacrylate, It is preferable that it is a single substance or a mixture of two or more selected from pentaerythritol tetraacrylate, dipentaerythritol hydroxy pentaacrylate, and dipentaerythritol hexaacrylate, and the oligomer-based crosslinking agent is a urethane acrylate oligomer, epoxy acrylate oligomer It is preferable that it is a single substance or a mixture of two or more selected from among polyester, acrylate, and polyether.

After the addition of the first crosslinking agent of step (S3), the swelling process is further performed for 8 hours or less under a temperature condition of 50 to 80 ° C for the seed polymer particles, and then the crosslinking reaction of step (S4) is performed. It is preferable to proceed. In general, the crosslinking agent having a high degree of crosslinking is mostly dispersed in a solvent phase, but a part of the crosslinking agent may penetrate into the inside of the seed polymer particle through a swelling process. The swelling process does not require a special temperature or time, but it is preferable to proceed for up to 8 hours at a temperature of 50 to 80 ℃ or less due to the manufacturing process and manufacturing cost. In addition, the swelling process can be carried out at a temperature of 50 ℃ or less, but the reaction temperature is 50 to 80 ℃ because the additional cooling process has to be carried out, there is a disadvantage in that the manufacturing process is long, it was carried out at the reaction temperature. In addition, the swelling time is not particularly limited, but if it exceeds 8 hours, since the crosslinking of the first crosslinking agent proceeds by the initiator remaining in the reactant, it is not necessary to proceed the swelling process for more than 8 hours. On the other hand, even if the swelling process is omitted and the reaction proceeds, the object of the present invention can be sufficiently achieved.

In the step (S3), it is preferable to further include the step of further adding a radical polymerization initiator in an amount corresponding to 0.1 to 10 parts by weight of the amount of the first crosslinking agent.

In the above-mentioned composition for producing monodisperse crosslinked polymer particles and a method for producing the same, each of the component materials is preferably used, but is not necessarily limited thereto.

The vinyl monomer is a substance belonging to one selected from an aromatic vinyl monomer and an acrylic vinyl monomer, and the aromatic vinyl monomer is a single substance or a mixture of two or more selected from styrene, alphamethylstyrene, and chlorostyrene. Preferably, the acrylic vinyl monomer is methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and It is preferable if it is a single substance selected from benzyl (meth) acrylate or a mixture consisting of two or more.

The solvent is preferably used so that the content of 200 to 2,000 parts by weight with respect to 100 parts by weight of the vinyl monomer. In relation to the numerical range for the content of the solvent, the concentration of the polymer particles generated when the lower limit is less than the high concentration of the polymer particles are generated is not preferable due to the collision between particles occurs, the concentration of the polymer particles produced when the upper limit is exceeded Yield is lowered because the yield is low, the resulting nucleus is not uniformly grown due to the lack of concentration of the monomer has a disadvantage of poor dispersion.

Moreover, the said solvent can also be used in mixture with other solvents, such as water, deionized water, benzene, toluene, and xylene, in order to adjust solubility. In general, as the solubility of the solvent in the polymer formed by the monomer and the crosslinking agent increases, larger particles can be obtained, and vice versa, smaller particles are obtained.

The solvent is a substance belonging to one selected from alcohols and cellosolves, and the alcohols solvent is methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, methoxy methanol, It is preferable that it is a single substance selected from methoxy methanol, methoxy propanol, ethoxy propanol, and diacetone alcohol, or a mixture consisting of two or more, and the cellosolve solvents are methyl solosolve, ethyl cellosolve, and isopropyl cell. It is preferable that it is a single substance or a mixture consisting of two or more selected ones of rosolves.

The dispersion stabilizer serves as a nucleus for the growth of monomers at the beginning of the polymerization and stabilizes the surface of the particles thus formed to prevent aggregation between the particles. Dispersion stabilizers are divided into ionic and nonionic, and ionicity stabilizes particles by electrical repulsive force. Nonionicity prevents aggregation between particles due to long chain steric hindrance. Especially in dispersion polymerization, it is preferable to use a form which prevents aggregation due to steric hindrance of long chains or to use an ionic dispersion stabilizer having a long chain.

