Matting agent comprising emulsion polymer particles, matting polymer composition comprising the matting agent, and method for producing the same

Abstract

The present invention relates to a matting agent comprising emulsion polymer particles, a matting polymer composition comprising the matting agent, and a method for producing the same, the emulsion polymer particles being producible by a simple process such as emulsion polymerization, and having the advantage of being relatively easy to adjust the crosslinking degree. Furthermore, when a matting polymer composition is produced using a matting agent comprising the emulsion polymer particles, a molded product having excellent matting effect while having a beautiful appearance without lowering the mechanical properties such as impact strength and tensile strength of the existing thermoplastic polymer can be produced, and in particular, an excellent matting effect that has been difficult to achieve in the past in extrusion processing can be achieved.

Description

TECHNICAL FIELD

[0001] The present invention relates to a matting agent comprising emulsion polymer particles, a matting polymer composition comprising the same, and a method for manufacturing the same. BACKGROUND

[0002] With the popularization of electric vehicles, the lightening problem of the automobile industry becomes more important, and various efforts are attempted for this purpose. Representatively, there are attempts to replace the metal material of the vehicle body with a lightweight high-strength engineering plastic, or to remove the metal material by fixing the portion joined by the combination of the existing bolt nut with an adhesive, etc.

[0003] In addition, in terms of expressing various color and texture in the interior / exterior materials of the vehicle, there is a tendency that the preference for products having a texture with low gloss or no gloss is increasing due to the lightening problem, the environmental problem, the driver's driving problem caused by the light reflection of the coated surface, and the sophistication of interior decoration, etc.

[0004] As a method for reducing gloss, resin can be injection molded into a corrosion surface mold, but it cannot show sufficient matting effect, or inorganic fillers can be added, but an excessive amount must be used to exert sufficient matting effect, and the mechanical strength is weakened when used in excess, so its use is very limited.

[0005] In US Patent Publication US5580924A, in order to reduce the gloss of PC, a styrene-acrylonitrile copolymer is synthesized, mixed with 3,4-epoxycyclohexyl-3,4-epoxycyclohexyl carboxylate, and manufactured into a cross-linked SAN by a reaction extruder, but the above prior art has limitations in manufacturing a molded product of excellent quality, for example, surface foreign matter such as black spots is generated during reaction extrusion, it is difficult to improve the color, it is difficult to adjust the cross-linking point, it is not dissolved during processing, appearance defects are generated, etc.

[0006] Therefore, there is an urgent need to develop a matting additive that has excellent matting effect, does not have a decrease in mechanical properties, and can exhibit an appearance of excellent quality. SUMMARY

[0007] In order to solve the problems of the prior art as described above, the present invention aims to provide a matting agent comprising a novel emulsion polymer particle and a method for manufacturing the same.

[0008] Another object of the present invention is to provide a matting polymer composition comprising a specific matting agent as described above, and to provide a molded product having excellent matting effect, mechanical properties, and an appearance of excellent quality by extrusion or injection molding processing of the above composition.

[0009] The inventors of the present invention have manufactured emulsion polymer particles from a polymerizable composition containing an aromatic vinyl compound, an unsaturated nitrile compound, and an alicyclic epoxy compound by an emulsion polymerization method that has not been attempted before, in order to solve the above problems. The above emulsion polymer particles can be adjusted in crosslinking degree with relative ease, and when a matting agent and a matting polymer composition containing the same are used, surprisingly, it has been found that a molded product having excellent appearance quality that exhibits an excellent matting effect with only a small amount of addition while not causing a decrease in the physical properties of a conventional thermoplastic polymer can be manufactured, thereby completing the present invention.

[0010] The present invention provides an emulsion polymer particle manufactured from a polymerizable composition containing an aromatic vinyl compound, an unsaturated nitrile compound, and an alicyclic epoxy compound, the epoxy group of the alicyclic epoxy compound being ring-opened.

