KR20220170474A - Manufacturing Method of organic-inorganic hybrid particles with High heat resistance - Google Patents

Abstract

The present invention relates to a method for producing organic-inorganic hybrid cross-linked particles and organic-inorganic hybrid cross-linked particles. According to the present invention, the method for producing organic-inorganic hybrid cross-linked particles can have a simple process and make mass production efficiently possible since non-emulsification or multi-step non-emulsion polymerization is used, and can produce cross-linked particles with monodisperse and high degree of cross-linking since an acrylic monomer with a polar group and a metal cross-linking agent. In addition, the cross-linked particles have excellent solvent stability even when added to a solvent since the cross-linked particles have a small time-variant change in viscosity. It is possible to produce high heat-resistant organic-inorganic hybrid cross-linked particles of various average particle sizes through the production method of the present invention, and the high heat-resistant organic-inorganic hybrid cross-linked particles produced thereby can be applied to various industrial fields, including a filler for light diffusion films for LCDs, an irregularity forming agent for anti-fingerprint (AG) films, an anti-blocking agent, a conductive ball, paint, ink, and cosmetics.

Description

Manufacturing method of organic-inorganic hybrid particles with high heat resistance

The present invention relates to highly heat-resistant organic-inorganic hybrid crosslinked particles and a method for preparing the same. Specifically, the present invention relates to highly heat-resistant monodisperse organic-inorganic hybrid crosslinked particles having excellent solvent stability by imparting a high degree of crosslinking and a method for preparing the same.

Highly heat-resistant monodisperse crosslinked particles are applied in various fields depending on the shape, size and uniformity of the particles. For example, it is applied to various industrial fields such as fillers for light diffusion films for LCDs, irregularities forming agents for anti-fingerprint (AG) films, column fillers for GPC, anti-blocking agents, anisotropic conductive balls, additives for paints, inks and cosmetics. there is. These cross-linked particles have a spherical shape with an average particle diameter of several nm to several tens of μm. It is required.

In general, methods for producing spherical crosslinked particles satisfying the above physical properties include suspension polymerization, emulsion polymerization, dispersion polymerization, and seed polymerization. Particularly, in the case of dispersion polymerization, as a method capable of producing organic polymer particles having a monodisperse distribution with a size of several microns, there is an advantage in that polymerization can be performed in an aqueous or non-aqueous system regardless of the polarity of monomers and polymerization solvents. Dispersion polymerization is very advantageous in preparing non-crosslinked particles, but in the case of crosslinked particles, since the nucleus is crosslinked during the growth process, a new nucleation reaction proceeds in the continuous phase, resulting in difficulty in preparing monodisperse particles.

In addition, a seed polymerization method has been proposed in which monodisperse particles are prepared using the emulsion and dispersion polymerization and then reacted with a crosslinking agent using the same as seed particles, but the compatibility between the seed particles and the crosslinking agent is poor and aggregation during the reaction is poor. There are fatal disadvantages in that this easily occurs and the uniformity (monodispersity) of the particles is poor. In addition, the conventional seed polymerization method has a complicated process and a long process time, making efficient mass production difficult.

Therefore, there is an urgent need for research and development on a method for producing crosslinked particles having excellent monodispersity while imparting a high degree of crosslinking through a simple process.

KR 10-2006-0075259 A (2006.07.04)

An object of the present invention is to provide a method for producing highly heat-resistant organic-inorganic hybrid crosslinked particles using an acrylic monomer having a polar group and a metal crosslinking agent.

In addition, an object of the present invention is to provide a method for producing highly heat-resistant organic-inorganic hybrid crosslinked particles capable of efficient mass production through a simple process.

Another object of the present invention is to provide monodisperse organic-inorganic hybrid crosslinked particles having high degree of crosslinking, excellent heat resistance and solvent stability, and a method for preparing the same.

In order to achieve the above object, the inventors of the present inventors have conducted endless research to develop monodisperse organic-inorganic hybrid crosslinked particles having a simple process, high crosslinking degree, and excellent heat resistance and solvent stability, and surprisingly, acrylic monomers and metals having polar groups In the case of using a crosslinking agent, the polymerization process is very simple, but monodispersity and high degree of crosslinking can be imparted to the crosslinked particles, and the invention is completed by discovering that the heat resistance is excellent and the change in viscosity with time is small even when added to a solvent, and the solvent stability is excellent. did

The present invention comprises the steps of preparing a dispersion of organic polymer particles having a polar group; and cross-linking by adding a metal cross-linking agent to the dispersion in a basic atmosphere.

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the dispersion of organic polymer particles may be prepared by dispersion polymerization, non-emulsion polymerization, or multi-step non-emulsion polymerization.

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the organic polymer particles may be acrylic polymer particles.

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the polar group may be at least one polar group selected from a hydroxy group and a carboxy group.

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the acrylic polymer particles may be polymer particles polymerized using a methyl methacrylate monomer as a main component.

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the polar group of the acrylic polymer particle may be derived from a polar acrylic monomer having at least one selected from a hydroxy group, a carboxy group, and salts thereof. .

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the acrylic polymer particles may be prepared by including 0.01 to 10 parts by weight of the polar acrylic monomer based on 100 parts by weight of the total monomer mixture.

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the basic atmosphere may be controlled by adding alkali or alkaline earth metal hydroxide.

