WO2017003228A1 - 폴리머 비드，폴리머 비드의 제조방법 및 이를 이용한 광학용 필름 - Google Patents

폴리머 비드，폴리머 비드의 제조방법 및 이를 이용한 광학용 필름 Download PDF

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WO2017003228A1
WO2017003228A1 PCT/KR2016/007061 KR2016007061W WO2017003228A1 WO 2017003228 A1 WO2017003228 A1 WO 2017003228A1 KR 2016007061 W KR2016007061 W KR 2016007061W WO 2017003228 A1 WO2017003228 A1 WO 2017003228A1
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group
compound
polymer
polymer beads
based compound
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PCT/KR2016/007061
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English (en)
French (fr)
Korean (ko)
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김영신
임동홍
채헌승
김시민
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코오롱인더스트리 주식회사
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Publication of WO2017003228A1 publication Critical patent/WO2017003228A1/ko

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the present invention relates to polymer beads, a method for producing polymer beads, and an optical film. More specifically, the present invention relates to a polymer bead having an excellent durability, heat resistance and light resistance through a nano-sized multilayer structure, and having optical properties having discoloration properties when irradiated with light in an ultraviolet region, and a method of manufacturing the same.
  • Polymer beads generally refer to spherical particles having a uniform particle size distribution produced by emulsion polymerization, suspension polymerization, or the like. Polymer beads are used in a wide variety of applications, not only for use in light-diffusion films, protective films and construction of liquid crystal monitors, but also widely used in coating transparent films for color inks. Polymer beads used for this purpose are generally suspended polymer '(Suspension Polymer i zat i on) and dispersion polymer (Di spers ion).
  • the polymer beads are prepared by dispersing the monomer present in the aqueous solution by mechanical force.
  • the polymer beads produced by this method have a bead size of at least 100 // m or more, and the bead distribution tends to be wide because the beads are dispersed by mechanical force.
  • the polymer beads prepared by the conventional polymerization process may provide hiding power because the refractive index of the polymer is different from that of the conventional resin, and thus, the polymer beads are widely used when they are produced by extruding a light diffusion plate or a lighting fixture. In this way, when the product is made by extrusion, the product is mixed at a high temperature. Because of its use, excellent thermal stability is required.
  • the weight change reduction width is large and may cause physical and chemical changes in the environment in which the beads are used. That is, the physical properties of the final product may be changed due to the decrease in compatibility, the formation of fume or by-products, and the change of properties such as the shape of the beads is severely deformed when read by SEM photographs.
  • the present invention is to provide a polymer bead having an excellent durability, heat resistance and light resistance through the nano-sized multilayer structure, the optical properties that absorb the maximum light in the ultraviolet region, and exhibits discoloration.
  • the present invention is to provide a method for producing the polymer beads.
  • the present invention is to provide an optical film using the polymer beads.
  • a light emitter that emits visible light at wavelengths of 380 nm-750 nm after maximum light absorption at wavelengths less than and including an amide group, an amine group, a thiol group, an ester group, on the surface of the emitter;
  • the plymer bead In the present specification, the plymer bead; And a binder resin; an optical film is provided.
  • (meth) acrylic acid is meant to include both acrylic acid and methacrylic acid.
  • (meth) acrylate is also meant to include both acrylates and methacrylates.
  • a light emitter which emits visible light having a wavelength of 380 nm to 750 nm after maximum light absorption at a wavelength less than a wavelength, wherein the surface of the light emitter includes an amide group, an amine group,
  • polymer beads in which at least one semi-active functional group selected from the group consisting of 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 /
  • the inventors of the present invention use the specific polymer beads described above to improve the thermal stability and have excellent heat resistance, as well as to secure stability by ultraviolet rays, and have excellent light resistance, thereby absorbing ultraviolet rays and emitting them in the form of visible light. It was confirmed through experiments that the optical properties unique to the light-emitting body can be realized at the same level even when contained in the polymer beads, and completed the invention.
  • the polymer bead consists of a core portion, a shell layer and a protective layer
  • a light emitter By containing a light emitter in the triple layer structure, it is possible to prevent the phenomenon of the light emitter to ensure excellent weather resistance and durability. In addition, it is possible to prevent the change of physical properties of the polymer resin during the shaking at high temperature or high pressure, the extrusion process, to prevent the sensitivity of the light emitter from changing according to the temperature or to decompose the light emitter itself by heat, thereby ensuring excellent heat resistance.
  • the polymer beads may be used as printing inks, cosmetic additives, plastic materials, display materials, and the like for security, light blocking, and light sensors.
  • the polymer bead core A shell layer formed on the core portion; And a protective layer formed on the shell layer.
  • the polymer bead may have a three-layer structure in which core parts and shell layer protective layers are stacked in order from the inside to the outer surface.