[0011] According to an embodiment of the present invention, the alicyclic epoxy compound can have two or more epoxy groups, and the alicyclic epoxy compound can be one or more selected from the group consisting of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate, diethylene glycol bis(3,4-epoxycyclohexane-carboxylate), 2-ethyl-1,3-hexanediol bis(3,4-epoxycyclohexane-carboxylate), diethylene glycol bis(3,4-epoxy-6-methylcyclohexane-carboxylate), 3-methyl-1,5-pentanediol bis(3,4-epoxycyclohexane-carboxylate), 1,5-pentanediol bis(3,4-epoxycyclohexane-carboxylate), ethylene glycol bis(3,4-epoxycyclohexane-carboxylate), ethylene glycol bis(3,4-epoxy-6-methylcyclohexane-carboxylate), bis(3,4-epoxycyclohexylmethyl)oxalate, bis(3,4-epoxycyclohexylmethyl)succinate, bis(3,4-epoxycyclohexylmethyl)adipate, and 1,2,8,9-diepoxy limonene.

[0012] According to an embodiment of the present invention, the polymerizable composition can be manufactured to contain 20 to 45 parts by weight of the unsaturated nitrile compound and 3 to 25 parts by weight of the alicyclic epoxy compound, with respect to 100 parts by weight of the aromatic vinyl compound.

[0013] According to an embodiment of the present invention, the polymerizable composition can further contain one or more acid compounds selected from the group consisting of R1COOH, R2SO3H, and salts thereof, wherein R1and R2are each independently C 6-30 alkyl, C 6-30 aryl, or C 6-30 aryl C 6-30 alkyl.

[0014] According to an embodiment of the present application, the above-mentioned polymerizable composition can contain 0.05 to 1 parts by weight of the above-mentioned acid compound per 100 parts by weight of the aromatic vinyl compound.

[0015] According to an embodiment of the present application, the above-mentioned polymerizable composition can be mixed with water to form a dispersed phase, and the above-mentioned acid compound can be located at the interface between the dispersed phase and an aqueous phase, so that the above-mentioned polymerizable composition is polymerized.

[0016] According to an embodiment of the present application, the surface of the above-mentioned emulsion polymer particle can be negatively charged.

[0017] According to an embodiment of the present application, the average particle diameter of the above-mentioned emulsion polymer particle can be 90 to 250 nm.

[0018] The present application can provide an optical extinction agent containing the above-mentioned emulsion polymer particle.

[0019] The present application can provide a master batch scrap containing the above-mentioned optical extinction agent.

[0020] The present application can provide an optical extinction polymer composition containing the above-mentioned optical extinction agent and a thermoplastic polymer.

[0021] According to an embodiment of the present application, the above-mentioned thermoplastic polymer can be one or more selected from the group consisting of polypropylene (PP), polyacrylate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamide, styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylate (ASA), and a mixture thereof.

[0022] The present application can provide a molded product manufactured by extruding or injection molding the above-mentioned optical extinction polymer composition.

[0023] The present application can provide a method of manufacturing an emulsion polymer particle, including the steps of: manufacturing a core layer by emulsion polymerization of a first polymerizable composition containing an aromatic vinyl compound and an alicyclic epoxy compound; and manufacturing a shell layer by emulsion polymerization of a second polymerizable composition containing an aromatic vinyl compound, an unsaturated nitrile compound, and an alicyclic epoxy compound in the presence of the above-mentioned core layer.

[0024] According to an embodiment of the present application, the above-mentioned first polymerizable composition can contain 1 to 20 parts by weight of the alicyclic epoxy compound per 100 parts by weight of the aromatic vinyl compound, and the above-mentioned second polymerizable composition can contain 2 to 18 parts by weight of the alicyclic epoxy compound per 100 parts by weight of the sum of the aromatic vinyl compound and the unsaturated nitrile compound.

[0025] According to an embodiment of the present application, the step of manufacturing the core layer can include the steps of:

[0026] (a) a step of adding the first polymerizable composition, deionized water, an emulsifier, and an acid compound in a reactor and stirring, thereby manufacturing a pre-emulsion; and

[0027] (b) a step of adding a water-soluble initiator, initiating a reaction, and performing emulsion polymerization.

[0028] According to an embodiment of the present application, the acid compound can be any one or a combination of two or more selected from R1COOH, R2SO3H, and salts thereof, wherein R1and R2are each independently C 6-30 alkyl, C 6-30 aryl, or C 6-30 aryl C 6-30 alkyl.

[0029] According to an embodiment of the present application, the step of manufacturing the shell layer can include the step of adding the second polymerizable composition dropwise in the presence of the core layer, performing emulsion polymerization, thereby manufacturing an emulsion polymer particle dispersion.