The dispersion stabilizer is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the solvent. Regarding the numerical range of the content of the dispersion stabilizer, if it is less than the lower limit, the amount of dispersion stabilizer is insufficient to cause aggregation between particles, resulting in poor stability and poor dispersion. It is undesirable because the amount of dispersion stabilizer remaining is high and an additional process of removing the dispersion stabilizer is required.

The dispersion stabilizer is a single or two or more selected from methylcellulose, ethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylmethyl ether, polyvinylacetate, polyacrylic acid, and polyvinylsulfonic acid. It is preferable that it is a mixture which consists of a compound, and it is preferable if it is a copolymer of two or more substances selected from these materials.

The radical polymerization initiator, it is preferable to use 0.1 to 10 parts by weight relative to 100 parts by weight of the vinyl monomer. In relation to the numerical range of the content of the radical polymerization initiator, if the lower limit is not reached, the yield of converting the vinyl monomer into the polymer particles is reduced and the polymerization time is long, which is not preferable because it does not reach an amount effective for initiating the radical polymerization reaction, When the upper limit is exceeded, the radical polymerization time is shortened, but the dispersion degree of the resulting polymer particles is poor, which is not preferable. In general, as the amount of the radical polymerization initiator increases, the size of the polymer particles to be produced increases and the degree of dispersion tends to deteriorate. In addition, it is preferable to carry out radical polymerization reaction in the temperature range of 50-80 degreeC. In relation to the numerical range for the polymerization temperature, when the lower limit is reached, the half-life of the radical polymerization initiator is long, so that the polymerization time is too long, which is not preferable. When the upper limit is exceeded, the radical polymerization time is shortened, but the degree of dispersion of the particles produced. Since it becomes bad and it is unpreferable, special attention is paid to maintenance of radical polymerization reaction temperature conditions.

The radical polymerization initiator is a substance belonging to one selected from peroxide and azo, wherein the peroxide compound is benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl A single substance or a mixture of two or more selected from hydroperoxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisobutyrate Preferably, the azo compound is 2,2'-azobisisobutyronitrile, 2,2'-azobis (2methylisobutyronitrile), and 2,2'-azobis (2,4dimethyl A single compound selected from azo compounds such as valeronitrile) or a mixture of two or more thereof is preferable, but any solvent can be dissolved in the solvent and the vinyl monomer to form free radicals. It is possible.

The second crosslinking agent which may be used in addition to the composition for preparing the seed polymer particles may be used in an amount of less than 5 parts by weight based on 100 parts by weight of the vinyl monomer. Regarding the numerical range for the content of the second crosslinking agent, when the upper limit is exceeded, a phenomenon in which the polymer particles, which are reaction products, are agglomerated, is not preferable because monodisperse polymer particles cannot be obtained. When the seed polymer particles are manufactured without additionally using the second crosslinking agent, the non-crosslinked monodisperse seed polymer particles in a state in which no crosslinking occurs may be prepared.

The second crosslinking agent is preferably a substance belonging to one selected from vinylbenzene, a polyfunctional monomer crosslinking agent, and an oligomer crosslinking agent. The polyfunctional acrylate crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate, pentaerythritol triacrylate, tri Methylene propyl triacrylate, propoxylated glycerol triacrylate, trimethylropropane ethoxy triacrylate, propoxylated glycerol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxy pentaacrylate, and One selected from dipentaerythritol hexaacrylate or a mixture of two or more thereof is preferable, and the oligomer-based crosslinking agent is selected from urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylate, and polyether. It is preferable if the danilmul or a mixture of two or more.

According to the present invention, seed dispersion polymerization is performed by adding a crosslinking agent having a high degree of crosslinking to a dispersion solution containing uncrosslinked and crosslinked crosslinked seed polymer particles having a crosslinking degree of less than 5% by weight. Excellent stability to organic solvents and monodisperse crosslinking can also be produced crosslinked polymer particles of 5% by weight or more.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to facilitate understanding of the present invention. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

Example  One

<Production Step of Seed Polymer Particles>

50 g of styrene as a vinyl monomer, 450 g of ethanol as a solvent and 50 g of deionized water, 2 g of polyvinylpyrrolidone as a dispersion stabilizer, and 2 g of 2,2'-azobisisobutyronitrile as a radical polymerization initiator were placed in a jacketed reactor at 70 ° C. The reaction was performed for 20 hours to prepare non-crosslinked seed polymer particles.