  • a well-known core-shell structure may have a triple layer structure in which a protective layer is stacked on the shell layer again.
  • Each of the shell layer and the protective layer included in the polymer beads not only have a stable and robust structure, but also are bonded or crosslinked with each other in a sequentially stacked state, thereby providing an outer layer or surface layer having improved mechanical properties, shape stability, and solvent resistance. It is possible to form and the polymer beads to be produced can be stably dispersed without agglomeration.
  • Examples of the form of the polymer beads are not limited to a large, for example, spherical, spherical, polyhedral, etc., the cross section of the polymer beads It may be round, elliptical, 3 to 50 polygons.
  • the average particle diameter of the polymer beads may be 10 nm to 900 nm, or 30 nm to 700 ⁇ , or 50 nm to 500 nm.
  • the core may have a maximum diameter of 10 nm to 200 ran, the thickness of the shellworm may be 10 nm to 300 ran, and the thickness of the protective layer may be 10 ran to 100 ran.
  • At least one of the core portion, the shell layer, and the protective layer may include a light emitter having a maximum light absorption wavelength at a wavelength of less than 400 nm, or 200 nm to 390 nm, or 300 nm to 390 nm.
  • the light emitter may mean a material that emits light.
  • the light emitter may be a dye (Dye) or a pigment (Pigment) and the like, preferably a dye may be used.
  • the polymer bead contains a light emitter therein, and in the process of applying the light emitter to the film, it is possible to prevent the phenomenon of the light emitter transition to ensure excellent weather resistance and durability.
  • the polymer bead including the light emitter-can also have a high absorbance for a wavelength of less than 400 nm, or 200 nm to 390 nm, or 300 nm to 390 nm, the light emitter is a core portion of the polymer bead, Including polymer resin contained in the shell layer and the protective layer. It can be effectively combined with general purpose resins to realize high color performance, high contrast, and light conversion efficiency.
  • the polymer beads may have a maximum light absorption wavelength at a wavelength of less than 400 nm, or 200 nm to 390 nm, or 300 nm to 390 ran.
  • 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.
  • Light absorbance means the ratio of the actual measured absorbance to the maximum measurable absorbance, and as shown in Table 3 and Table 4 below, the maximum absorbance is 2.0.
  • the polymer beads have a light absorption at a wavelength of 400 nm to 800 nm Or 0.02% or less.
  • the light absorbance means the ratio of the actual measured absorbance to the maximum measurable absorbance, and as shown in Tables 3 and 4 below, the maximum absorbance is 2.0.
  • the polymer beads exhibited a very low value close to zero at absorbances of less than 0.05 at wavelengths of 400 ran to 800 ran, from which the polymer beads hardly absorb light in the visible region. .
  • the polymer beads may have a selective absorption of light in the ultraviolet region, and hardly absorbs visible light having a wavelength of 400 ran to 800 nm, and usually appears to be white to ivory to our eyes. Therefore, when the polymer beads including the polymer resin and the light emitter are mixed with the polymer beads or the polymer resin not including the light emitter until irradiated with ultraviolet rays, they may not be easily distinguished visually.
  • the polymer beads may emit visible light having a wavelength of 380 nm to 750 nm after maximum light absorption at a wavelength of less than 400 nm. That is, the polymer beads may absorb the ultraviolet rays and absorb the ultraviolet rays and emit them in the form of a specific visible ray, and may be colored. Therefore, the polymer beads can be clearly distinguished by changing the color of the wavelength band emitted by the polymer beads containing the light emitter after irradiating ultraviolet rays.
  • the polymer beads which do not usually show color differences with the naked eye and show color differences due to irradiation of ultraviolet rays in a specific wavelength range, can be utilized in security products.
  • At least one of the core portion, the shell layer and the protective layer includes 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, or a core portion, a shell layer and a protective layer. can do.
  • the surface of the light emitter may be substituted with at least one semi-ung functional group selected from the group consisting of amide group, amine group, thiol group, ester group, vinyl group, hydroxy group, phenol group, (meth) acrylic functional group and carboxyl group.
  • the surface of the light emitting body means the terminal of the light emitting compound molecular structure
  • the (meth) acrylic type means an acrylic or methacrylic system.
  • the light emitter may be effectively combined with a general-purpose resin including a polymer resin included in a core part, a shell insect, and a protective layer of the polymer bead, thereby realizing high color rendering power and high contrast ratio light conversion efficiency.
  • the light emitter may be effectively dissolved in the monomer composition of the polymer resin by a reactive functional group substituted on the surface of the light emitter. Accordingly, after polymerization of the monomer of the polymer resin, the light emitter may be included in the polymer resin contained in the core portion, shell layer and protective layer of the polymer bead, the polymer beads can implement excellent optical properties have.