[0030] According to an embodiment of the present application, the emulsion polymer particle can include 5 to 60 wt% of the core layer and 40 to 95 wt% of the shell layer.

[0031] According to an embodiment of the present application, the solid content of the emulsion polymer particle dispersion can be 20 to 45 wt%.

[0032] The emulsion polymer particle according to the present application can be manufactured through a simple process such as an emulsion polymerization method, and has the advantage of being relatively easy to adjust the crosslinking degree. In addition, when a matting agent including the emulsion polymer particle is used to manufacture a matting polymer composition, the matting effect can be effectively exhibited without reducing other physical properties, and thus is preferred.

[0033] In addition, when the matting polymer composition is used, a molded product having a beautiful appearance while having excellent matting effect without reducing the mechanical properties such as impact strength and tensile strength of the existing thermoplastic polymer can be manufactured, and in particular, an excellent matting effect that has been difficult to achieve in the past in extrusion processing can be exhibited, and thus is very preferred.

[0034] The matting agent according to the present application and the matting polymer composition including the same can be applied to various product groups such as interior / exterior materials for automobiles, interior decoration, and household electrical products. DETAILED DESCRIPTION

[0035] Hereinafter, the present application will be described in more detail by way of specific examples or embodiments. However, the following specific examples or embodiments are only for a reference to describe the present application in detail, and the present application is not limited thereto, and can be implemented in various forms.

[0036] In addition, unless otherwise defined, all technical and scientific terms used have the same meaning as would be understood by one of ordinary skill in the art to which this application belongs. The terminology used in the present application is only for effectively describing specific examples, and is not intended to limit the present application.

[0037] In addition, the singular forms used in the specification and the appended claims, unless otherwise indicated, are also intended to include the plural forms.

[0038] In addition, when a certain part is said to "include" a certain component, unless otherwise specifically stated, it means that other components can be further included, rather than excluding other components.

[0039] The term "matting property" of the present specification means a property of reducing gloss by a difference in shrinkage and refractive index between polymers in the incompatible polymer composition and between the polymers and the additive, or surface processing, using a diffuse reflection effect.

[0040] The term "dispersed phase" of the present specification means a discontinuous phase distributed throughout a dispersion medium, and specifically, can mean a discontinuous phase in which a polymerizable composition is distributed in the form of droplets with water as a medium.

[0041] The term "pre-emulsion" of the present specification means a stable state composition in which a polymerizable composition, an emulsifier, and a solvent (deionized water) are uniformly mixed.

[0042] The term "emulsion" of the present specification means a dispersion liquid in which one of two liquids that are not compatible with each other is dispersed in the other in the form of small particles.

[0043] Hereinafter, preferred embodiments and physical property measurement methods of a matting agent including an emulsion polymer particle of the present application, a matting polymer composition including the matting agent, and a method for manufacturing the same will be described in detail.

[0044] The present application can be better understood by the following examples, which are provided for the purpose of illustration of the present application, and are not intended to limit the scope of protection defined by the appended claims.

[0045] Hereinafter, an embodiment of the present application will be described in more detail.

[0046] The present application provides an emulsion polymer particle produced from a polymerizable composition containing an aromatic vinyl compound, an unsaturated nitrile compound, and an alicyclic epoxy compound, the alicyclic epoxy compound having an open ring.

[0047] The alicyclic epoxy compound contained in the emulsion polymer particle can have an open ring, and specifically, the open ring can be opened by reaction with other compounds contained in the polymerizable composition. More specifically, the alicyclic epoxy compound can be chemically bound to the polymer and contained in the emulsion polymer particle, but is not necessarily limited thereto.

[0048] According to an embodiment of the present application, as a non-limiting example, the aromatic vinyl compound can be one or more selected from the group consisting of styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, t-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinyl naphthalene, and styrene can be preferably used.

[0049] As a non-limiting example, the unsaturated nitrile compound can be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethylacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, and acrylonitrile can be preferably used.

