KR20180002278A - Polymeric beads and process for preparing polymeric beads - Google Patents

Abstract

The present invention relates to polymeric beads and a production method of the polymeric beads. More particularly, the present invention relates to polymeric beads having excellent durability, heat resistance, and light resistance through a nano-sized multi-layer structure, and having optical characteristics of absorbing light in the visible light region to the maximum; and to a method for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer bead and a polymer bead,

The present invention relates to a process for preparing polymer beads and polymer beads. More particularly, the present invention relates to a polymer bead having excellent durability, heat resistance and light resistance through a nano-sized multi-layer structure, and having optical properties that absorb light in the visible light region to the maximum, and a method for producing the same.

Polymer beads are collectively referred to as spherical particles having a uniform particle diameter distribution prepared by emulsion polymerization or suspension polymerization. Polymer beads have a wide variety of uses, and they are widely used not only for a light diffusion film, a protective film and a construction for a liquid crystal monitor but also for a transparent film for a color ink.

Polymer beads used for this purpose are generally manufactured by methods such as suspension polymerization, dispersion polymerization and emulsion polymerization.

In conventional suspension polymerization, polymer beads are prepared by dispersing monomers present in the aqueous phase by mechanical force. The polymer beads prepared by this method have a bead size of at least 100 mu m and the bead distribution tends to be wide because the beads are dispersed by the mechanical force.

Since the polymer beads produced through the conventional polymerization process have different refractive indexes from those of conventional resins, the polymer beads can provide hiding power, and thus they are widely used in extruding and manufacturing a light diffuser or a lighting fixture. As the product is made by extrusion, it is required to have excellent thermal stability because the product is used by mixing at a high temperature.

However, when such a conventional polymer bead is stagnated at high temperature for 30 minutes or more, the weight loss reduction width is large, which may lead to physical and chemical changes to the environment in which the bead is used. That is, there may be a change in physical properties of the final product due to lowered compatibility, fume or byproducts, and there is a problem in that physical properties such as the shape of the bead are seriously deformed when read by an SEM photograph.

Therefore, when applied to various applications such as a light diffusion film, it is possible to minimize the generation of fumes and to improve the thermal stability at high temperatures, Research on the development of a composition and process for preparing polymer beads is needed.

At the same time, there is also a need for research into the development of compositions and processes capable of producing polymer beads that can absorb the light of the ultraviolet region to the maximum and have unique optical properties with high reactivity to ultraviolet rays.

The present invention is to provide a polymer bead having excellent durability, heat resistance and light resistance through a nano-sized multi-layer structure and having optical properties that absorb light in the visible light region to the maximum.

The present invention also provides a method for producing the polymer bead.

In this specification, the term " core portion " A shell layer formed on the core portion; And a protective layer formed on the shell layer, wherein the core portion, the shell layer, and the protective layer each include a polymer resin including a vinyl-based repeating unit, and at least one of the core portion, the shell layer, A polymeric bead comprising a colorant having a maximum light absorption wavelength at a wavelength equal to or greater than the wavelength of the light is provided.

The present specification also discloses a method for producing a polymer composition, which comprises polymerizing a first monomer composition containing a vinyl-based monomer to form a core portion; Adding a second monomer composition containing a vinyl monomer to the core portion and polymerizing to form a shell layer; And adding a third monomer composition containing a vinyl monomer to the shell layer and polymerizing to form a protective layer, wherein at least one of the first monomer composition, the second monomer composition, and the third monomer composition is There is provided a process for producing a polymer bead comprising a colorant having a maximum light absorption wavelength at a wavelength of 550 nm or more.

In the present specification, the polymer beads; And a binder resin.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A polymer bead according to a specific embodiment of the present invention will be described in detail below.

In the present specification, (meth) acrylic acid means both acrylic acid and methacrylic acid.

In the present specification, (meth) acrylate is also meant to include both acrylate and methacrylate.

According to an embodiment of the invention, A shell layer formed on the core portion; And a protective layer formed on the shell layer, wherein the core portion, the shell layer, and the protective layer each include a polymer resin including a vinyl-based repeating unit, and at least one of the core portion, the shell layer, A polymeric bead comprising a colorant having a maximum light absorption wavelength at a wavelength equal to or greater than the wavelength of the light is provided.

The present inventors have found that the use of the above-mentioned specific polymer beads improves thermal stability and has excellent heat resistance, so that even when the optical characteristic peculiar to the colorant that absorbs visible light is contained in the polymer bead, Was confirmed through experiments and the invention was completed.

Particularly, the polymer bead can contain a coloring agent in the inside of a triple-layer structure composed of a core portion, a shell layer, and a protective layer, thereby preventing migration of the coloring agent and ensuring excellent weather resistance and durability. It is also possible to prevent changes in the physical properties of the polymer resin in the kneading and extruding process at a high temperature or a high pressure, prevent the sensitivity of the coloring agent from changing with temperature, and also prevent the coloring agent itself from being decomposed by heat, thereby ensuring excellent heat resistance.

Specifically, the polymer bead comprises a core portion; A shell layer formed on the core portion; And a protective layer formed on the shell layer. That is, the polymer bead may have a three-layer structure in which a core portion, a shell layer, and a protective layer are laminated in this order from the inside to the outer surface. Layer structure in which a protective layer is further laminated on the shell layer in a generally known core-shell structure.

Each of the shell layer and the protective layer included in the polymer bead has a stable and rigid structure and is bonded or crosslinked with each other in a sequentially laminated state to form an outer film or a surface layer having improved mechanical properties, And the polymer beads to be produced can be stably dispersed without aggregation.

Examples of the shape of the polymer beads are not limited to a wide range. For example, the shape of the polymer beads may be spherical, spherical, or polyhedral, and the cross section of the polymer beads may be circular, elliptical, or polygonal of 3 to 50. The average particle diameter of the polymer beads may be 10 nm to 900 nm, or 30 nm to 700 nm, or 50 nm to 500 nm.