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the metal crosslinking agent may be a metal alkoxide-based compound.

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the metal crosslinking agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the organic polymer particle dispersion.

In the method for preparing organic-inorganic hybrid cross-linked particles according to an embodiment of the present invention, the organic-inorganic hybrid cross-linked particles may have a viscosity of 100 cps or less after 24 hours measured by dispersing 20 wt% in toluene.

In the method for producing crosslinked organic-inorganic hybrid particles according to an embodiment of the present invention, the weight loss of the organic-inorganic hybrid crosslinked particles may be less than 10% when the temperature is raised from room temperature to 300°C at 10°C/min.

In the method for preparing organic-inorganic hybrid cross-linked particles according to an embodiment of the present invention, the organic-inorganic hybrid cross-linked particles may be monodisperse and have an average particle diameter of 0.5 to 30 μm.

The present invention provides organic-inorganic hybrid crosslinked particles in which polar groups of organic polymer particles having polar groups are crosslinked by a metal crosslinking agent. Preferably, the organic-inorganic hybrid crosslinked particles may have a viscosity of 100 cps or less after 24 hours measured by dispersing 20 wt% in toluene.

Organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention may be acrylic polymer particles.

According to one embodiment of the present invention, the polar group may be at least one polar group selected from a hydroxy group and a carboxy group.

According to one embodiment of the present invention, the acrylic polymer particles may be polymer particles polymerized with a methyl methacrylate monomer as a main component.

According to one embodiment of the present invention, the polar group of the acrylic polymer particle may be derived from an acrylic monomer having at least one selected from a hydroxy group, a carboxy group, and salts thereof.

According to one embodiment of the present invention, the metal crosslinking agent may be a metal alkoxide-based compound.

According to one embodiment of the present invention, the organic-inorganic hybrid crosslinked particles may be monodisperse and have an average particle diameter of 0.5 to 30 μm.

According to one embodiment of the present invention, the organic-inorganic hybrid crosslinked particles may have a weight loss of less than 10% when the temperature is raised from room temperature to 300 °C at 10 °C/min.

The method for producing organic-inorganic hybrid crosslinked particles according to the present invention enables efficient mass production of crosslinked particles with a relatively simple process using dispersion polymerization, non-emulsion polymerization or multi-step non-emulsion polymerization, and uses an acrylic monomer having a polar group and a metal crosslinking agent. By doing so, crosslinked particles having monodispersity and a high degree of crosslinking can be produced. In addition, the crosslinked particles have an advantage of excellent heat resistance and solvent stability.

Highly heat-resistant monodisperse organic-inorganic hybrid crosslinked particles having various average particle diameters can be prepared through the manufacturing method of the present invention, and using the same, fillers for light diffusion films for LCDs and concavo-convex formers for anti-fingerprint (AG) films , column filler for GPC, anti-blocking agent, anisotropic conductive ball, additive for paint, ink and cosmetics.

1 is an image obtained by analyzing organic-inorganic hybrid crosslinked particles according to Example 1 with a field emission scanning electron microscope (FE-SEM).
2 is a result of analyzing the organic-inorganic hybrid crosslinked particles according to Example 1 by thermogravimetric analysis (TGA).
3 is an image obtained by analyzing organic-inorganic hybrid crosslinked particles according to Example 2 with a field emission scanning electron microscope (FE-SEM).
4 is an image obtained by analyzing organic-inorganic hybrid crosslinked particles according to Example 7 with a field emission scanning electron microscope (FE-SEM).

Hereinafter, the present invention will be described in more detail. However, the following specific examples or examples are only one reference for explaining the present invention in detail, but the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms used in the description in the present invention are merely to effectively describe specific embodiments and are not intended to limit the present invention.

Also, the singular forms used in the specification and appended claims may be intended to include the plural forms as well, unless the context dictates otherwise.

In addition, units used in this specification without special mention are based on weight, and as an example, the unit of % or ratio means weight% or weight ratio, and unless otherwise defined, weight% is any one component of the entire composition It means the weight percent occupied in the composition.

Further, as used herein, numerical ranges include lower and upper limits and all values within that range, increments logically derived from the shape and breadth of the defined range, all values defined therebetween, and the upper limit of the numerical range defined in a different form. and all possible combinations of lower bounds. Unless otherwise specifically defined in the specification of the present invention, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.

As used herein, "comprising" is an open description having the same meaning as "includes", "includes", "has", or "characterized by", and is an element or material not additionally listed. or do not rule out the process.

"Acrylic" as described herein includes acrylic and methacrylic.

"Monodispersity" as used herein refers to the uniformity of the shape and particle size of the particles in the dispersed phase. In other words, a state in which the shape and diameter of the particles are uniform is called monodispersity. Preferably, the shape of the particles is spherical, the average particle diameter is uniform, and the narrower the particle size distribution, the more monodisperse it can be determined.

The "organic polymer particle dispersion" described herein includes a primary seed particle dispersion and a secondary seed particle dispersion, and the "organic polymer particle" may include a primary seed particle and a secondary seed particle.

Hereinafter, the present invention will be described in detail.

The present invention comprises the steps of preparing a dispersion of organic polymer particles having a polar group; and cross-linking by adding a metal cross-linking agent to the dispersion in a basic atmosphere.

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the dispersion of organic polymer particles may be prepared by dispersion polymerization, non-emulsion polymerization, or multi-step non-emulsion polymerization.