1 is an optical photomicrograph of seed polymer particles by dispersion polymerization according to Example 1 of the present invention. According to Figure 1, it can be seen that the non-crosslinked seed polymer particles have a diameter of 2.5 μm or less and are formed very uniformly.

<Production Step of Crosslinked Polymer Particles>

5 g of dipentaerythritol hydroxy pentaacrylate was added to the seed polymer particle solution maintained at 70 ° C. as a first crosslinking agent, and then 0.2 g of 2,2′-azobisisobutyronitrile was added as a radical polymerization initiator. Crosslinked polymer particles were prepared by allowing time-radical polymerization to occur.

2 is a view showing the conversion (conversion,%) over time of the seed polymer particles by dispersion polymerization according to Example 1 of the present invention. According to FIG. 2, the conversion rate of the non-crosslinked seed polymer particles is shown to be saturated at 7 hours. As such, after the conversion rate of the non-crosslinked seed polymer particles is saturated, an effective crosslinking polymerization may be achieved by adding a crosslinking agent. The conversion rate was determined by measuring 5g of the reactant according to the polymerization time and drying the resultant in an oven at 130 ° C. for 1 hour, and then weighing the mass of the polymer remaining after drying with respect to the weight of the monomers.

3 is an optical micrograph of a crosslinked polymer particle according to Example 1 of the present invention. According to Figure 3, the resulting crosslinked polymer is a uniform particle having a diameter of about 2.8㎛, the increase in diameter shows that the particles grew by the crosslinking of the crosslinking agent having a high degree of crosslinking.

Example  2

Crosslinked polymer particles were prepared in the same manner as described in Example 1 except that dipentaerythritol hydroxy pentaacrylate used in Example 1 was replaced with dipentaerythritol hexaacrylate.

Figure 4 is an optical micrograph of the crosslinked polymer particles according to Example 2 of the present invention. According to FIG. 4, the resulting crosslinked polymer particles are uniform particles having a diameter of about 2.8 μm, and the increase in diameter shows that the particles grew by crosslinking of a crosslinking agent having a high degree of crosslinking.

Comparative Example  One

Crosslinked polymer particles were prepared in the same manner as described in Example 1 except that dipentaerythritol hydroxy pentaacrylate used in Example 1 was replaced with ethylene glycol dimethacrylate.

Comparative Example  2

Crosslinked polymer particles were prepared in the same manner as described in Example 1, except that the pentaerythritol hydroxy pentaacrylate (5 g) used in Example 1 was increased to 30 g.

Comparative Example  3

The crosslinked seed polymer particles were prepared in the same manner as described in Example 1, except that styrene 45g and divinylbenzene 5 were used instead of 50g of styrene used in the preparation of the seed polymer particles of Example 1. .

5 is an optical micrograph of the crosslinked polymer particles according to Comparative Example 3 compared to the embodiment of the present invention. According to Figure 5, the diameter of the primary particles of the resulting cross-linked polymer particles is 2 ㎛ or less, due to the aggregation between the particles shows that the diameter of the secondary particles is multi-dispersed to ~ several hundred ㎛.

<Measurement of particle size and dispersion degree>

Particle size and dispersion of the seed polymer particles of Example 1 and the crosslinked polymer particles of Examples 1 and 2 and Comparative Examples 1 to 3 were measured using a particle size analyzer, and are shown in Table 1 below.

<Organic Solvent Stability Evaluation>

10 g of toluene was added to the seed polymer solution of Example 1 and 1 g of the crosslinked polymer particle solutions of Examples 1 and 2 and Comparative Examples 1 to 3, and the stability of the organic solvent was visually observed, and evaluated according to the following criteria. It was.

<Evaluation Criteria>

○: When visually observed after 24 hours, the particles are not dissolved in the organic solvent, there is no change in turbidity, and the particles are well dispersed without aggregation of the particles.