  • the content of the light emitter with respect to the polymer beads may be 0.01 weight 3 ⁇ 4> to 20 weight%, or 0.1 weight% to 10 weight%, or 1 weight% to 8 weight%.
  • the content of the light emitter in the polymer beads is excessively reduced, it is difficult to fully realize the optical characteristics to absorb the light in the ultraviolet region to the maximum.
  • the solubility of the light emitter is reduced, migration of some of the light-emitting body may occur (migrat ion) phenomenon, the polymerization degree of the polymer resin to be described later decreases the heat resistance of the polymer bead The degree may decrease.
  • the polymer beads may include 0.1 to 20 parts by weight, or 1 to 10 parts by weight, or 3 to 8 parts by weight of the light emitter with respect to 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 polymer contained in the polymer bead, and specifically, the sum of the content of all the polymer resin contained in the core portion, the shell layer, and the protective layer.
  • the content of the light emitter to the polymer resin is excessively reduced, it is difficult to realize the optical properties to absorb the light in the ultraviolet region to the maximum.
  • the solubility of the light emitter is reduced, migration of some light emitter may occur, the polymerization degree of the polymer resin is reduced, the heat resistance of the polymer resin is reduced can do.
  • the light emitter has a solubility in vinyl monomers of 60% or more, or 60% To 100%.
  • the light emitter may have high solubility with respect to the vinyl monomer, and thus may be dissolved in the vinyl monomer in the reaction solution to implement excellent optical properties and durability.
  • the solubility of the light emitter in the vinyl monomer is less than 60%, the light emitter may be difficult to stably and evenly dispersed in the reaction solution, and a phenomenon may occur in the final bead surface.
  • the illuminant is perylene compounds, isoquinoline compounds, europium-based complex compounds, cyano-based compounds, Scotland Kurashiki-based compounds, phthalocyanine-based compounds, anthraquinone-based compounds, acridine dongye compound, a cyanine compound, azo compound, poma jeungye A compound or two or more kinds thereof may be included.
  • an isoquinoline compound, a europium complex, a cyanazole compound or two or more kinds thereof may be used as the light emitter.
  • the isoquinoline-based compound includes an isoquinoline compound or a compound in which various substituents are introduced into the isozunoline compound.
  • substituted means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent may be substituted, and when two or more are substituted, 2
  • the above substituents may be the same or different from each other.
  • substituents examples 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, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, and a 6 to 20 carbon atoms.
  • Aryl alkyl group, 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, a C1-C20 alkoxy group, etc. are mentioned.
  • the isoquinoline-based complex may include a derivative compound of benzoisoquinoline.
  • the derivative refers to a similar compound obtained by chemically changing a part of a compound, and generally refers to a compound in which a hydrogen atom or a specific atomic group in the compound is substituted by another atom or atomic group. That is, the derivative compound of the benzoisoquinoline
  • benzo [de] isoquinoline-1,3-dione substituted with an alkyl, hydroxy or alkoxy group having 1 to 10 carbon atoms This can be used.
  • the alkyl group having 1 to 10 carbon atoms is a monovalent functional group derived from alkane, for example, as the linear, branched or cyclic, preferably branched alkyl group having 5 to 10 carbon atoms can be used.
  • the alkyl group having 1 to 10 carbon atoms may be bonded to a nitrogen atom included in the benzo [de] isoquinoline-1, 3-dione.
  • the alkoxy group having 1 to 10 carbon atoms is a form in which the alkoxy group is a combination of an alkyl group and an oxygen atom as defined above, for example, methoxy, ethoxy, propoxy, appendix, phenoxy, nucleosiloxy, hexyloxy, octyl Oxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, nuxadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy C, eicosanyloxy, or all possible isomers thereof, but may not be limited thereto.
  • a linear alkyl group having 1 to 5 carbon atoms and an oxygen atom bonded thereto can be used.
  • the alkoxy group and hydroxy group having 1 to 10 carbon atoms may be bonded to a carbon atom included in the benzo [de] isoquinoline _1,3-dione.
  • Specific examples of the benzo [de] isoquinoline-1,3-dione substituted with the alkyl group, hydroxy group or alkoxy group having 1 to 10 carbon atoms include BL blue-OH dyes represented by the following Chemical Formula 1 [6-hydroxy-7 -methoxy-2- (octan-3-yl) -1H ⁇ benzo [de] i soquinol ine_l, 3 (2H) ⁇ dione].
  • the thiazole compound may include a thiazole compound or a derivative compound having various substituents introduced into the thiazole compound, and specifically, the thiazole compound may include a derivative compound of benzothiazol.
  • the derivative compound of the benzoxazole is a compound obtained through a chemical reaction from the benzoxazole compound.