The dispersion polymerization method is not particularly limited and can be applied as long as it is a conventionally used or known method. Specifically, a solvent, an acrylic monomer, an acrylic monomer having a polar group (hereinafter referred to as a polar acrylic monomer), a fat-soluble initiator, and a dispersion stabilizer may be used to prepare the dispersion. can Specifically, a solvent and a dispersion stabilizer may be added and dissolved for 10 to 60 minutes, and then a monomer mixture including an acrylic monomer and a polar acrylic monomer and a lipophilic initiator may be introduced into a reactor to perform polymerization. More specifically, a solvent, a dispersion stabilizer, a monomer mixture, and an initiator are added to a reactor, and polymerization is performed at 60 to 80° C. for 5 to 20 hours, and then cooled to obtain an organic polymer particle dispersion. In addition, the monomer mixture may be included in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the solvent, but is not limited thereto.

The solvent includes alcohols such as methanol, ethanol, butanol, and octanol; Polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin, water, or mixtures thereof may be used, but are not particularly limited as long as the dispersion polymerization can proceed.

The acrylic monomer is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate It may be one or more selected from the like, and preferably may be methyl methacrylate.

The polar group of the polar acrylic monomer may be at least one polar group selected from a hydroxy group and a carboxy group. In addition, it is not particularly limited as long as it is an acrylic monomer having the above polar group, but, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, acrylic acid, methacrylic acid and itaconic acid, etc. It may be one or more selected, preferably one or more selected from 2-hydroxyethyl methacrylate and methacrylic acid. Through the process of cross-linking the polar group and the metal cross-linking agent, organic-inorganic hybrid cross-linked particles having excellent solvent stability, high heat resistance, high degree of cross-linking, and excellent monodispersity, which are the objects of the present invention, can be prepared.

According to one embodiment of the present invention, the polar acrylic monomer may be prepared by being included in 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total monomer mixture. However, it is not limited thereto, and when the organic polymer particle dispersion is prepared satisfying the above range, the uniformity of the shape and particle diameter of the particles can be increased, and a high yield of the particle dispersion can be obtained, and as a result, organic-inorganic hybrid It is good because the solvent stability, heat resistance, degree of crosslinking, and monodispersity of the crosslinked particles can be improved.

The fat-soluble initiator is 2,2'-azobisisobutyronitrile, 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2-methyl butyronitrile) and 2, Azo-based initiators such as 2'-azobis (2,4-dimethylvalenonitrile) and benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, and 3,3',5-trimethyl hexanoyl peroxide may be peroxide-based initiators, but , Any known initiator or commonly used for dispersion polymerization can be used without any limitation. The fat-soluble initiator may be included in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the total monomer mixture, but is not limited thereto.

The dispersion stabilizer can be added to improve the stability of the dispersed particles and to control the degree of distribution. For example, polyvinylpyrrolidone, polyvinylmethyl ether, polyethyleneimine, polyacrylic acid, polyvinyl alcohol, vinyl acetate copolymer, Ethyl cellulose and hydroxypropyl cellulose and the like can be used. The dispersion stabilizer may be included in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the solvent, but is not limited thereto.

The organic polymer particles prepared by the dispersion polymerization method are non-crosslinked particles, and the total solid content of the dispersion may be 5 to 50%, preferably 5 to 30%. In addition, the average particle diameter of the organic polymer particles prepared by the above method may be 0.5 to 30 μm, preferably 1 to 10 μm, and preferably 2 to 6 μm, but is not limited thereto.

In addition, the non-emulsion polymerization method can prepare an organic polymer particle dispersion through an emulsion polymerization mechanism without adding a separate emulsifier. In addition, a multi-step non-emulsion polymerization method can be used to control the average particle diameter of the polymer particles or to treat the surface of the particles. may be in progress.

The non-emulsion polymerization method according to the present invention may be prepared by including water, an acrylic monomer, a polar acrylic monomer, and a water-soluble initiator. Specifically, a monomer mixture including an acrylic monomer and a polar acrylic monomer and water may be introduced into a reactor, and then a water-soluble initiator may be introduced into the reactor to perform polymerization. More specifically, after adding water and a monomer mixture to the reactor, raising the temperature to 60 to 80 ° C, adding a water-soluble initiator dissolved in water, polymerizing for 5 to 20 hours, and cooling after the reaction is completed to obtain a primary seed particle dispersion. can be obtained

In the non-emulsion polymerization method according to the present invention, the monomer mixture may be included in 10 to 50 parts by weight, preferably 20 to 30 parts by weight, based on 100 parts by weight of water, but is not limited thereto. In the case of organic-inorganic hybrid crosslinked particles prepared by satisfying the above range, it is more spherical and has excellent monodispersity, and it is good that it can be mass-produced efficiently with high yield.

The description of the acrylic monomer and the polar acrylic monomer and examples of specific compounds may be the same as or different from those described in the dispersion polymerization method above.

The water-soluble initiator is at least one selected from potassium persulfate, ammonium persulfate, benzoyl peroxide, lauryl peroxide, sodium persulfate, hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, para-menthane peroxide, and peroxy carbonate. The water-soluble initiator may be prepared by including 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the monomer mixture, but is not limited thereto.