The maximum diameter of the core portion may be 10 nm to 200 nm, the thickness of the shell layer may be 10 nm to 300 nm, and the thickness of the protective layer may be 10 nm to 100 nm.

At least one of the core portion, the shell layer, and the protective layer may include a colorant having a maximum light absorption wavelength at a wavelength of 600 nm or more, or 600 nm to 700 nm. As the coloring agent, a dye (Dye) or a pigment may be used, and a dye may be preferably used.

Further, since the polymer bead contains a coloring agent therein, it is possible to prevent the phenomenon that the coloring agent migrates in the process of applying the coloring agent to a film or the like, thereby ensuring excellent weather resistance and durability. It is also possible to prevent changes in the physical properties of the polymer resin in the kneading and extruding process at a high temperature or a high pressure, prevent the sensitivity of the coloring agent from changing with temperature, and also prevent the coloring agent itself from being decomposed by heat, thereby ensuring excellent heat resistance.

The polymer beads including the colorant may have a high absorbance at a wavelength of 550 nm or more, or 600 nm to 700 nm, and the colorant may be a polymer contained in the core portion, the shell layer, and the protective layer of the polymer bead Can be effectively combined with a general-purpose resin including a resin, thereby realizing a high color rendering power, an ancient roughness, and a light conversion efficiency.

The polymer bead may have a maximum light absorption wavelength at a wavelength of 550 nm or more, or 600 nm to 700 nm. The maximum light absorption wavelength means a wavelength value showing the highest light absorption rate as a result of measuring light absorption according to the wavelength. The light absorption rate means a ratio of the actually measured absorbance to the maximum measurable absorbance, and the maximum measurable absorbance is 2.0 as shown in Table 2 below.

On the other hand, the polymer beads may have a light absorptivity of 0.02% or less at a wavelength of 450 nm to 500 nm, or 750 nm or more. As described above, the light absorptance means a ratio of the actually measured absorbance to the measurable maximum absorbance, and the maximum measurable absorbance is 2.0, as shown in Table 2 below.

That is, the polymer bead exhibits a very low value of approximately 450 nm to 500 nm, or an absorbance of less than 0.05 at a wavelength of 750 nm or more, which is substantially close to zero, from which the polymer bead has a wavelength of 450 nm to 500 nm, It can be confirmed that it hardly absorbs the light of FIG.

At least one of the core portion, the shell layer and the protective layer includes both a core portion, a shell layer, a protective layer, a core portion and a shell layer, a shell layer and a protective layer, a protective layer and a core portion, can do.

More specifically, at least one reactive functional group selected from the group consisting of an amide group, an amine group, a thiol group, an ester group, a vinyl group, a hydroxyl group, a phenol group, a (meth) acrylic functional group and a carboxyl group is substituted on the surface or terminal of the colorant Or may be unsubstituted. The surface of the colorant means the end of the molecular structure of the colorant compound, and the (meth) acrylic system means acrylic or methacrylic system. Accordingly, the colorant can be effectively combined with a general-purpose resin including a polymer resin contained in the core portion, the shell layer, and the protective layer of the polymer bead, thereby realizing high color rendering power, ancient roughness, and light conversion efficiency.

Specifically, when the reactive functional group is substituted on the surface of the colorant, the colorant can be effectively dissolved in the monomer composition of the polymer resin. Accordingly, after the polymerization of the monomer of the polymer resin, the polymeric resin contained in the core portion, the shell layer, and the protective layer of the polymer bead can contain the colorant in a high content, so that the polymer bead can realize excellent optical properties .

Specifically, the content of the coloring agent relative to the polymer beads may be from 0.01 wt% to 20 wt%, or from 0.1 wt% to 10 wt%, or from 1 wt% to 8 wt%. If the content of the colorant relative to the polymer beads is excessively reduced, it is difficult to sufficiently realize the optical property of absorbing light in the ultraviolet ray region to the maximum. If the content of the coloring agent in the polymer beads is excessively increased, the solubility of the coloring agent may decrease, migration of some coloring agents may occur, and the degree of polymerization of the polymer resin to be described later may decrease, .

The polymer beads may contain the colorant in an amount of 0.1 to 20 parts by weight, or 1 to 10 parts by weight, or 3 to 8 parts by weight based on 100 parts by weight of the polymer resin. The content of the polymer resin means the content of all the vinyl-based repeating unit-containing polymers contained in the polymer beads, specifically, the sum of all the polymer resin contents included in the core portion, the shell layer and the protective layer.

If the content of the coloring agent in the polymer resin is excessively reduced, it is difficult to sufficiently realize the optical property of absorbing light in the visible light region to the maximum. Also, if the content of the colorant in the polymer resin is excessively increased, the solubility of the colorant may decrease, migration of a part of the colorant may occur, and the degree of polymerization of the polymer resin may decrease to decrease the heat resistance of the polymer resin. .

The colorant may have a solubility in the vinyl monomer of 60% or more, or 60% to 100%. Since the colorant can have a high solubility with respect to the vinyl monomer, the colorant can be dissolved in the vinyl monomer in the reaction solution to realize excellent optical characteristics and durability.

When the solubility of the colorant in the vinyl monomer is less than 60%, the colorant may not be stably and uniformly dispersed in the reaction solution, and the phenomenon of transition to the finally produced bead surface may occur.

The colorant may include an anthraquinone compound, an acridone compound, a cyanine compound, an azo compound, a formalin compound, a triarylmethane compound, or a mixture of two or more thereof. Preferably, the colorant is cyanine Based compound or a triarylmethane-based compound can be used.

The cyanine compound includes a cyanine compound, a compound in which various substituents are introduced into the cyanine compound, or a derivative compound derived from a cyanine compound. The term "substituted" means that another functional group is bonded in place of a hydrogen atom in the compound, and the position to be substituted is not limited as far as the position where the hydrogen atom is substituted, that is, The substituents may be the same or different from each other.

Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An aryl group, an arylalkyl group having 6 to 20 carbon atoms, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carbamate group, .