[0050] The alicyclic epoxy compound can preferably have two or more epoxy groups, and specifically, the alicyclic epoxy compound can be one or more selected from the group consisting of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate, diethylene glycol bis(3,4-epoxycyclohexane-carboxylate), 2-ethyl-1,3-hexanediol bis(3,4-epoxycyclohexane-carboxylate), diethylene glycol bis(3,4-epoxy-6-methylcyclohexane-carboxylate), 3-methyl-1,5-pentanediol bis(3,4-epoxycyclohexane-carboxylate), 1,5-pentanediol bis(3,4-epoxycyclohexane-carboxylate), ethylene glycol bis(3,4-epoxycyclohexane-carboxylate), ethylene glycol bis(3,4-epoxy-6-methylcyclohexane-carboxylate), bis(3,4-epoxycyclohexylmethyl)oxalate, bis(3,4-epoxycyclohexylmethyl)succinate, bis(3,4-epoxycyclohexylmethyl)adipate, and 1,2,8,9-diepoxy limonene, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate can be preferably used. As commercially available products, CEL-2021, CEL-3000, and CEL-2081 of Daicel Chemical Industries, Ltd. can be used.

[0051] According to an embodiment of the present application, the above-mentioned polymerizable composition can contain 1 to 90 parts by weight, preferably 10 to 70 parts by weight, and more preferably 20 to 45 parts by weight of the unsaturated nitrile compound, and can contain 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, and more preferably 3 to 25 parts by weight of the alicyclic epoxy compound, with respect to 100 parts by weight of the aromatic vinyl compound. When the above-mentioned ranges are satisfied, the reaction stability can be maintained, and emulsion polymer particles having the object properties of the present application can be produced, and thus it is preferred, and even if a small amount of the matting agent containing the same is added, the matting effect can be effectively exerted, and thus it is more preferred.

[0052] According to an embodiment of the present application, the above-mentioned polymerizable composition can further contain an acid compound selected from any one or two or more of R1COOH, R2SO3H, and a salt compound thereof, and the above-mentioned R1and R2may each independently be C 6-30 alkyl, C 6-30 aryl, or C 6-30 aryl C 6-30 alkyl, and in addition, the salt compound of the above-mentioned acid compound can be represented by R1COOM and R2SO3M, the above-mentioned R1and R2are the same as described above, and M can be a cation. The above-mentioned M can be an alkali metal cation or an ammonium cation, and as non-limiting examples, M can be one or more selected from sodium ion, potassium ion, and lithium ion, but is not limited thereto.

[0053] It is preferred that the above-mentioned acid compound be R2SO3H, and the above-mentioned R2may be C 6-12 aryl C 6-18 alkyl, and as one example, can be selected from butylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, and pentadecylbenzenesulfonic acid, but is not limited thereto. The above-mentioned acid compound can be contained in an amount of 0.005 to 5 parts by weight, and preferably 0.05 to 1 part by weight, with respect to 100 parts by weight of the aromatic vinyl compound of the above-mentioned polymerizable composition.

[0054] Specifically, the above-mentioned polymerizable composition can be mixed with water (medium) to form a dispersed phase, and the above-mentioned acid compound or the salt compound thereof can be located at the interface between the dispersed phase and the aqueous phase, so that the above-mentioned polymerizable composition is polymerized. The specific description is the same as described in the method of producing the emulsion polymer particles described below. When emulsion polymerization is performed by further adding the above-mentioned acid compound to the above-mentioned polymerizable composition, the reaction rate can be effectively increased, and emulsion polymer particles in which a strong crosslinked network is formed can be produced, and thus it is very preferred.

[0055] In addition, the emulsion polymer particles described above can include a divalent -SO3- or -CO3- substituent, and specifically, can include a -SO3- substituent. The divalent substituent described above can be formed by the reaction of an acid compound and an alicyclic epoxy compound included in the polymerizable composition, and the divalent substituent can each be bound to a hydrocarbon group. The divalent substituent described above can be included by being bound to a high molecular chain. In addition, the divalent substituent described above can exist mainly on the surface of the emulsion polymer particles, and can have a concentration gradient in which the concentration of the divalent substituent decreases from the surface of the emulsion polymer particles toward the inside of the particles. The concentration gradient described above can be derived from the emulsion polymerization mechanism. Specifically, because the acid compound is located at the interface of the dispersed phase, the divalent substituent described above can exist at a high concentration on the surface of the emulsion polymer particles through the reaction of the acid compound and the alicyclic epoxy compound located at the interface at the interface. The average particle diameter of the emulsion polymer particles having the structure described above can be uniform, and can exert an excellent matting effect, and thus is more preferred.