The primary seed particles prepared by the above method are non-crosslinked particles, and the total solid content of the dispersion may be 5 to 50%, preferably 10 to 30%. In addition, the average particle diameter of the primary seed particles prepared by the above method may be 0.1 to 5 μm, preferably 0.2 to 3 μm, but is not limited thereto.

According to one embodiment of the present invention, after preparing the primary seed particle dispersion, secondary seed particles may be additionally prepared using a multi-step emulsion-free polymerization method. The polymerization method may be the same as or different from the method for preparing the primary seed particle dispersion. Specifically, it may be prepared by including a primary seed particle dispersion, an acrylic monomer, a polar acrylic monomer, a water-soluble initiator, and water. Specifically, 1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight of the primary seed particle dispersion based on 100 parts by weight of water is introduced into the reactor, followed by acrylic monomer and polar acrylic monomer. The monomer mixture may be introduced into the reactor. The monomer mixture may be included in 10 to 50 parts by weight, preferably 20 to 30 parts by weight, based on 100 parts by weight of water, but is not limited thereto. In the case of the prepared organic polymer particles prepared by satisfying the above range, they are more spherical, have high monodispersity, and can be efficiently mass-produced with good yield.

Subsequently, polymerization may be performed while slowly introducing a water-soluble initiator into the reactor. More specifically, after adding water and a monomer mixture to the reactor and raising the temperature to 60 to 80 ° C, slowly adding a water-soluble initiator dissolved in water for 10 to 60 minutes, polymerizing and cooling for 1 to 20 hours to obtain a secondary seed particles can be obtained.

The acrylic monomer, the polar acrylic monomer and the water-soluble initiator may be the same as or different from those described in the method for preparing the primary seed particle dispersion.

The secondary seed particles prepared by the above method are non-crosslinked particles, and the total solid content of the dispersion may be 5 to 50%, preferably 10 to 40%. In addition, the average particle diameter of the secondary seed particles prepared by the above method may be 0.2 to 30 μm, preferably 1 to 20 μm or 1 to 10 μm, but is not limited thereto.

In addition, in the dispersion polymerization method, non-emulsion polymerization method or multi-stage non-emulsion polymerization method according to the present invention, a molecular weight regulator may be further included in the monomer mixture. The molecular weight modifier is not limited as long as it is a compound well known in the art, and is preferably a (C _1-15 )alkyl mercaptan having one thiol functional group or a polythiol mer having two or more thiol functional groups. Captan may be used, and for example, n-dodecyl mercaptan or octyl mercaptan may be used, but is not limited thereto. The molecular weight modifier may be prepared by being included in 0.01 to 10 parts by weight based on 100 parts by weight of the total monomer mixture, but is not particularly limited as long as it does not impair the desired physical properties in the present invention, and the molecular weight and molecular weight of the polymer by adjusting the content It may be to adjust the distribution.

Preferably, the organic polymer particle according to an embodiment of the present invention may be an acrylic polymer particle, and more preferably, the acrylic polymer particle may be a polymer particle polymerized using a methyl methacrylate monomer as a main component. When organic-inorganic hybrid crosslinked particles are prepared using the acrylic polymer particles, specifically, polymer particles containing methyl methacrylate as a main component, optical properties are excellent due to excellent transparency and refractive index, and properties such as chemical resistance, heat resistance and wear resistance Due to its excellent properties, it can be applied to cosmetic additives, paints, paints, antiblocking agents, lubricants, lightweight agents, and functional panels such as light guide plates or diffusion plates in the display industry.

In addition, the polar group of the acrylic polymer particle may be derived from a polar acrylic monomer having at least one selected from a hydroxyl group, a carboxy group, an amino group, an amide group, and salts thereof, and specifically, the polar group of the acrylic polymer particle It can be internal or on the surface. In addition, the description of the polar acrylic monomer and examples of specific compounds may be the same as or different from those of the polar acrylic monomer described above.

According to one embodiment of the present invention, the step of crosslinking by adding a metal crosslinking agent to the dispersion in a basic atmosphere is adding dropwise a solution in which the metal crosslinking agent is dissolved in water to the prepared dispersion for 10 to 60 minutes, and then the pH is 8 to 10. It may be to form a basic atmosphere of, and react for 1 to 10 hours by raising the temperature to a temperature of 70 to 90 ℃. Specifically, the concentration of the metal crosslinking agent may be 0.1 to 10 wt%, and the solution in which the metal crosslinking agent is dissolved is 1 to 150 parts by weight, preferably 1 to 100 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the dispersion. It may be included in 100 parts by weight. When the above range is satisfied, organic-inorganic hybrid cross-linked particles having excellent monodispersity and high degree of cross-linking and excellent heat resistance and solvent stability can be produced in high yield, which is very good.

In the method for producing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the basic atmosphere may be adjusted by adding alkali or alkaline earth metal hydroxide, wherein the alkali or alkaline earth metal hydroxide is potassium hydroxide, It may be selected from sodium hydroxide, calcium hydroxide, and the like, but is not limited thereto.

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the metal crosslinking agent may be a metal alkoxide-based compound. The metal crosslinking agent reacts with the polar group of the polar acrylic monomer to crosslink the inside and surface of the particle, thereby producing monodisperse organic-inorganic hybrid crosslinked particles having a high degree of crosslinking.