Specifically, the cyanine-based compound may include a phthalocyanine-based complex compound. The phthalocyanine-based complex compound means a compound in which a phthalocyanine compound is bound as a ligand to a central metal containing a transition metal or a transition metal ion. Specifically, the phthalocyanine-based complex compound may be a ligand including a phthalocyanine-based compound; And a center metal including a transition metal.

The phthalocyanine compound includes a phthalocyanine compound or a compound having various substituents introduced into the phthalocyanine compound. The term "substituted" means that another functional group is bonded in place of a hydrogen atom in the compound, and the position to be substituted is not limited as far as the position where the hydrogen atom is substituted, that is, The substituents may be the same or different from each other. Specific examples of the substituent are as described above for the cyanine compound.

Examples of the central transition metal contained in the phthalocyanine-based complex compound are not particularly limited, and examples thereof include zinc, copper, nickel, titanium, chromium, manganese, iron and vanadium.

The surface of the phthalocyanine-based complex compound may have a structure in which an amide group, an amine group, a thiol group, an ester group, a vinyl group, a hydroxyl group, a phenol group, a (meth) acrylic functional group and a carboxyl group (Meth) acrylic functional group bonded and formed on the bead), it is possible to ensure higher heat resistance and to more effectively prevent the change in physical properties of the dye due to the heat treatment.

More specific examples of the cyanine compound include phthalocyanine dyes represented by the following formula (1).

[Chemical Formula 1]

R ₁ , R ₂ , R ₃ , and R ₄ are the same or different from each other and each independently represents an amide group, an amine group , A thiol group, an ester group, a vinyl group, a hydroxyl group, a phenol group, a (meth) acrylic functional group or a carboxyl group.

The phthalocyanine-based dye represented by the above formula (1) can absorb a visible light having a wavelength of 600 nm or more, specifically 660 nm to 680 nm.

More specifically, the phthalocyanine-based dye represented by Formula 1 may be a zinc phthalocyanine dye represented by Formula 2 below.

 (2)

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different from each other and each independently represents an amide group, an amine group, a thiol group, an ester group, a vinyl group, a hydroxyl group, a phenol group, Functional group or a carboxyl group.

On the other hand, the triarylmethane-based compound includes a triarylmethane-based compound, a compound having various substituent groups introduced into the triarylmethane-based compound, or a derivative compound derived from a triarylmethane-based compound.

Specifically, the triarylmethane-based compound may include a triarylmethane-based derivative compound. The triarylmethane-based derivative compound is a compound derived from a triarylmethane-based compound, and may include a compound having a conjugated structure modified to satisfy a chemically stable aromatic property.

The surface of the triarylmethane derivative may further contain an amide group, an amine group, a thiol group, an ester group, a vinyl group, a hydroxyl group, a phenol group, a (meth) acrylic functional group and a carboxyl group (for example, (Meth) acrylic functional group bonded to the polymer bead and formed on the polymer bead), it is possible to ensure higher heat resistance and to prevent the change of physical properties of the dye more effectively by heat treatment .

More specifically, the triarylmethane derivative may be a compound represented by the following formula (3).

(3)

In Formula 3, X ^- is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion, and R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently hydrogen, Or a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms, and R ₁₅ includes a functional group represented by the following structural formula (1).

 [Structural formula 1]

In the above structural formula 1, n is an integer of 1 to 10, R ₁₇ is hydrogen or methyl, and "*" is a bonding point.

The triarylmethane-based dye represented by the above formula (3) is capable of absorbing visible light having a wavelength of 550 nm or more, specifically 600 nm to 620 nm.

Preferably, in the above formula (3), R ₁₁ to R ₁₄ represent an alkyl group having 1 to 5 carbon atoms, and R ₁₅ represents a cyclohexyl group whose terminal is substituted with a methacryl functional group.

 Specifically, the triarylmethane-based derivative compound may be a compound represented by the following formula (4).

[Chemical Formula 4]

In the above formula (4), X < ^- > is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion.

The triarylmethane compound may be a polymer compound obtained by using a triarylmethane compound represented by the formula (3) as a monomer, and may further include a homopolymer or a copolymer containing a structure represented by the following formula (5) in the polymer.

[Chemical Formula 5]

Wherein X- is trifluoromethanesulfonic acid or a bistrifluoromethanesulfonimide anion, and R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently hydrogen, substituted or unsubstituted An aromatic hydrocarbon having 6 to 10 carbon atoms, and R ₂₅ includes a functional group represented by the following structural formula (2).

[Structural formula 2]

In the above structural formula 2, n is an integer of 1 to 10, m is an integer of 1 or more, and R ₂₆ is hydrogen or methyl.

The polymer beads include the polymer resin and the colorant bound thereto to have higher heat resistance. For example, when the absorbance is measured by heating at a high temperature after mixing with a predetermined solvent, the change is not significant before and after the heat treatment Points can be confirmed.

In order to improve the optical characteristics of the colorant, a metal compound of iron oxide, CrCu or Carbon Balck, a phthalocyanine blue, a phthalocyanine green, a diarylide yellow, a diarylide AAOT yellow, Quinacridone, azo, rhodamine, perylene pigment series or colored pigment compounds of Hansa yellow G particles.

The core portion, the shell layer, and the protective layer may each include a polymer resin containing a vinyl-based repeating unit. The core part, the shell layer, and the protective layer may include a polymer resin including a vinyl-based repeating unit. The polymer resin contained in each of the core part, the shell layer, and the protective layer may be the same or different.

The vinyl-based repeating unit means a repeating unit derived from a repeating unit contained in a homopolymer of a vinyl-based monomer, that is, a vinyl-based monomer, which is a compound containing a carbon-carbon double bond in a molecule.

The vinyl-based repeating unit may be an aromatic vinyl compound, a (meth) acrylic acid compound having 1 to 20 carbon atoms, a (meth) acrylic acid alkyl ester compound having 1 to 20 carbon atoms, and a (meth) acrylic acid fluoroalkyl ester compound having 1 to 20 carbon atoms And a repeating unit derived from at least one compound selected from the group consisting of

Examples of the aromatic vinyl compound are not particularly limited, but styrene or divinylbenzene can be used, for example.