  • benzo [d] cyazole substituted with a phenol group may be used.
  • Specific examples of the benzo [d] cyazole substituted with the phenol group include BL GreenI 0H dye [2— (benzo [d] thiazol—2—yl) phenol] represented by the following general formula (2).
  • BL Green-OH dye [2- (benzo [d] thiazol-2-yl) phenol] represented by Chemical Formula 2 has a wavelength of less than 400 nm, specifically after maximum light absorption at 320 nm to 330 nm, from 520 nm to It can emit green light with a wavelength of 570 nm.
  • the europium-based complex compound refers to a compound in which the europium metal or the ion is the central metal, and various ligands are bonded to the central metal.
  • the europium-based complex compound is a ligand containing an enolate ion derived from a heteroaromatic polycyclic compound or 1,3-diketone; And a central metal including europium.
  • the heteroaromatic polycyclic compound may include at least one or two or more hetero atoms, such as oxygen, nitrogen, phosphorus, sulfur, and at least two aromatic rings.
  • heteroaromatic polycyclic compound are not particularly limited, and for example, there may be mentioned phenanthroline.
  • the enolate ion derived from the 1,3-diketone is an anion formed through spontaneous equilibrium shift of a 1,3-diketone compound, and the 1,3-diketone is an example of 1 being substituted with halogen.
  • -(Thiophen-2-yl) butane-1,3-dione can be used.
  • europium-based complex compounds include BL Red-Vinyl dyes represented by the following general formula (3).
  • the BL Red-Vinyl dye represented by Chemical Formula 3 may emit red light by emitting visible light having a wavelength of less than 400 nm, specifically, wavelengths of 600 nm to 700 nm after maximum light absorption at 340 ran to 350 nm.
  • the perylene-based compound isoquinoline-based compound, europium-based compound, squalene-based compound, phthalocyanine-based compound, ' anthrazonone-based compound, acridon-based compound
  • the surface of a cyanine compound, an azo compound, a formazone compound, or a mixture of two or more thereof includes 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.
  • One or more reactive functional groups selected from the group may be substituted.
  • the surface of the light emitting body means the terminal of the light emitting compound molecular structure
  • the (meth) acrylic type means an acrylic or methacrylic system. Accordingly, the light emitter can be effectively combined with a general-purpose resin including a polymer resin included in the core portion, the shell layer, and the protective layer of the polymer bead, thereby realizing high color performance, high contrast ratio, and light conversion efficiency.
  • the polymer beads may have a higher heat resistance by including the polymer resin and the light emitter bonded thereto, and for example, when the absorbance is measured by heating at a high temperature after mixing with a predetermined solvent, the change before and after heat treatment is not so large. You can check the point.
  • the surface of the light emitting body has 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 (e.g., (meth) acrylic acid is introduced to substitute one or more semi-ung functional groups selected from the group consisting of (meth) acrylic functional groups bonded and formed on the polymer beads)
  • a (meth) acrylic functional group and a carboxyl group e.g., (meth) acrylic acid is introduced to substitute one or more semi-ung functional groups selected from the group consisting of (meth) acrylic functional groups bonded and formed on the polymer beads
  • a metal compound of iron oxide, CrCu or Carbon Balck, phthalocyanine blue, phthalocyanine green, diaryl i de yellow, diarylide MOT It may further include yellow, and colored pigment compounds of quinacr i done, azo, arhodamine, perylene ene pigment series or Hansa ye l low G particles.
  • the core portion, the shell layer, and the protective layer may each include a polymer number including a vinyl-based repeating unit. "The core portion, both the shell layer, and a protective layer can contain a polymeric resin, including a vinyl-based batbok unit, the polymeric resin contained in the core portion, the shell layer, and a protective layer each may be the same or may be different.
  • the vinyl repeating unit means a repeating unit included in a homopolymer of a vinyl monomer that is a compound containing a carbon-carbon double bond in a molecule, that is, a repeating unit derived from a vinyl monomer.
  • the vinyl-based repeating unit is an aromatic vinyl-based compound, "having 1 to 20 carbon atoms
  • a (meth) acrylic acid compound, a (meth) acrylic acid alkyl ester compound having 1 to 20 carbon atoms, and a repeating unit derived from at least one compound selected from the group consisting of (meth) acrylic acid fluoroalkyl ester compounds having 1 to 20 carbon atoms Can be.
  • aromatic vinyl compound examples are not particularly limited, but for example, styrene or divinyl benzene may be used.
  • Examples of the (meth) acrylic acid ester compound having 1 to 20 carbon atoms are also not particularly limited.
  • methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, trimethylolmethane tetra Acrylate , trimethylolmethane triacrylate , trimethylbutane Triacrylate, ethylene glycol dimethacrylate or two or more kinds thereof can be used.