One example of the metal crosslinking agent may be a metal alkoxide-based compound. The metal alkoxide-based compound is not significantly limited as long as the metal is substituted with two or more alkoxy substituents capable of a crosslinking reaction. For example, it may be a tetraalcoxymetal or a metal chelate-based compound having two or more alkoxy substituents, and the alkoxy substituent may mean a C _1-20 alkoxy substituent. For example, without limitation, the metal alkoxide-based compound may be represented by Formula 1 below, and the metal chelate-based compound may be represented by Formula 2 below.

[Formula 1] M (OR ₁ ) ₄

In Formula 1, R ₁ may be a straight-chain or branched C _1-20 alkyl, and M may be a tetravalent metal element.

[Formula 2]

In Formula 2, R ₂ is straight-chain or branched C _1-20 alkyl, R ₃ is straight-chain or branched C _1-7 alkylene or alkenylene, M is a tetravalent metal element, and Y is It may be heterohydrocarbyl. Specifically, Y may be represented by the following structure.

In the above structure, R ₄ is C _1-7 alkyl, R ₅ is C _1-7 alkyl, ammonium salt or sodium salt, and R ₆ may be C _1-7 alkylene.

More specifically, the metal alkoxide represented by Chemical Formula 1 reacts with active hydrogens of a hydroxyl group, an amino group, an amido group, a carboxy group, and a thiol group to undergo crosslinking, and its reactivity is also very high. For example, it may be at least one selected from tetraisopropyl titanate, tetra-n-butyl titanate, tetrakis (2-ethylhexyl) titanate, and the like.

In addition, the metal chelate-based compound represented by Chemical Formula 2 may be formed through a coordinate bond with a metal ion using acetylacetone, triethanolamine, lactic acid, or the like as a chelating agent. The metal chelate compound has a crosslinking mechanism similar to that of the metal alkoxide compound, and reactivity can be increased through pH and temperature control. For example, it may be at least one selected from acetylacetonate titanate chelate, ethyl acetoacetate titanate chelate, triethanolamine titanate chelate, latic acid titanate chelate, and ammonium salt.

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the metal crosslinking agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the organic polymer particle dispersion (or seed polymer particle dispersion). It may preferably be included in 0.1 to 7 parts by weight, more preferably 0.5 to 5 parts by weight. In addition, the organic polymer particle dispersion may have a solid content of 1 to 50%, preferably 5 to 40%, more preferably 5 to 30%, and the metal crosslinking agent may be added to the organic polymer particle dispersion satisfying the above solid content range. It may be included in the range, but is not limited thereto, and the input amount of the metal crosslinking agent may be adjusted according to the solid content of the organic polymer particle dispersion. Preferably, assuming that the solid content of the dispersion of organic polymer particles is 100%, 0.1 to 100 g of the metal crosslinking agent, specifically 1 to 50 g, and more specifically 5 to 40 g of the metal crosslinking agent may be added. As a non-limiting example, 0.01 to 10 g, specifically 0.1 to 5 g, and more specifically 0.5 to 4 g of the metal crosslinking agent may be added to 100 g of the 10% organic polymer particle dispersion, but the monodispersity and heat resistance that are the object of the present invention and solvent stability, the input amount of the metal crosslinking agent is not limited thereto.

When the metal crosslinking agent according to the present invention is used, a high yield can be obtained due to excellent compatibility with the particle dispersion, and the crosslinking degree can be adjusted according to the content, so that monodisperse organic-inorganic hybrid crosslinked particles having desired physical properties can be obtained. very good. In particular, organic-inorganic hybrid crosslinked particles capable of imparting high degree of crosslinking and having excellent monodispersity, heat resistance and solvent stability can be prepared.

In the method for producing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the organic-inorganic hybrid crosslinked particles have excellent solvent stability, and the solvent stability is measured by dispersing 20 wt% in toluene and measuring the viscosity after 24 hours, It can be evaluated that the solvent stability is excellent, so that the viscosity change is small. That is, when the crosslinked organic-inorganic hybrid particles according to the present invention do not dissolve in organic solvents and are evenly dispersed, solvent stability can be evaluated as excellent. The viscosity after 24 hours measured by dispersing 20 wt% of the organic-inorganic hybrid crosslinked particles according to the present invention in toluene may be 100 cps or less, preferably 50 cps or less, more preferably 20 cps or less and 1 cps or more, and the lower limit is particularly Not limited.

In addition, the viscosity after 24 hours measured by dispersing 20 wt% of the organic-inorganic hybrid crosslinked particles according to the present invention in toluene is 10 times or less, preferably 7 times or less, more preferably 5 times or less of the viscosity measured immediately after dispersion. , The viscosity after 24 hours may be 7 times or less, preferably 5 times or less, and more preferably 3 times or less of the viscosity measured after 1 hour. It can be evaluated that the solvent stability is excellent as the change in viscosity is small, and the crosslinked organic-inorganic hybrid particles according to the present invention have a high degree of crosslinking and thus are excellent in change in viscosity and stability in solvent.

In the method for producing crosslinked organic-inorganic hybrid particles according to an embodiment of the present invention, the organic-inorganic hybrid crosslinked particles have a weight loss of less than 10%, preferably 6%, when the temperature is raised from room temperature to 300°C at 10°C/min. Within, it may be more preferably 3.5% to 0.1%. The organic-inorganic hybrid crosslinked particles according to the present invention form a solid crosslinked structure on the surface of the particles, so that they have excellent heat resistance as well as monodispersity and solvent stability.