(Triangle | delta): When visually observed after 24 hours, when a particle | grain does not melt | dissolve in an organic solvent and there is no change of turbidity but there is a little aggregate of particle | grains

■: When observed visually after 24 hours, the particles dissolve in the organic solvent and have a change in turbidity or become transparent.

division Particle size (탆) Dispersion (Standard Deviation) Organic Solvent Stability Example 1 (seed polymer) 2.6 0.49 ■ Example 1 (crosslinked polymer) 2.8 0.52 ○ Example 2 2.8 0.53 ○ Comparative Example 1 2.6 0.51 ■ Comparative Example 2 Not measurable Polydispersion (gel) △ Comparative Example 3 2.0-hundreds Dispersed △

As shown in Table 1, it can be seen that the crosslinked polymer particles prepared through seed dispersion polymerization using the crosslinking agents having high degree of crosslinking in Examples 1 and 2 are particles having monodispersity and stability in an organic solvent. On the other hand, the crosslinked polymer particles of Comparative Example 1, which was seed dispersed polymerization using the seed polymer of Example 1 and the crosslinking agent having two functional groups without crosslinking, showed monodispersity but low stability to organic solvents. Can be. In addition, when using a crosslinking agent having a high degree of crosslinking in excess of 50% by weight relative to the monomer in Comparative Example 2, agglomeration between the particles and gelation occurs due to polymerization of the crosslinking agent having a high degree of crosslinking present on the solvent, and is present in an aggregated state without being dispersed in an organic solvent. It can be seen that. In Comparative Example 3, in the case of the polymer particles having a crosslinking agent of 5% by weight or more relative to the monomers through dispersion polymerization, the crosslinking agent present in the solvent phase causes agglomeration between the particles to obtain monodisperse particles. You can see that they exist in a cluster.

Optimal embodiments of the present invention described above have been disclosed. Although specific terms have been used herein, they are only used for the purpose of describing the present invention in detail to those skilled in the art and are not intended to limit the scope of the present invention as defined in the claims or the claims.

The following drawings are attached to this specification together with the detailed description of the invention described above as being presented only as a material for understanding the technical spirit of the present invention in more detail, the present invention is not limited to the matters described only in those drawings is not interpreted. It should be obvious.

1 is an optical photomicrograph of seed polymer particles by dispersion polymerization according to Example 1 of the present invention.

2 is a view showing the conversion (conversion,%) over time of the seed polymer particles by dispersion polymerization according to Example 1 of the present invention.

3 is an optical micrograph of a crosslinked polymer particle according to Example 1 of the present invention.

Figure 4 is an optical micrograph of the crosslinked polymer particles according to Example 2 of the present invention.

5 is an optical micrograph of the crosslinked polymer particles according to Comparative Example 3 compared to the embodiment of the present invention.

Claims (31)