  • acrylic acid or methacrylic acid fluoroalkyl ester compound having 1 to 20 carbon atoms examples include fluoromethyl (meth) acrylate, fluoroethyl (meth) acrylate, fluorobutyl (meth) acrylate, and the like. 2 or more types of mixtures are mentioned.
  • the core portion, the shell layer and the protective layer may each further include one or more additives selected from the group comprising emulsifiers, crosslinkers, chain transfer agents, initiators, and curing agents.
  • the emulsifier may include a surfactant, and examples thereof include anionic emulsifiers such as sodium, ammonium, or potassium salts of alkyl sulfates having 4 to 30 carbon atoms, in-situ emulsifiers or amphiphilic emulsifiers.
  • the emulsifier may be used sodium dodecyl sulfate, sodium dioctylsulfosuccinate or sodium dodecylbenzene sulfate.
  • the crosslinking agent may include a polyfunctional (meth) acrylate-based compound, and examples of the polyfunctional (meth) acrylate-based compound include 1,2-ethanedioldiacrylate and 1,3-propanedioldiacrylate.
  • the chain transfer agent may play a role of inhibiting thermal decomposition around 250 ° C., and in the termination reaction of the polymer chain, by transferring the radical at the end of the growing chain to other monomers, uneven reaction during chain growth during termination reaction It can play a role of reducing.
  • Examples of the chain transfer agent may be 1-dodecanethiol, t-dodecylmercaptan, t-nuxadecylmercaptan, or a combination of two or more thereof.
  • the initiator may include a water-soluble initiator or a fat-soluble initiator, and examples of the water-soluble initiator include potassium persulfate, sodium persulfate, ammonium persulfate, azo- based water-soluble initiators, or two or more kinds thereof.
  • examples of benzoyl peroxide, azobisisobutyronitrile, azobisphenylbutyronitrile and azobiscyclonucleic acid carbonitrile or two or more kinds thereof can be used.
  • curing agent examples are not particularly limited, and for example, 1, 2-ethanediol dimethacrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1, 5- Pentanediol dimethacrylate, 1, 6-nucleic acid diol dimethacrylate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol dimethacrylate, triethylene glycol dimethacryl
  • One or more selected from the group consisting of ethylene glycol, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, and allyl methacrylate can be used.
  • the polymer beads may have a maximum absorbance reduction rate of 1% to 9> before and after heat treatment at a temperature of 200 ° C. to 300 ° C., or 240 ° C. to 300 ° C. represented by Equation 1 below. [Equation 1]
  • the maximum absorbance before and after the heat treatment in Equation 1 after heating the polymer beads at 270 ° C. for 30 minutes, after measuring the absorbance after mixing the polymer beads before and after the heat treatment in the DMS0 solvent, respectively 0.01% content Measurement was carried out using an instrument (UV-Vis Spectroscopy, EVOLUTION 600 from Thermo Fisher Scient if ic).
  • the polymer bead is represented by 200 ° C.
  • the polymer beads contain dyes in the multilayer structure including the core part, the shell layer, and the protective insect, and heat treatment at high temperature. It can be seen that the dye can be stably maintained under the conditions.
  • the polymer beads may have a maximum absorbance reduction rate of 1% to 10% before and after UV irradiation for 40 to 60 hours, which is represented by Equation 2 below.
  • Maximum absorbance reduction rate (%) before and after ultraviolet irradiation [(maximum absorbance of polymer beads before ultraviolet irradiation-maximum absorbance of polymer beads after ultraviolet irradiation) / maximum absorbance of polymer beads before ultraviolet irradiation] X 100
  • the maximum absorbance before and after the ultraviolet irradiation in the equation (2) the polymer beads were injected into the acrylic plate of 1.0T (1 ⁇ ) UV light for 50 hours using a Q-UV tester equipped with a fluorescent lamp After the irradiation, the absorbance before and after ultraviolet irradiation was determined by a method using an absorbance measuring instrument (UV-Vis Spectroscopy, Thermo Fisher Scient if ic EVOLUTION 600).
  • the polymer beads have a lower value of 1% to 10% of the maximum absorbance decrease before and after UV irradiation for 40 to 60 hours represented by Equation (2).
  • the dye can be stably maintained at high energy UV treatment conditions.
  • the polymer beads are used for light diffusing films, light diffusing plates, protective films and construction of liquid crystal monitors, as well as display materials or color plastic materials for display, including color ink films, LCDs and 0LED elements, 3D printing materials. It can be used widely. Meanwhile, another implementation of the invention .