In the method for preparing organic-inorganic hybrid crosslinked particles according to an embodiment of the present invention, the organic-inorganic hybrid crosslinked particles may be monodisperse and have an average particle diameter of 0.5 to 10 μm. It may be preferably 0.5 to 7 μm, but may vary depending on the final product and use, and the average particle diameter is not particularly limited.

Through the manufacturing method according to an embodiment of the present invention, monodisperse organic-inorganic hybrid crosslinked particles having various average particle diameters can be prepared, and using the same, it is possible to prepare fillers for light diffusion films for LCDs and anti-fingerprint (AG) films. It can be applied to various industrial fields such as concavo-convex forming agent, column filler for GPC, anti-blocking agent, anisotropic conductive ball, additive for paint, ink and cosmetics.

In addition, the present invention provides organic-inorganic hybrid crosslinked particles in which the polar groups of organic polymer particles having polar groups are crosslinked by a metal crosslinking agent. Preferably, the organic-inorganic hybrid crosslinked particles may have a viscosity of 100 cps or less after 24 hours measured by dispersing 20 wt% in toluene. The organic polymer particles may be acrylic polymer particles, and the polar group may be at least one polar group selected from a hydroxyl group and a carboxyl group. Descriptions of the organic polymer particles, the polar group, and the metal crosslinking agent, examples of specific compounds, and specific descriptions of the organic-inorganic hybrid crosslinking particles are the same as described above.

Organic-inorganic hybrid crosslinked particles according to the present invention can impart a more robust degree of crosslinking by crosslinking the polar groups of the organic polymer particles having polar groups with a metal crosslinking agent, and have excellent compatibility between the organic polymer particles having polar groups and the metal crosslinking agent, resulting in high It is good because it can be efficiently mass-produced with high yield. In addition, excellent monodispersity, heat resistance and solvent stability can be secured, which is very good.

The method for preparing organic-inorganic hybrid crosslinked particles according to the present invention will be described in more detail through the following examples. However, the following examples are only one reference for explaining the present invention in detail, but the present invention is not limited thereto, and may be implemented in various forms. Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, terms used in description in the present invention are only for effectively describing specific embodiments, and are not intended to limit the present invention.

[Physical property evaluation method]

1. Weight loss rate at 300 ° C

The organic-inorganic hybrid crosslinked particles prepared in Examples and Comparative Examples were heated from 30 to 500 ° C at a rate of 10 ° C using a thermal gravimetric analysis, and the weight at 300 ° C compared to the initial weight in the analysis result graph Reduction (%) was calculated.

2. Solvent stability

The organic-inorganic hybrid crosslinked particles prepared in Examples and Comparative Examples were added to toluene in an amount of 20 wt%, and the viscosity (cP) was measured immediately after addition, 1 hour, 3 hours, and 24 hours later, and the change in viscosity was observed. Viscosity was measured at room temperature (23 ± 1 ° C) at 50 rpm with a spindle No. 2 using a Brookfield viscometer, and the smaller the change in viscosity, the better the stability of the solvent.

3. Average particle diameter

In Examples and Comparative Examples, the organic-inorganic hybrid crosslinked particles before centrifugation were analyzed with a particle size analyzer (PSA, CILAS 1090L) to measure the average particle diameter of the particles.

[Example 1]

- Preparation of organic polymer particle dispersion

627.2 g of organic solvent methanol and 268.8 g of distilled water were added to a three-necked flask reactor equipped with a cooler in the continuous phase, and 4 g of polyvinylpyrrolitone (PVP, K-90) as a dispersion stabilizer was added, stirring at a stirring speed of 200 rpm to 20 was sufficiently dissolved in a minute. Then, 96 g of methyl methacrylate (MMA), 2 g of methacrylic acid (MAA), 1 g of octyl mercaptan (n-ODM) as a molecular weight modifier, and 2,2-azobisisobutyronitrile as an initiator under a nitrogen stream A mixture of 1 g of (AIBN) was put into a reactor and sufficiently stirred. Dispersion polymerization was carried out for 8 hours at an internal temperature of 65 ° C and a stirring speed of 100 rpm, and after the reaction was completed, it was cooled to 40 ° C or less to prepare a dispersion of organic polymer particles (Poly (MMA-co-MAA)). The average particle diameter of the particles was measured to be 4.1 μm.

- Preparation of organic-inorganic hybrid cross-linked particles

The organic polymer particles (Poly (MMA-co-MAA)) dispersion (solid content of about 10%) in a three-necked flask reactor A solution in which 2 g of Tyzor ^® LA was dissolved in 98 g of distilled water in 100 g was slowly added for 30 minutes. Subsequently, while adjusting the pH of the mixture to 9.5 using 0.5 M sodium hydroxide, the mixture was slowly stirred at 100 rpm for 1 hour at room temperature, and then heated to 80 ° C. and reacted for 4 hours to prepare an organic-inorganic hybrid crosslinked particle dispersion.

After the reaction was completed and cooled to 40° C. or less, crosslinked particles were obtained by centrifugation. FE-SEM analysis and weight loss were measured, and the results are shown in FIGS. 1 and 2. In addition, the obtained crosslinked particles were dried at 90° C. for 12 hours to evaluate solvent stability, and the results are shown in Table 1.