Examples of the (meth) acrylic acid ester compound having 1 to 20 carbon atoms are not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, trimethylolmethane tetra Acrylate, trimethylolmethane triacrylate, trimethylolbutane triacrylate, ethylene glycol dimethacrylate, or a mixture of two or more thereof.

Examples of the acrylic acid or methacrylic acid fluoroalkyl ester compound having 1 to 20 carbon atoms include fluoromethyl (meth) acrylate, fluoroethyl (meth) acrylate, fluorobutyl (meth) acrylate, And mixtures of two or more.

The core portion, the shell layer, and the protective layer may each further include at least one additive selected from the group including an emulsifier, a crosslinking agent, a chain transfer agent, an initiator, and a curing agent.

The emulsifier may be a surfactant, and examples thereof include anionic emulsifiers such as sodium, ammonium or potassium salts of alkyl sulfates having 4 to 30 carbon atoms, reactive emulsifiers of the same type or amphiphilic emulsifiers. Specifically, the emulsifier may be sodium dodecyl sulfate, sodium dioctylsulfosuccinate, sodium dodecylbenzene sulfate, or the like.

The crosslinking agent may include a polyfunctional (meth) acrylate compound. Examples of the polyfunctional (meth) acrylate compound include 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate , 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, divinylbenzene, ethylene glycol diacrylate, propylene But are not limited to, glycol diacrylate, butylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polybutylene glycol diacrylate, allyl acrylate, 1,2-ethanediol Dimethacrylate, 1,3-propanediol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6 - hexanediol dimethase Propylene glycol dimethacrylate, butylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, ethylene glycol dimethacrylate, Glycol dimethacrylate, triethylene glycol methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, allyl methacrylate, diallyl maleate or their 2 Mixtures of two or more species may be used.

The chain transfer agent can suppress the thermal decomposition at about 250 ° C. In the termination reaction of the polymer chain, the terminal radical of the growing chain is transferred to the other monomer, so that the uneven reaction during the chain reaction during the termination reaction It can play a role. Examples of the chain transfer agent include 1-dodecanethiol, t-dodecylmercaptan, t-hexadecylmercaptan, or a mixture of two or more thereof.

The initiator may include a water-soluble initiator or a liposoluble initiator. Examples of the water-soluble initiator include potassium persulfate, sodium persulfate, ammonium persulfate, azo-based water-soluble initiator or a mixture of two or more thereof, May be selected from benzoyl peroxide, azobisisobutyronitrile, azobisphenylbutyronitrile and azobiscyclohexanecarbonitrile, or a mixture of two or more thereof.

Examples of the curing agent include, but are not limited to, 1,2-ethanediol dimethacrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5- Hexanediol dimethacrylate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, At least one selected from the group consisting of polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate and allyl methacrylate can be used.

Meanwhile, the polymer bead may have a maximum absorbance reduction rate of 1% to 5% before and after the heat treatment at a temperature of 200 ° C to 300 ° C or 240 ° C to 300 ° C expressed by the following formula (1).

[Equation 1]

(%) = [(Maximum absorbance of polymer bead before heat treatment - maximum absorbance of polymer bead after heat treatment) / maximum absorbance of polymer bead before heat treatment] X 100

Specifically, in the formula (1), the maximum absorbance before and after the heat treatment was obtained by heating the polymer beads at 250 DEG C for 30 minutes, mixing the polymer beads before and after the heat treatment in PGEMA in an amount of 10% UV-Vis Spectroscopy, and Thermo Fisher Scientific EVOLUTION 600).

As such, since the polymer bead has a low maximum absorbance reduction rate of 1% to 5% before and after the heat treatment at a temperature of 200 ° C to 300 ° C expressed by Equation (1), the polymer bead has a core portion, It can be confirmed that the dyestuff can be stably held in a high-temperature heat treatment condition by including the dye in the multilayer structure including the protective layer.

The polymer beads are used not only for a light diffusion film, a light diffusion plate, a protective film, and a construction for a liquid crystal monitor, but also for a display dye or a color plastic material including a color ink film, an LCD and an OLED device, And the like.

According to another embodiment of the present invention, there is provided a method for producing a polymer electrolyte fuel cell, comprising the steps of: polymerizing a first monomer composition containing a vinyl monomer to form a core part; Adding a second monomer composition containing a vinyl monomer to the core portion and polymerizing to form a shell layer; And adding a third monomer composition containing a vinyl monomer to the shell layer and polymerizing to form a protective layer, wherein at least one of the first monomer composition, the second monomer composition, and the third monomer composition is A method of producing a polymer bead including a colorant having a maximum light absorption wavelength at a wavelength of 550 nm or more can be provided.

The contents of the core portion, the shell layer, the protective layer and the coloring agent are as described above in the embodiment.

The method of producing the polymer bead includes a step of at least one of the first monomer composition, the second monomer composition and the third monomer composition including a colorant that absorbs visible light having a wavelength of 550 nm or more, or 600 nm to 700 nm at a maximum can do.

The colorant may be contained in at least one of the first monomer composition, the second monomer composition and the third monomer composition, and specifically, the first monomer composition, the second monomer composition, the third monomer composition, the first monomer composition, The second monomer composition, the third monomer composition, the first monomer composition and the third monomer composition, or the first monomer composition, the second monomer composition and the third monomer composition.

In the monomer composition, 0.1 to 10 parts by weight of the colorant may be added to 100 parts by weight of the vinyl monomer. The content of the vinyl-based monomer means the content of all the vinyl-based monomers contained in the monomer composition containing the colorant when the polymer bead is produced.

If the content of the colorant relative to the vinyl monomer is excessively reduced, it is difficult to sufficiently realize the optical property of absorbing light in the ultraviolet region to the maximum. If the content of the colorant in the vinyl monomer is excessively increased, the solubility of the colorant may decrease, migration of a part of the colorant may occur, and the degree of polymerization of the vinyl monomer may decrease, .