  • a step of polymerizing a first monomer composition containing a vinyl monomer to form a core portion Adding a second monomer composition flame 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 includes A light emitter which emits visible light having a wavelength of 380 nm to 750 nm after a maximum light absorption at a wavelength of less than 400 nm, wherein the surface of the light emitter includes an amide group, an amine group, a thiol group, an ester group, a vinyl group, a hydroxyl group, A method for producing a polymer bead substituted with at least one reactive functional group selected from the group consisting of a phenol group, a (meth) acrylic functional group and a carboxyl
  • core portion Details of the core portion, the shell layer, and the protective layer include those described above in the embodiment.
  • the method of preparing the polymer beads may include at least one of the first monomer composition, the second monomer composition, and the third monomer composition at a maximum light absorption at a wavelength of less than 400 nm, or 200 nm to 390 nm, or 300 nm to 390 nm. Thereafter, the light emitting device may include a light emitter that emits visible light having a wavelength of 380 nm to 750 nm.
  • the light emitter may be included in at least one of the first monomer composition, the second monomer composition, and the ⁇ 3 monomer composition, and specifically, the first monomer composition, the second monomer composition, the third monomer composition, the first monomer composition, and the agent. It may be included in the two monomer composition, the second monomer composition and 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.
  • the light emitter may be included in an amount of 0.1 part by weight to 20 parts by weight, or 1 part by weight to 15 parts by weight, or 5 parts by weight to 15 parts by weight, based on 100 parts by weight of the vinyl monomer.
  • the content of the vinyl monomer refers to the content of all vinyl monomers contained in the monomer composition including the light emitter when preparing the polymer beads.
  • the method for producing a polymer bead comprises the steps of polymerizing a first monomer composition containing a vinyl 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 dance and polymerizing to form a protective layer.
  • the vinyl monomer included in the first monomer composition, the second monomer composition, and the third monomer composition is an aromatic vinyl compound, (meth) acrylic acid having 1 to 20 carbon atoms. It may include at least one compound selected from the group consisting of a compound, 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.
  • aromatic vinyl compound examples are not particularly limited, but for example, styrene or divinyl benzene may be used.
  • Examples of the (meth) acrylic acid ester compound having 1 to 20 carbon atoms are also not particularly limited, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, trimethylolmethane tetra Acrylate, Trimethylolmethane Triacrylate, Trimethylolbutane Triacrylate, ethylene glycol dimethacrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate or two or more kinds thereof can be used.
  • acrylic acid or methacrylic acid fluoroalkyl ester compound having 1 to 20 carbon atoms examples include fluoromethyl (meth) acrylate, fluoroethyl (meth) acrylate, fluorobutyl (meth) acrylate or the like 2 or more types of mixtures are mentioned.
  • the first monomer composition, the second monomer composition, or the third monomer composition may further include 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, and preferably has a low cation content, and may use ultrapure water having a resistance value of 5 ⁇ or more under a nitrogen stream generated through an ion exchanger.
  • 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.
  • 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.
  • the content of the emulsifier and the crosslinking agent may be less than 0.01% by weight. The less than 0. 2% by weight means that the emulsifier and crosslinker content is very fine or not included in the third monomer composition.
  • the content of the emulsifier, crosslinking agent, chain transfer agent, initiator, curing agent may include the above-mentioned details in the embodiment.
  • the weight ratio of the polyfunctional (meth) acrylate compound used as the vinyl monomer and the crosslinking agent in the first monomer composition, the crab di monomer composition, or the third monomer composition is 10: 1 to 100: 1, or 20: 1 to 80: 1, or 40: 1 to 60: 1.
  • the content of the polyfunctional (meth) acrylate compound is excessively increased, there is a concern that the physical properties of the polymer resin obtained by the polymerization of the vinyl monomer may be affected, and a phenomenon may occur between the final polymer beads.
  • the polymerization of the first monomer composition in the step of forming the core portion for example, may be performed for 10 minutes to 200 minutes, or 10 minutes to 80 minutes at a temperature of 50 to 200 ° C.
  • the ratio (conversion) of the vinyl monomer to the polymer may be 90% or more, or 90% to 95%.
  • conversion rate is less than 90%, the thermal stability of the polymer is lowered, and thermal decomposition may occur during processing.
  • the polymerization of the second monomer composition in the step of forming the shellworm may be carried out for 10 minutes to 300 minutes, or 100 minutes to 300 minutes at a temperature of 50 to 20CTC.
  • the ratio (conversion) of the vinyl monomer to the polymer may be 90% or more, or 91% to 95%. When the conversion rate is less than 90%, the thermal stability of the polymer is lowered, and thermal decomposition may occur during processing.
  • the polymerization of the trimeric composition in the step of forming the protective layer may be performed for 10 minutes to 600 minutes, or 100 minutes to 300 minutes at a temperature of 50 to 20CTC.