A monodisperse crosslinked polymer particle comprising a crosslinking product of a seed polymer particle and a first crosslinking agent formed on the seed polymer particle and having a crosslinking degree of 5% by weight or more, 100 parts by weight of the vinyl monomer capable of radical polymerization of the seed polymer particles; 200 to 2,000 parts by weight of the solvent based on 100 parts by weight of the vinyl monomer; 0.1 to 10 parts by weight of a dispersion stabilizer based on 100 parts by weight of the solvent; And It is a polymerization product of the composition for preparing the seed polymer particles comprising 0.1 to 10 parts by weight of a radical polymerization initiator relative to 100 parts by weight of the vinyl monomer, The vinyl monomer is a material belonging to one selected from an aromatic vinyl monomer and an acrylic vinyl monomer, The solvent is a substance belonging to one selected from alcohols and cellosolves The first crosslinking agent is a multifunctional acrylate crosslinking agent, 5 or 6 functional groups of the first crosslinking agent, The content of the first crosslinking agent is 5 to 50 parts by weight based on 100 parts by weight of the vinyl-based monomer monodisperse crosslinked polymer particles. The method of claim 1, The composition for preparing the seed polymer particles further comprises a second crosslinking agent having a content of more than 0 and less than 5 parts by weight with respect to 100 parts by weight of the vinyl monomer, The second crosslinking agent is a monodisperse crosslinked polymer particle, characterized in that the material belonging to one selected from divinylbenzene, polyfunctional acrylate crosslinking agent, and oligomer crosslinking agent. delete 3. The method of claim 2, The polyfunctional acrylate crosslinking agent is ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate, pentaerythritol triacrylate, trimethylene propyl triacryl Latex, propoxylated glycerol triacrylate, trimethylropropane ethoxy triacrylate, propoxylated glycerol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxy pentaacrylate, and dipentaerythritol hexa A single one or a mixture of two or more selected from acrylates, The oligomer-based crosslinking agent is a monodisperse crosslinked polymer particle, characterized in that the urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylate, one or a mixture of two or more selected from polyether. delete The method of claim 1, The aromatic vinyl monomer is a single substance or a mixture consisting of two or more selected from styrene, alphamethylstyrene, and chlorostyrene, The acrylic vinyl monomers are methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acryl. Monodisperse crosslinked polymer particles, characterized in that the mixture is composed of one or two or more selected from the rate. delete The method of claim 1, The alcohol solvent is one selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, methoxy methanol, ethoxy methanol, methoxy propanol, ethoxy propanol, and diacetone alcohol Single or a mixture of two or more of The cellosolve solvent is a monodisperse crosslinked polymer particles, characterized in that the mixture consisting of one or two or more selected from methyl solosolve, ethyl cellosolve, and isopropyl cellosolve. The method according to any one of claims 1, 2 or 4, The dispersion stabilizer is a single or two or more selected from methylcellulose, ethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylmethyl ether, polyvinylacetate, polyacrylic acid, and polyvinylsulfonic acid. Monodisperse crosslinked polymer particles, characterized in that the mixture consisting of. The method according to any one of claims 1, 2 or 4, The dispersion stabilizer is a copolymer of two or more materials selected from methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, polyvinylacetate, polyacrylic acid, and polyvinylsulfonic acid. Monodisperse crosslinked polymer particles, characterized in that. The method according to any one of claims 1, 2 or 4, The radical polymerization initiator, monodisperse crosslinked polymer particles, characterized in that the material belonging to one selected from the peroxide-based and azo-based. 12. The method of claim 11, The peroxide compound is benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, t Single or a mixture of two or more selected from -butylperoxy-2-ethylhexanoate and t-butylperoxyisobutyrate, The azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2methylisobutyronitrile), and 2,2'-azobis (2,4dimethylvaleronitrile Monodisperse crosslinked polymer particles, characterized in that a single or a mixture of two or more selected from azo compounds such as). delete The method of claim 1, The polyfunctional acrylate-based crosslinking agent is a monodisperse crosslinked polymer particle, characterized in that a single or a mixture of two selected from dipentaerythritol hydroxy pentaacrylate and dipentaerythritol hexaacrylate. (S1) A vinyl monomer capable of radical polymerization, 200 to 2,000 parts by weight of a solvent based on 100 parts by weight of the vinyl monomer, 0.1 to 10 parts by weight of a dispersion stabilizer, and 0.1 to 100 parts by weight of the vinyl monomer, based on 100 parts by weight of the solvent. Preparing a seed polymer particle preparing composition including to 10 parts by weight of a radical polymerization initiator; (S2) preparing the seed polymer particles by adding the prepared seed polymer particle preparation composition into a reactor and reacting for 5 to 72 hours at a temperature condition of 50 to 80 ° C .; And (S3) adding 5 to 50 parts by weight of the first crosslinking agent to 100 parts by weight of the vinyl monomer to the prepared seed polymer particle solution; (S4) cross-polymerizing