Specifically, the method of producing the polymer bead includes: polymerizing a first monomer composition containing a vinyl monomer to form a core part; Adding a second monomer composition containing a vinyl monomer to the core portion and polymerizing to form a shell layer; And adding a third monomer composition containing a vinyl monomer to the shell layer and polymerizing to form a protective layer.

The vinyl monomer contained in the first monomer composition, the second monomer composition and the third monomer composition may be an aromatic vinyl compound, a (meth) acrylic acid compound having 1 to 20 carbon atoms, a (meth) acrylic acid alkyl ester compound having 1 to 20 carbon atoms And (meth) acrylic acid fluoroalkyl ester compounds having 1 to 20 carbon atoms.

Examples of the aromatic vinyl compound are not particularly limited, but styrene or divinylbenzene can be used, for example.

Examples of the (meth) acrylic acid ester compound having 1 to 20 carbon atoms are not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, trimethylolmethane tetra Acrylate, trimethylol methane triacrylate, trimethylol butane triacrylate, ethylene glycol dimethacrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, or a mixture of two or more thereof .

Examples of the acrylic acid or methacrylic acid fluoroalkyl ester compound having 1 to 20 carbon atoms include fluoromethyl (meth) acrylate, fluoroethyl (meth) acrylate, fluorobutyl (meth) acrylate, And mixtures of two or more.

The first monomer composition, the second monomer composition or the third monomer composition may further comprise an aqueous solvent. The aqueous solvent may include water or a hydrophilic solvent, and preferably ion exchanged water may be used. The ion-exchanged water mainly refers to pure water purified by ion exchange. Preferably, the ion-exchanged water has a low cation content and can use ultrapure water having a resistance value of 5 M? Or more under a nitrogen stream generated through an ion exchanger.

 In addition, the first monomer composition, the second monomer composition, or the third monomer composition may further include an additive including an emulsifier, a crosslinking agent, a chain transfer agent, an initiator, a curing agent, or a mixture of two or more thereof. However, in the case of the third monomer composition, the content of the emulsifier and the crosslinking agent may be less than 0.01% by weight. The content less than 0.01% by weight means that the content of the emulsifier and the crosslinking agent is very small or not contained in the third monomer composition. The contents of the emulsifier, the crosslinking agent, the chain transfer agent, the initiator, and the curing agent may include those described in the above embodiment.

Also, the weight ratio of the polyfunctional (meth) acrylate compound used as the vinyl monomer and the crosslinking agent in the first monomer composition, the second monomer composition or the third monomer composition is from 10: 1 to 100: 1, or from 20: 1 to 80: 1, or 40: 1 to 60: 1. If the content of the polyfunctional (meth) acrylate compound is excessively increased, there is a fear that the physical properties of the polymer resin obtained by polymerization of the vinyl monomer may be affected, and the aggregation phenomenon may occur between the finally formed polymer beads .

Specifically, in the step of forming the core portion, the polymerization of the first monomer composition may be carried out at a temperature of, for example, 50 to 200 DEG C for 10 minutes to 200 minutes, or 10 minutes to 80 minutes. The conversion ratio (conversion ratio) of the vinyl-based monomer to the polymer in the step of forming the core portion may be 90% or more, or 90% to 95%. If the conversion is less than 90%, the thermal stability of the polymer is lowered and pyrolysis may occur during processing.

Further, the polymerization of the second monomer composition in the step of forming the shell layer can be carried out, for example, at a temperature of 50 to 200 DEG C for 10 minutes to 300 minutes, or for 100 minutes to 300 minutes. In the step of forming the shell layer, the conversion ratio (conversion ratio) of the vinyl-based monomer to the polymer may be 90% or more, or 91% to 95%. If the conversion is less than 90%, the thermal stability of the polymer is lowered and pyrolysis may occur during processing.

Further, in the step of forming the protective layer, the polymerization of the third monomer composition can be carried out, for example, at a temperature of 50 to 200 DEG C for 10 minutes to 600 minutes, or for 100 minutes to 300 minutes. The conversion ratio (conversion ratio) of the vinyl-based monomer to the polymer in the step of forming the protective layer may be 90% or more, or 92% to 95%. If the conversion is less than 90%, the thermal stability of the polymer is lowered and pyrolysis may occur during processing.

Examples of the specific polymerization method used in the method for producing the polymer bead are not limited to a great degree. For example, emulsion polymerization, dispersion polymerization, or suspension polymerization may be used. Emulsion polymerization may be preferably used.

For example, the first step of forming the core part may include the step of making a crosslinked glass phase. Specifically, in order to control the size of the glass-like emulsion, The crosslinking agent and the initiator are added while controlling the amount of the emulsifier and the amount of the emulsifier to obtain a crosslinked glass phase.

In the second step of forming the shell layer, the step of grafting the vinyl-based monomer onto the glass polymerized in the first step may be included. Specifically, while using a small amount of a vinyl monomer, a cross-linking agent and an emulsifier are added and an initiator is added to prepare a crosslinked polymer resin phase. In order to avoid the aggregation of dendrites, the vinyl monomer is gradually added dropwise and the reaction time is increased.

And the third step of forming the protective layer may include grafting the vinyl-based monomer onto the polymerized phase in the second step. Specifically, by using the same monomer as the matrix resin of the first step and without using an emulsifier and a crosslinking agent to obtain a polymer which is not crosslinked, it acts as a matrix itself or improves the mixing property with the matrix resin . In the third step, a chain transfer agent can be used to control the molecular weight.

More specifically, a method for producing the polymer beads will be described below. An ion exchange water, an emulsifier, a cross-linking agent and a part of monomers having a resistance value of 1 M? Or more are put in a nitrogen stream and polymerization is carried out by adding an initiator when the internal temperature reaches 50 to 90 占 폚. When the polymerization proceeds and the emulsion is formed, the remaining amount of the first-stage monomer is gradually added dropwise and then polymerized. At the final stage of the polymerization, an initiator is further added to complete the first stage polymerization.