  • the ratio (conversion) of the vinyl monomer to the polymer may be 90% or more, or 92% to 95%. When the conversion rate is less than 90%, the thermal stability of the polymer is lowered, and thermal decomposition may occur during processing.
  • Examples of the specific polymerization method used in the production method of the polymer beads are not particularly limited, for example, emulsion polymerization, dispersion polymerization, or suspension polymerization may be used, preferably emulsion polymerization may be used.
  • the step of forming the core portion may include a step of forming a crosslinked glass phase, and specifically, in order to control the size of the glass phase emulsion.
  • the crosslinked glass phase is obtained by adding a crosslinking agent and an initiator while lowering the content and controlling the amount of the emulsifier.
  • the second step of forming the shell layer may include a step of grafting the vinyl monomer on the glass polymerized in the first step. Specifically, while using a small amount of vinyl monomer, a crosslinking agent, an emulsifier is added to the initiator By adding, a crosslinked polymer resin phase is prepared. In order to avoid agglomeration of the dendritic particles, the vinyl monomer was slowly added dropwise and the reaction time was long.
  • the third step may include grafting the vinyl monomer on the polymerized phase in the second step.
  • a chain transfer agent can be used to control the molecular weight.
  • the method for preparing the polymer beads is as follows. Under nitrogen stream, ion-exchanged water, emulsifier, crosslinking agent and some monomers with resistance of 1M ⁇ or more are added, and polymerization is performed by adding an initiator when the internal temperature reaches 50-90 ° C. When the polymerization proceeds to form an emulsion, the remaining amount of one-stage monomer is slowly added dropwise to the polymerization. At the end of the polymerization further initiator is added to complete the one-step polymerization /
  • the average particle diameter of the crosslinked glass-like polymer produced here is from 10 to 100 nm, the size of the particles can be controlled by adjusting the amount, type, and stirring speed of the emulsifier, and the size of the obtained particles is very uniform.
  • the stirring of the first monomer composition may proceed for 10 minutes to 60 minutes at a speed of 50rpm to 200rpm, and examples of the specific stirring method are not particularly limited, for example, putting the composition in a reaction vessel , A method of stirring using a mechanical stirrer may be used.
  • the two-stage monomer, the crosslinking agent, the emulsifier, and the like are mixed, and then gradually added dropwise to the solution to carry out the polymerization, and the polymerization is carried out by further adding the initiator in the final stage of polymerization in the same manner as in the first stage.
  • Complete The average thickness of the crosslinked dendritic polymer is about 30 to 300 nm, and the size of the particles is very uniform.
  • Stirring of the second monomer composition may also proceed for 10 minutes to 60 minutes at a rate of 50rpm to 200rpm.
  • step 13 polymerization is carried out using a monomer and an initiator without adding an emulsifier.
  • the initiator is added at the end of step 2, and the monomer is slowly added dropwise to the solution before polymerization. When the polymerization is almost done, finally An initiator is added to complete the polymerization.
  • the average thickness of the final glassy polymer is 10 to 100Onm, or 30 ran to 700 nm, or 50 nm to 500 nm . Degree, and the particle size is very uniform.
  • the innermost core part and the intermediate layer shell layer is a hardened state using a curing agent in 0.5 to 2.5 parts by weight relative to the monomer, and the outermost protective layer is simply grafted or cured to the intermediate layer shell layer as a curing agent compared to the monomer It is manufactured using within 1.0 weight part.
  • filtration, washing and drying may further include a step.
  • the filtration, washing and drying methods can be used without limitation various methods commonly used.
  • a grinding step may be further included, if necessary.
  • the grinding method may include a grinder such as a jet mill, a ball mill atomizer or a hammer mill.
  • the polymer bead of the embodiment; And a binder resin; an optical film may be provided.
  • the polymer beads may maintain the polymer bead property in the binder resin, the shape of the beads may be broken.
  • the polymer beads may exist in a separated phase dispersed in the binder resin through a molding process such as extrusion, pressurization, warming, or the like, or may exist in a contiguous phase combined with the binder resin. Can be.
  • the polymer beads may be dispersed in the binder resin while maintaining the spherical, spherical, and polyhedral bead shapes, as shown in FIG. 5.
  • the emitter included in the beads may realize high heat resistance and durability even in the optical film.
  • the polymer beads disappear in the form of beads, such as spherical, spherical, and polyhedral, and continue with the binder resin. It can exist as a state.
  • the content of the polymer beads includes the content described above in the embodiment.
  • binder resin examples include polyolefin (meth) acrylate, polystyrene, polycarbonate polybutylene terephthalate, polyethylene terephthalate, polyvinyl chloride, and the like. In consideration of the compatibility and solubility in monomers, it is preferable to use poly (meth) acrylates.