[Example 2]

In Example 1, the procedure was the same as in Example 1 except that 2 g of 2-hydroxyethyl methacrylate (2-HEMA) was added instead of methacrylic acid (MAA), and the average particle diameter of the particles was 3.7 μm. was measured, and the FE-SEM analysis image is shown in FIG. Table 1 shows the results of evaluation of solvent stability and weight reduction of the obtained crosslinked particles.

[Example 3]

In Example 1, the same procedure as in Example 1 was performed except that Tyzor ^® TOT was added instead of Tyzor ^® LA. Table 1 shows the results of evaluation of solvent stability and weight loss of the obtained crosslinked particles.

[Examples 4 to 6]

The same procedure as in Example 1 was performed except that the input amount of Tyzor ^® LA was adjusted in Example 1. The input amount of the crosslinking agent was carried out in the same manner as described in Table 1 below. Table 1 shows the results of evaluation of solvent stability and weight reduction of the obtained crosslinked particles.

[Example 7]

-Preparation of primary seed polymer particle dispersion

770 g of ion-exchanged water was added to a three-necked flask reactor equipped with a cooler, and 190 g of methyl methacrylate (MMA), 4 g of methacrylic acid (MAA), and 4 octyl mercaptan (n-ODM) as a molecular weight regulator were added under a nitrogen stream. The mixture of g was put into a reactor, and the temperature was raised to an internal temperature of 70°C. A solution of 2 g of potassium persulfate completely dissolved in 30 g of distilled water at an agitation speed of 100 rpm was introduced into the reactor for 10 hours while the polymerization reaction proceeded. After the reaction was completed, the mixture was cooled to below 40° C. to prepare a dispersion of primary seed polymer particles (Poly(MMA-co-MAA)), and the average particle diameter of the particles was measured to be 370 nm (0.37 μm).

- Preparation of secondary seed polymer particle dispersion

609.6 g of ion-exchanged water and 20 g of the primary seed polymer particle (Poly (MMA-co-MAA)) dispersion (solid content of about 20%) prepared in Example 1 were added to a three-necked flask reactor equipped with a cooler, and nitrogen was added. A mixture of 152.1 g of methyl methacrylate (MMA), 3.1 g of methacrylic acid (MAA), and 3.2 g of n-octyl mercaptan as a molecular weight regulator was put into a reactor under an air stream, and the temperature was raised to an internal temperature of 70 ° C. . A solution in which 1.6 g of potassium persulfate was completely dissolved in 30.4 g of distilled water at an agitation speed of 100 rpm was introduced into the reactor for 30 minutes, followed by a polymerization reaction for 8 hours. After the reaction was completed, the mixture was cooled to 40° C. or less to prepare a secondary seed polymer particle dispersion, and the average particle diameter of the particles was measured to be 4.8 μm.

- Preparation of organic-inorganic hybrid cross-linked particles

A mixture of 155 g of distilled water and 4 g of Tyzor ^® LA in 100 g of the secondary seed polymer particle dispersion was slowly introduced into a three-necked flask reactor for 30 minutes. Subsequently, while adjusting the pH of the mixture to 9.5 using 0.5 M sodium hydroxide, the mixture was slowly stirred at 100 rpm for 1 hour at room temperature, and then heated to 80 ° C. and reacted for 4 hours to prepare an organic-inorganic hybrid crosslinked particle dispersion.

After the reaction was completed and cooled to 40° C. or less, cross-linked particles were obtained by centrifugation. This was analyzed by FE-SEM and the results are shown in FIG. 4 . In addition, the obtained crosslinked particles were dried at 90° C. for 12 hours to evaluate solvent stability, and the results are shown in Table 1.

[Comparative Example 1]

Only the preparation step of the organic polymer particle dispersion of Example 1 was performed, and the same procedure as in Example 1 was performed except that MAA was removed and 98 g of methyl methacrylate (MMA) was added. Table 1 shows the results of solvent stability evaluation and weight loss rate of the obtained particles.

[Comparative Example 2]

Only the preparation step of the organic polymer particle dispersion of Example 1 was performed, and the results of solvent stability evaluation and weight loss rate of the obtained particles are shown in Table 1.

[Comparative Example 3]

In Example 1, the same procedure as in Example 1 was performed except that MAA was removed and 98 g of methyl methacrylate (MMA) was added. The solvent stability of the obtained particles was evaluated and the results are shown in Table 1.

polarity
acrylic monomer metal crosslinker Solvent stability (viscosity, cps) weight
decrease rate
(%) Kinds input amount (g) input
right after 1 hours 3 hours 24 hours Example 1 MAA Tyzor ^® LA 2 5.1 6.0 6.1 6.1 3.0 Example 2 2-HEMA Tyzor ^® LA 2 8.6 9.4 13.5 25 3.2 Example 3 MAA Tyzor ^® TOT 2 15.3 18.9 27.8 32.1 5.5 Example 4 MAA Tyzor ^® LA 0.5 8.4 12.1 34.1 59.3 9.3 Example 5 MAA Tyzor ^® LA One 7.2 8.4 15.6 17.2 5.2 Example 6 MAA Tyzor ^® LA 3 6.4 8.1 8.9 8.9 3.5 Example 7 MAA Tyzor ^® LA 4 6.4 7.8 8.3 8.5 3.1 Comparative Example 1 - - - 109 341 1,810 3,700 85.7 Comparative Example 2 MAA - - 97 231 1,020 3,100 78.3 Comparative Example 3 - Tyzor ^® LA 2 90 194 990 3,000 75.1

As shown in Table 1, in the case of the monodisperse crosslinked particles according to Examples 1 to 7 prepared by crosslinking the metal crosslinking agent and organic polymer particles polymerized by dispersion polymerization or multi-step non-emulsion polymerization including polar acrylic monomers, 24 It was confirmed that the viscosity after time was 100cps or less, and in particular, Example 1 in which 2 g of Tyzor ^® LA was added as a metal crosslinking agent had the best solvent stability and heat resistance.