The average particle diameter of the crosslinked glass-like polymer thus produced is 10 to 100 nm. The particle size can be controlled by controlling the amount, type and stirring speed of the emulsifier, and the size of the obtained particles is very uniform.

For example, the first monomer composition may be stirred at a speed of 50 rpm to 200 rpm for 10 minutes to 60 minutes. Although the specific stirring method is not limited to a specific example, for example, the composition may be placed in a reactor, And stirring with a mechanical stirrer can be used.

Then, the monomer of the second step is mixed with a crosslinking agent, an emulsifier, etc., while being kept at the same temperature, and then gradually added dropwise to the solution to perform polymerization. In the same manner as in the first step, Complete. The average thickness of the crosslinked dendritic polymer is about 30 to 300 nm, and the particle size is very uniform. Stirring of the second monomer composition may also be carried out at a rate of 50 rpm to 200 rpm for 10 minutes to 60 minutes.

In the third step, the polymerization is carried out using monomers and an initiator without the addition of an emulsifier. The initiator is added at the end of the second step, the monomer is slowly added dropwise to the solution, and polymerization is carried out. When the polymerization has almost progressed, an initiator is finally added to complete the polymerization. The average thickness of the final glassy polymer is about 10 to 1000 nm, or about 30 to 700 nm, or about 50 to 500 nm, and the particle size is very uniform.

On the other hand, the core portion of the innermost angle and the shell layer as the intermediate layer are used in a cured state, and the curing agent is used in an amount of 0.5 to 2.5 parts by weight based on the monomer, and the protective layer as the outermost layer is simply grafted or cured to the intermediate shell layer. 1.0 parts by weight or less.

On the other hand, prior to the step of polymerizing the first monomer composition, the second monomer composition and the third monomer composition, at least one composition selected from the group consisting of the first monomer composition, the second monomer composition and the third monomer composition And processing with an ultrasonic wave having an output intensity of 100W to 1000W. The ultrasonic treatment may be performed for 10 minutes to 60 minutes. Through this, the components contained in the monomer composition can be uniformly dispersed.

Examples of the method of treating at least one composition selected from the group consisting of the first monomer composition, the second monomer composition and the third monomer composition with an ultrasonic wave having an output intensity of 100 W to 1000 W are not limited to a wide range. For example, (ULTRASONIC, Hielscher Ultrasonics GmbH (Germany)) in an ultrasonic wave of 400W for 30 minutes.

Further, the step of polymerizing the first monomer composition, the second monomer composition and the third monomer composition may further include a step of filtration, washing and drying. The filtration, washing and drying methods can be used without any limitations in various methods conventionally used.

In addition, after the drying step, it may further include a pulverizing step, if necessary. Examples of the pulverizing method include a pulverizer such as a jet mill, a ball mill atomizer or a hammer mill.

INDUSTRIAL APPLICABILITY According to the present invention, there can be provided a polymer bead having optical resistance that has excellent light resistance and heat resistance and absorbs light in the ultraviolet ray region to the maximum, and a method for producing the same.

FIG. 1 is a photograph of a polymer bead prepared in Example 1, which was measured by a scanning electron microscope (SEM).
2 is a photograph of a polymer bead prepared in Example 4, which was measured by a scanning electron microscope (SEM).

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

< Example  1 to 8: Polymer Bead  Manufacturing>

Example 1

(1) Core part manufacturing (step 1)

541 g of secondary distilled water was charged into a 2 L reactor and heated to an internal temperature of 80 캜 under a nitrogen stream. Then, 13.8 g of methyl methacrylate, 8.0 g of ethyl acrylate, 5.6 g of allylmethacrylate, 21.8% And 6.8 g of pseudosinicate was added to the reactor, followed by stirring at 100 rpm for 15 minutes. Then, 1.3 g of a 2.56% potassium persulfate solution was added to the reactor, followed by emulsification for 60 minutes to prepare a core part.

(2) shell layer manufacturing (step 2)

1.8 g of a 2.25% potassium persulfate solution was added to the glass polymer emulsion containing the core portion and stirred at 150 rpm for 15 minutes. Then, 141.2 g of methyl methacrylate, 33.9 g of vinyl-zinc phthalocyanine substituted with a vinyl group, A mixed solution of 3.0 g of acrylate, 2.0 g of allylmethacrylate, and 5.7 g of 21.8% sodium dioctylsulfosuccinate was added dropwise to the reactor at a rate of 0.1 kg per minute. After completion of the dropwise addition, 1.8 g of 2.25% potassium persulfate solution was added and emulsified for 120 minutes to prepare a core-shell type emulsion having a shell layer formed on the core portion.

(3) Production of protective layer (step 3)

A mixed solution of 109.2 g of methyl methacrylate, 5.7 g of ethyl acrylate, 0.2 g of dodecylmercaptan and 0.1 g of azobisisobutyronitrile was added to the reactor containing the core-shell type emulsion at a temperature of 50 ° C . After the temperature was gradually raised to 80, the polymerization was carried out for 120 minutes to form a protective layer on the shell layer, and then a polymer bead as a powdery end product was prepared by using a spray dryer.

Example  2

In the same manner as in Example 1, except that acrylic-zinc phthalocyanine was used instead of vinyl-zinc phthalocyanine substituted in vinyl group in the second step of preparing the shell layer, .

Example  3

In the same manner as in Example 1 except that methacryl-zinc phthalocyanine was used instead of vinyl-zinc phthalocyanine substituted with vinyl group in the second step of preparing the shell layer, Beads were prepared.

Example  4

In the second step of preparing the shell layer, a blue KS001 (methacryl-substituted; N- (4 - ((4- (diethylamino) phenyl) The polymer beads were prepared in the same manner as in Example 1, except that 4- (methacryloyloxy) cyclohexylamino) naphthalen-1-yl) methylene) cyclohexa-2,5-dienylidene) -N-ethylethanaminium was used.

Example  5

In the second step of preparing the shell layer, a polymer bead was prepared in the same manner as in Example 1, except that vinyl-zinc phthalocyanine was used in place of vinyl-zinc phthalocyanine substituted with a vinyl group.