the seed polymer particle solution to which the first crosslinking agent was added by a radical polymerization reaction at a temperature of 50 to 80 ° C. for 3 to 48 hours to prepare a crosslinked polymer particle; The vinyl monomer is a substance belonging to one selected from an aromatic vinyl monomer and an acrylic vinyl monomer, The solvent is a substance belonging to one selected from alcohols and cellosolves, The first crosslinking agent is a polyfunctional acrylate crosslinking agent, 5 or 6 functional groups of the first crosslinking agent, The crosslinked polymer particles are monodisperse crosslinked polymer particle production method, characterized in that it has a crosslinking degree of 5% by weight or more. 16. The method of claim 15, The composition for preparing the seed polymer particles of step (S1) is made of a second crosslinking agent having a content of more than 0 and less than 5 parts by weight with respect to 100 parts by weight of the vinyl monomer, The second crosslinking agent is a monodisperse crosslinked polymer particle production method, characterized in that the material belonging to one selected from divinylbenzene, polyfunctional acrylate crosslinking agent, and oligomer crosslinking agent. delete 17. The method of claim 16, The polyfunctional acrylate crosslinking agent is ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate, pentaerythritol triacrylate, trimethylene propyl triacryl Latex, propoxylated glycerol triacrylate, trimethylropropane ethoxy triacrylate, propoxylated glycerol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxy pentaacrylate, and dipentaerythritol hexa A single one or a mixture of two or more selected from acrylates, The oligomer-based crosslinking agent is a monodisperse crosslinked polymer particle production method, characterized in that the urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylate, and a single one or a mixture of two or more selected from polyethers. 16. The method of claim 15, The addition of the first crosslinking agent in the step (S3), monodisperse crosslinked polymer particle production method, characterized in that is made after the seed particle conversion prepared in the step (S1) is saturated. 16. The method of claim 15, After the addition of the first crosslinking agent of step (S3), the swelling process is further performed for 8 hours or less under a temperature condition of 50 to 80 ° C for the seed polymer particles, and then the crosslinking reaction of step (S4) is performed. Process for producing monodisperse crosslinked polymer particles, characterized in that it proceeds. 16. The method of claim 15, In the step (S3), monodisperse crosslinking further comprising the step of additionally adding a radical polymerization initiator in an amount corresponding to 5 to 15% of the amount of the radical polymerization initiator used in the step (S1). Polymer particle manufacturing method. delete 16. The method of claim 15, The aromatic vinyl monomer is a single substance or a mixture consisting of two or more selected from styrene, alphamethylstyrene, and chlorostyrene, The acrylic vinyl monomers are methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acryl. A monodisperse crosslinked polymer particle production method, characterized in that a single substance selected from the rate or a mixture consisting of two or more. delete 16. The method of claim 15, The alcohol solvent is one selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, methoxy methanol, ethoxy methanol, methoxy propanol, ethoxy propanol, and diacetone alcohol Single or a mixture of two or more of The cellosolve solvent is a monodisperse crosslinked polymer particle production method, characterized in that a single or a mixture of two or more selected from methyl solosolve, ethyl cellosolve, and isopropyl cellosolve. The method according to any one of claims 15, 16 and 18 to 21, The dispersion stabilizer is a single or two or more selected from methylcellulose, ethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylmethyl ether, polyvinylacetate, polyacrylic acid, and polyvinylsulfonic acid. Method for producing a monodisperse crosslinked polymer particles, characterized in that the mixture consisting of. The method according to any one of claims 15, 16 and 18 to 21, The dispersion stabilizer is a copolymer of two or more materials selected from methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, polyvinylacetate, polyacrylic acid, and polyvinylsulfonic acid. Method for producing monodisperse crosslinked polymer particles, characterized in that. The method according to any one of claims 15, 16 and 18 to 21, The radical polymerization initiator, monodisperse crosslinked polymer particle production method, characterized in that the material belonging to one selected from the peroxide-based and azo-based. The method of claim 28, The peroxide compound, benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t- butyl hydroperoxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, t Single or a mixture of two or more selected from -butylperoxy-2-ethylhexanoate and t-butylperoxyisobutyrate, The azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2methylisobutyronitrile), and 2,2'-zobis (2,4dimethylvalero A method for producing monodisperse crosslinked polymer particles, characterized in that a single substance or a mixture of two or more selected from azo compounds such as nitrile). delete 16. The method of claim 15, The multifunctional acrylate-based crosslinking agent is a monodisperse crosslinked polymer particle production method, characterized in that a single or a mixture of two selected from dipentaerythritol hydroxy pentaacrylate and dipentaerythritol hexaacrylate.

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