In addition, in Example 7, a polymer particle dispersion was prepared through a multi-stage non-emulsion polymerization method, and the concentration of the metal crosslinking agent relative to the solid content of the dispersion was adjusted to be the same as in Example 1, and as a result, the stability of the solvent and the weight reduction rate were improved. It was confirmed that it was similar to Example 1, and when comparing Examples 1 and 4 to 6, it was confirmed that better physical properties were exhibited when 0.5 to 5 parts by weight was included with respect to 100 parts by weight of the organic polymer particle dispersion.

As described above, the present invention has been described with specific details and limited examples, but this is only provided to help a more general understanding of the present invention, the present invention is not limited to the above examples, and the field to which the present invention belongs Those skilled in the art can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and it will be said that not only the claims to be described later, but also all modifications equivalent or equivalent to these claims belong to the scope of the present invention. .

Claims (21)

preparing a dispersion of organic polymer particles having a polar group; and
A method for producing organic-inorganic hybrid crosslinked particles comprising the step of crosslinking by adding a metal crosslinking agent to the dispersion in a basic atmosphere. According to claim 1,
The organic polymer particle dispersion is a method for producing organic-inorganic hybrid crosslinked particles prepared by dispersion polymerization, non-emulsion polymerization or multi-step non-emulsion polymerization. According to claim 1,
The method of producing organic-inorganic hybrid crosslinked particles in which the organic polymer particles are acrylic polymer particles. According to claim 1,
The method of producing organic-inorganic hybrid crosslinked particles, wherein the polar group is at least one polar group selected from a hydroxyl group and a carboxy group. According to claim 3,
The method of producing organic-inorganic hybrid crosslinked particles, wherein the acrylic polymer particles are polymer particles polymerized with a methyl methacrylate monomer as a main component. According to claim 3,
The method of producing organic-inorganic hybrid crosslinked particles, wherein the polar group of the acrylic polymer particles is derived from a polar acrylic monomer having at least one selected from a hydroxyl group, a carboxyl group, and salts thereof. According to claim 6,
The acrylic polymer particles are prepared by containing 0.01 to 10 parts by weight of the polar acrylic monomer based on 100 parts by weight of the total monomer mixture. According to claim 1,
The method of preparing organic-inorganic hybrid crosslinked particles, wherein the basic atmosphere is controlled by adding alkali or alkaline earth metal hydroxide. According to claim 1,
The method for producing organic-inorganic hybrid crosslinked particles, wherein the metal crosslinking agent is a metal alkoxide-based compound. According to claim 1,
The metal crosslinking agent is included in 0.01 to 10 parts by weight based on 100 parts by weight of the organic polymer particle dispersion. According to claim 1,
The organic-inorganic hybrid crosslinked particle is a method for producing organic-inorganic hybrid crosslinked particles having a viscosity of 100 cps or less after 24 hours measured by dispersing 20 wt% in toluene. According to claim 1,
The method for producing organic-inorganic hybrid crosslinked particles, wherein the organic-inorganic hybrid crosslinked particles have a weight loss of less than 10% when the temperature is raised from room temperature to 300 ° C at 10 ° C / min. According to claim 1,
The organic-inorganic hybrid cross-linked particles are monodisperse and have an average particle diameter of 0.5 to 30 μm. An organic-inorganic hybrid crosslinked particle in which the polar group of organic polymer particles having a polar group is crosslinked by a metal crosslinking agent, wherein the organic-inorganic hybrid crosslinked particle has a viscosity of 100 cps or less after 24 hours measured by dispersing 20 wt% in toluene. hybrid cross-linked particles. According to claim 14,
The organic-inorganic hybrid cross-linked particles are organic-inorganic hybrid cross-linked particles that are acrylic polymer particles. According to claim 14,
The organic-inorganic hybrid crosslinked particle, wherein the polar group is at least one polar group selected from a hydroxyl group and a carboxyl group. According to claim 14,
The organic-inorganic hybrid crosslinked particles of claim 1, wherein the acrylic polymer particles are polymer particles polymerized with a methyl methacrylate monomer as a main component. According to claim 14,
Organic-inorganic hybrid crosslinked particles, wherein the polar group of the acrylic polymer particles is derived from an acrylic monomer having at least one selected from a hydroxyl group, a carboxyl group, and salts thereof. According to claim 14,
The organic-inorganic hybrid crosslinking particle wherein the metal crosslinking agent is a metal alkoxide-based compound. According to claim 14,
The organic-inorganic hybrid crosslinked particles are monodisperse and have an average particle diameter of 0.5 to 30 ㎛ organic-inorganic hybrid cross-linked particles. According to claim 14,
The organic-inorganic hybrid cross-linked particles have a weight loss of less than 10% when the temperature is raised from room temperature to 300 ° C at 10 ° C / min.

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