[0056] According to an embodiment of the present application, the surface of the emulsion polymer particles described above can be negatively charged. The emulsion polymer particles described above are manufactured through emulsion polymerization, and by using an emulsifier, the dispersibility of the polymerizable composition and the particles present in the medium and the stability of the emulsion polymerization reaction, etc. can be improved. For example, the emulsifier described above can be an anionic emulsifier, which can cause the surface of the manufactured emulsion polymer to be negatively charged. When the surface charge of the particles described above is a negative charge, the dispersion stability of the micelles can be further improved, and thus is preferred.

[0057] According to an embodiment of the present application, the average particle diameter of the emulsion polymer particles described above can mean D50, and the D50 refers to the particle diameter at which the cumulative volume is 50% from the small particle diameter in the particle size distribution measurement using a laser scattering method. Here, the D50 can be obtained by collecting particles according to the KSA ISO 13320-1 standard and measuring the particle size distribution of the emulsion polymer particles using the Mastersizer 3000 of Malvern. Specifically, it can be measured by using water as a dispersion medium, and if necessary, using an ultrasonic disperser, and measuring the volume density (Volume density) after dispersion, but the present application is not limited thereto, and in order to measure the average particle diameter, a conventionally used or well-known method can be used.

[0058] The emulsion polymer particles according to an embodiment of the present application are manufactured by emulsion polymerization, and the emulsion polymer particles in which the particles dispersed in the emulsion phase of the medium (water) after the emulsion polymerization reaction is finished are defined as first emulsion polymer particles, and the particles in the coagulation state after the coagulation step is defined as second emulsion polymer particles. Hereinafter, the emulsion polymer particles can mean the first emulsion polymer particles unless otherwise specified, and can include both the first emulsion polymer particles and the second emulsion polymer particles according to circumstances.

[0059] The average particle diameter of the first emulsion polymer particles described above can be 50 to 1000 nm, preferably 70 to 500 nm, and more preferably 90 to 250 nm. When the emulsion polymer particles having the average particle diameter in the above range are used, an excellent matting effect can be exhibited without reducing other physical properties by a small amount of addition, and thus is preferred. In addition, the average particle diameter of the second emulsion polymer particles can be 1 to 3000 μm, 10 to 2500 μm, or 50 to 2000 μm, but is not limited thereto.

[0060] The particle size distribution of the first emulsion polymer particles described above can be 1 to 5, and specifically, can be 1 to 3, but is not limited thereto. The particle size distribution of the emulsion polymer particles satisfying the above range can be uniform, which can improve the matting effect and the appearance quality, and thus is preferred. The particle size distribution (SPAN) described above is measured using a light diffraction particle size analyzer (Malvern Mastersizer 3000), and the particle size distribution (SPAN) value represented by the following Equation 1 is obtained.

[0061] [Equation 1] Particle size distribution (SPAN) = (Dv90 - Dv10) / Dv50

[0062] In Equation 1, Dv50 represents the medium particle size of the polymer generated by polymerization, Dv90 represents the particle size corresponding to the first 90% (90% from the small particle size to the large particle size) in the polymer generated by polymerization, and Dv10 represents the particle size corresponding to the first 10% (10% from the small particle size to the large particle size) in the polymer generated by polymerization.

[0063] The present application can provide a matting agent including the emulsion polymer particles described above. The first emulsion polymer particles manufactured by emulsion polymerization are subjected to the steps of coagulation, dehydration, and drying, and thus the second emulsion polymer particles in the form of powder can be obtained, and can include the same used as a matting agent.

[0064] The present application can provide a master batch chip comprising the above-mentioned matting agent. The above-mentioned master batch chip can comprise a thermoplastic polymer and a matting agent, and further, can comprise one or more than two additives selected from the group consisting of an antioxidant, a UV absorber, a UV stabilizer, a lubricant, and a mixture thereof. The above-mentioned additives can be used without limitation as long as they are generally used or known. The above-mentioned matting agent can be contained in an amount of 0.1 to 50 wt%, and preferably 5 to 30 wt% based on the total weight of the master batch chip. When the master batch chip is used in the above-mentioned range, the dispersibility and uniformity of the matting agent and the additives are improved, so that a high-quality product (a molded product) can be manufactured, and thus, it is preferred.