Example  6

In the first step of producing the core part, a mixed solution of 141.2 g of methyl methacrylate, 33.9 g of zinc phthalocyanine, 3.0 g of ethyl acrylate, 2.0 g of allyl methacrylate, and 5.7 g of 21.8% sodium dioctylsulfosuccinate was added And a mixed solution of 13.8 g of methyl methacrylate, 8.0 g of ethyl acrylate, 5.6 g of allylmethacrylate and 6.8 g of 21.8% sodium dioctylsulfosuccinate in a second step of preparing the shell layer at a rate of 7.0 g per minute In the same manner as in Example 1, except that the polymer beads were added to the reactor.

Example  7

A mixed solution of 109.2 g of methyl methacrylate, 5.7 g of ethyl acrylate and 5.7 g of sodium dioctylsulfosuccinate in an amount of 7.0 g per minute was added dropwise to the reactor in the second step of preparing the shell layer, A mixture solution of 141.2 g of methyl methacrylate, 33.9 g of zinc phthalocyanine, 3.0 g of ethyl acrylate, 2.0 g of allyl methacrylate, 0.2 g of dodecylmercaptan and 0.1 g of azobisisobutyronitrile was used The polymer beads were prepared in the same manner as in Example 1 except for the following points.

Example  8

In the first step of producing the core part, a mixed solution of 13.8 g of methyl methacrylate, 8.0 g of ethyl acrylate, 5.6 g of allyl methacrylate, and 6.8 g of 21.8% sodium dioctylsulfosuccinate was added to an ultrasonic disperser Beads were prepared in the same manner as in Example 1, except that the mixture was treated in a 400 W ultrasonic wave for 30 minutes using ULTRASONIC and Hielscher Ultrasonics GmbH (Germany).

< Comparative Example  1 to 3: Polymer Bead  Manufacturing>

Comparative Example 1

A polymer bead was prepared in the same manner as in Example 1, except that zinc phthalocyanine substituted with a vinyl group was not added in the second step of preparing the shell layer.

Comparative Example 2

90 g of the polymer bead prepared in Comparative Example 1 and 10 g of zinc phthalocyanine substituted with a vinyl group were mixed to prepare a polymer bead mixture.

Comparative Example 3

90 g of the polymer bead prepared in Comparative Example 1 and 10 g of zinc phthalocyanine were mixed to prepare a polymer bead mixture.

< Experimental Example  : Example  And In the comparative example  Obtained Polymer Bead  Measurement of physical properties>

Experimental Example 1 . Polymer Bead  Measure size

The average diameter of the polymer beads obtained in the above Examples and Comparative Examples was measured using a laser spectroscope (Laser Spectroscopy, Otsuka ELSZ), and the results are shown in Table 1 below. A photograph of the bead obtained in Example 1 is shown in Fig. 1, and a photograph of the bead obtained in Example 4 is shown in Fig. 2 by a scanning electron microscope (SEM). .

For the polymer beads prepared in the above examples, the average diameter was measured at the completion of polymerization of each of the core part / shell layer / protective layer to determine the thicknesses of the core part / shell layer / protective layer.

The size measurement results of the polymer beads obtained in Examples and Comparative Examples division Average diameter (nm) Deviation (PD value) Example 1 246.5
(Core part: 73.2 nm, shell layer: 156.8 nm, protective layer: 16.5 nm) 0.084 Example 2 236.6
(Core part: 71.3 nm, shell layer: 140.4 nm, protective layer: 24.9 nm) 0.100 Example 3 132.8
(Core part: 77.5 nm, shell layer: 37.9 nm, protective layer: 17.4 nm) 0.033 Example 4 126.6
(Core portion: 70.8 nm, shell layer: 40.2 nm, protective layer: 15.6 nm) 0.038 Example 5 219.0
(Core part: 75.7 nm, shell layer: 118.9 nm, protective layer: 24.4 nm) 0.075 Example 6 231.0
(Core part: 74.3 nm, shell layer: 136.5 nm, protective layer: 20.2 nm) 0.083 Example 7 227.5
(Core part: 71.5 nm, shell layer: 136.6 nm, protective layer: 19.4 nm) 0.067 Example 8 216.1
(Core part: 65.7 nm, shell layer: 131.6 nm, protective layer: 18.8 nm) 0.031 Comparative Example 1 149.5 0.061 Comparative Example 2 149.5 0.061 Comparative Example 3 149.5 0.061

As shown in Table 1, it can be confirmed that the polymer beads obtained in Examples 1 to 8 have a nano size of 125 nm to 250 nm. Also, as shown in FIGS. 1 and 2, it was confirmed that the nanobeads of the above examples had a spherical shape.

Experimental Example 2 . Polymer Bead  Heat absorption measurement

The polymer beads obtained in the above Examples and Comparative Examples were heated at 250 占 폚 for 30 minutes, and the difference in heat resistance was measured. For this purpose, the polymer beads before and after the heat treatment were mixed in PGEMA in a concentration of 10%, and coated on a 5 × 5 cm glass with 2.0 μm. Using a UV absorbance meter (UV-Vis Spectroscopy, EVOLUTION 600 from Thermo Fisher Scientific) And the maximum absorption wavelength were measured. The results are shown in Table 2 below.

At this time, the maximum absorbance reduction ratio before and after the heat treatment was obtained by the following equation (1).

[Equation 1]

Maximum absorbance reduction rate (%) before and after heat treatment = [(maximum absorbance of polymer bead before heat treatment - maximum absorbance of polymer bead after heat treatment) / maximum absorbance of polymer bead before heat treatment] X 100.