  • the weight ratio of the polymer beads and the binder resin is not particularly limited, but may be, for example, 1: 0.5 to 1:10, or 1: 1.2 to 1: 5, or 1: 1.5 to 1: 4.
  • the example of the specific method of manufacturing the said optical film is not limited greatly,
  • molding to a film shape can be used.
  • the molding method may include coating, extrusion, injection, casting molding, and the like, and preferably, a coating method may be used.
  • examples of the coating method may include a method of coating using a Mayer bar on a base film, and various polymer films may be applied as the base film without limitation.
  • the mixture of the polymer beads and the binder resin may further include a curing agent or an organic solvent.
  • curing agent examples are not particularly limited, for example, (2,2'- azo-bis (isobutylonitrile)) (AIBN, 2,2'-azo-bis (isobutyronitrile)) or (2, 2 1 ⁇ azo-bis (2-methylbutylonite ⁇ )) (ABN, 2,2'-azo-bis (2-methylbutyronitrile)) and the like can be used.
  • the organic solvent may be used without any limitation as long as it is known to be used for preparing an optical film.
  • ketones such as methyl ethyl ketone cyclonucleanone
  • Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene
  • Ethylene glycol monoethyl ether ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether
  • Glycol ethers (cellosolves) such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether
  • Acetate esters such as dipropylene glycol monomethyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and carbyl; Aliphatic hydrocarbons such as octane and tecan; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; Amides, such as dimethylacetamide (DMAc) and dimethylformamide (DMF), etc. are mentioned. These solvents can be used alone or as a mixture of two or more thereof.
  • DMAc dimethylacetamide
  • DMF dimethylformamide
  • a polymer bead having a superior durability, heat resistance and light resistance through a nano-sized multilayer structure, and having optical properties having discoloration properties by irradiating light in the ultraviolet region and a manufacturing method thereof may be provided.
  • Figure 1 shows a photograph of the polymer beads prepared in Example 1 measured by a scanning electron microscope (SEM).
  • step 2 of preparing the shell layer a mixed solution of 10.92 kg of methyl methacrylate, 0.57 kg of ethyl acrylate, and 0.57 kg of 21.8% sodium dioctylsulfosuccinate was added dropwise to the reactor at a rate of 0.7 kg per minute, and the protective layer was In 3 steps to manufacture .
  • BL Red-Vinyl (ICB company, terminal vinyl, europium complex system instead of BL Blue 0H (ICB, terminal hydroxyl group, isoquinoline); (l, 10-Phenanthroline) tris Polymer beads were prepared in the same manner as in Example 1, except that [4.4.4 -trif luoro—1 thiolyl-1-l, 2-butane dionato] europium (m) was used.
  • BL Green-0H (ICB company, terminal hydroxyl group, benzothiazol-based) instead of BL Blue 0H (ICB, terminal hydroxyl group, isoquinoline); [2— (benzo [d] thiazol -2-yl) phenol]), except that polymer beads were prepared in the same manner as in Example 1.
  • step 2 of preparing the shell layer polymer beads were prepared in the same manner as in Example 1, except that BL Blue 0H was not added. Comparative Example 2
  • a polymer bead mixture was prepared by mixing the polymer beads 0.95 -kg prepared in Comparative Example 1 and 0.05 kg of BL Blue 0H (ICB, end group hydroxyl group, isoquinoline). Comparative Example 3
  • a polymer bead mixture was prepared by mixing 0.97 kg of the polymer beads prepared in Comparative Example 1 and 0.03 kg of BL Red-Vinyl (the end group vinyl group of ICB, Europium complex).
  • the average diameter was measured using a laser spectroscopy (Laser Spectroscopy, Otsuka Corporation ELSZ), the results are shown in Table 1 below.
  • the average diameter of the core / shell layer / protective layer was measured at each completion point, and the thickness of the core / shell layer / protective layer was obtained, and the scanning electron microscope ( The photo measured by SEM) is shown in Figure 1 below.
  • the difference in heat resistance was measured after heating at 270 ° C. for 30 minutes.
  • the polymer beads before and after the heat treatment were mixed with 0.01% of DMS0 solvent, and then the maximum absorbance and the maximum absorption wavelength were measured using an absorbance measuring instrument (UV-Vis Spectroscopy, Thermo Fisher Scientifi ( ⁇ EVOLUTION 600)). The results are shown in Table 3 below.
  • the maximum absorbance reduction rate before and after the heat treatment was calculated by the following Equation 1.
  • the polymer beads prepared in Examples 1 to 5 had a maximum absorbance reduction rate of less than 10% before and after UV irradiation. As it appears relatively smaller than Comparative Examples 2 and 3, it was confirmed that the light resistance of the dye was improved by containing the dye inside the polymer beads.

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