The results of measuring the heat absorbance of the polymer beads obtained in Examples and Comparative Examples [the maximum absorbance measurable is 2.0] division Maximum absorbance before heat treatment
(Maximum absorption wavelength [nm]) Maximum absorbance after heat treatment
(Maximum absorption wavelength [nm]) Maximum absorbance reduction rate (%) before and after heat treatment Example 1 1.47 (670) 1.46 (670) 0.7 Example 2 1.50 (667) 1.50 (667) 0 Example 3 1.57 (674) 1.56 (674) 0.6 Example 4 1.62 (613) 1.62 (613) 0 Example 5 1.35 (673) 1.34 (673) 0.7 Example 6 0.75 (671) 0.74 (671) 1.3 Example 7 1.57 (672) 1.53 (672) 2.5 Example 8 1.33 (672) 1.32 (672) 0.8 Comparative Example 1 0 0 - Comparative Example 2 1.08 (671) 1.01 (671) 6.5 Comparative Example 3 1.12 (670) 1.04 (670) 7.1

As shown in Table 3, the polymer beads prepared in Examples 1 to 8 exhibited a maximum absorbance reduction rate of less than 5% before and after the heat treatment and were relatively smaller than those of Comparative Examples 2 and 3, It was confirmed that the heat resistance of the dye was improved.

Claims (19)

A core portion; A shell layer formed on the core portion; And a protective layer formed on the shell layer,
Wherein the core portion, the shell layer and the protective layer each comprise a polymer resin containing a vinyl-based repeating unit,
Wherein at least one of the core portion, the shell layer, and the protective layer comprises a colorant having a maximum optical absorption wavelength at a wavelength of 550 nm or more.
The method according to claim 1,
Wherein the polymer bead has a maximum optical absorption wavelength at a wavelength of 600 nm to 700 nm.
The method according to claim 1,
Wherein the polymer bead has a light absorption coefficient of 450 nm to 500 nm, or a light absorptivity of 0.02% or less at a wavelength of 750 nm or more.
The method according to claim 1,
Wherein the polymer bead is a polymer bead having a maximum absorbance reduction rate of 1% to 5% before and after the heat treatment at a temperature of 200 ° C to 300 ° C,
[Equation 1]
Maximum absorbance reduction rate (%) before and after heat treatment = [(maximum absorbance of polymer bead before heat treatment - maximum absorbance of polymer bead after heat treatment) / maximum absorbance of polymer bead before heat treatment] X 100.
The method according to claim 1,
Wherein the average diameter of the polymer beads is 10 nm to 900 nm.
The method according to claim 1,
The maximum diameter of the core portion is 10 nm to 200 nm, the thickness of the shell layer is 10 nm to 300 nm, and the thickness of the protective layer is 10 nm to 100 nm.
The method according to claim 1,
Wherein the colorant comprises at least one member selected from the group consisting of an anthraquinone compound, an acridone compound, a cyanine compound, an azo compound, a formalin compound and a triarylmethane compound.
8. The method of claim 7,
Wherein the cyanine-based compound comprises a phthalocyanine-based complex compound or a triarylmethane-based compound.
9. The method of claim 8,
The phthalocyanine-based complex compound may be a ligand including a phthalocyanine-based compound; And a central metal comprising a transition metal.
9. The method of claim 8,
Wherein the triarylmethane-based compound comprises a triarylmethane-based derivative represented by the following formula (3): polymer bead:
(3)

Wherein X ^- is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, An aromatic hydrocarbon having 6 to 10 carbon atoms, R ₁₅ is a functional group represented by the following structural formula 1,
[Structural formula 1]

In the above structural formula 1, n is an integer of 1 to 10, R ₁₇ is hydrogen or methyl, and "*" is a bonding point.
The method according to claim 1,
Wherein the surface of the colorant is a polymer in which at least one reactive functional group selected from the group consisting of an amide group, an amine group, a thiol group, an ester group, a vinyl group, a hydroxyl group, a phenol group, a (meth) acrylic functional group and a carboxyl group is substituted or unsubstituted Bead.
The method according to claim 1,
The vinyl-based repeating unit may be an aromatic vinyl compound, a (meth) acrylic acid compound having 1 to 20 carbon atoms, a (meth) acrylic acid alkyl ester compound having 1 to 20 carbon atoms, and a (meth) acrylic acid fluoroalkyl ester compound having 1 to 20 carbon atoms Wherein the polymeric bead comprises a repeating unit derived from at least one compound selected from the group consisting of:
Polymerizing a first monomer composition containing a vinyl-based monomer to form a core portion;
Adding a second monomer composition containing a vinyl monomer to the core portion and polymerizing to form a shell layer; And
Adding a third monomer composition containing a vinyl monomer to the shell layer and polymerizing to form a protective layer,
Wherein at least one of the first monomer composition, the second monomer composition and the third monomer composition comprises a colorant having a maximum optical absorption wavelength at a wavelength of 550 nm or more.
14. The method of claim 13,
Wherein the step of forming the core portion, the step of forming the shell layer, or the step of forming the protective layer each proceeds at a temperature of 50 to 200 DEG C for 10 minutes to 600 minutes.
14. The method of claim 13,
Wherein the maximum diameter of the core portion is 10 nm to 200 nm, the thickness of the shell layer is 10 nm to 300 nm, and the thickness of the protective layer is 10 nm to 100 nm.
14. The method of claim 13,
The vinyl monomer may be an aromatic vinyl compound, a (meth) acrylic acid compound having 1 to 20 carbon atoms, a (meth) acrylic acid alkyl ester compound having 1 to 20 carbon atoms and a (meth) acrylate fluoroalkyl ester compound having 1 to 20 carbon atoms And at least one compound selected from the group consisting of at least one compound selected from the group consisting of the compounds.
14. The method of claim 13,
Wherein the content of the colorant relative to 100 parts by weight of the vinyl monomer in the monomer composition is 0.1 parts by weight to 10 parts by weight.
14. The method of claim 13,
Wherein the colorant comprises at least one selected from the group consisting of an anthraquinone compound, an acridone compound, a cyanine compound, an azo compound, and a formate compound and a triarylmethane compound.
14. The method of claim 13,
Further comprising treating the at least one composition selected from the group consisting of the first monomer composition, the second monomer composition and the third monomer composition with an ultrasonic wave having an output intensity of 100 W to 1000 W.

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