[0065] The present application can provide a matting thermoplastic polymer composition comprising the above-mentioned matting agent and a thermoplastic polymer. The above-mentioned matting agent can effectively exhibit matting properties without lowering the properties of the existing thermoplastic polymer by being added in a small amount, has a dense crosslinking degree and a uniform particle size distribution, and thus, has excellent dispersibility with the above-mentioned thermoplastic polymer. Accordingly, the problems of the prior art can be solved, and the above-mentioned matting thermoplastic polymer composition can be extruded and injection-molded, so that a low-gloss or no-gloss product having excellent mechanical strength can be manufactured.

[0066] According to an embodiment of the present application, the above-mentioned thermoplastic polymer can be one or more selected from the group consisting of polypropylene (PP), polyacrylate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamide, styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylate (ASA), and a mixture thereof, and specifically, a mixture of PC and SAN, a mixture of PC and ABS, or a mixture of PC and ASA can be used, but is not limited thereto.

[0067] According to an embodiment of the present application, the above-mentioned matting thermoplastic polymer composition can comprise the above-mentioned matting agent in an amount of 0.1 to 30 wt% and the above-mentioned thermoplastic polymer in an amount of 70 to 99.9 wt%, but is not limited thereto, and the amount of the matting agent can be adjusted according to the surface gloss of a product to be manufactured.

[0068] According to an embodiment of the present application, the above-mentioned matting thermoplastic polymer composition can further comprise additives generally used in the technical field. For example, an antioxidant, a UV absorber, a UV stabilizer, a lubricant, or the like can be further included. At this time, the above-mentioned additives can be included in an appropriate amount without lowering the object properties of the present application.

[0069] According to an embodiment of the present application, the above matting agent, which is manufactured in the form of a master batch scrap containing a thermoplastic polymer, can be mixed again with a thermoplastic polymer, and the above master batch scrap can further contain an additive. The above master batch scrap can be contained in an amount of 0.1 to 50 wt%, preferably 1 to 30 wt%, based on the total weight of the above matting polymer composition, and the amount of the above master batch scrap can be adjusted to determine the content of the matting agent in the finally manufactured product.

[0070] The present application can provide a molded product manufactured by extruding or injection-molding the above matting polymer composition. In the past, it has been very difficult to manufacture a molded product having an excellent matting effect in an extrusion process, but when the matting polymer composition containing the emulsion polymer particles according to the present application is used, not only can the appearance defects caused by the protrusion of the particles during the extrusion process be effectively suppressed, but also a molded product having an excellent matting effect and an excellent appearance quality can be manufactured without lowering the mechanical properties of the existing polymer, and thus is very preferable.

[0071] Hereinafter, the method for manufacturing the emulsion polymer particles according to the present application will be described in detail.

[0072] The present application can provide a method for manufacturing emulsion polymer particles, including the steps of: manufacturing a core layer by emulsion polymerization of a first polymerizable composition containing an aromatic vinyl compound and an alicyclic epoxy compound; and manufacturing a shell layer by emulsion polymerization of a second polymerizable composition containing an aromatic vinyl compound, an unsaturated nitrile compound, and an alicyclic epoxy compound in the presence of the above core layer.

[0073] According to an embodiment of the present application, the above first polymerizable composition can contain an alicyclic epoxy compound in an amount of 1 to 30 parts by weight, preferably 1 to 25 parts by weight, and more preferably 1 to 20 parts by weight, based on 100 parts by weight of the aromatic vinyl compound. The above first polymerizable composition can further contain an unsaturated nitrile compound, but is not limited thereto, and can contain 5 to 70 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the aromatic vinyl compound. When the above first polymerizable composition further contains an unsaturated nitrile compound, the matting effect and the mechanical properties such as impact strength or tensile strength can be improved during the extrusion process, and thus is preferable.

[0074] According to an embodiment of the present application, the second polymerizable composition can contain 5 to 80 parts by weight of the unsaturated nitrile compound, preferably 10 to 70 parts by weight, more preferably 20 to 60 parts by weight, with respect to 100 parts by weight of the aromatic vinyl compound, and 0.5 to 50 parts by weight of the alicyclic epoxy compound, preferably 1 to 25 parts by weight, more preferably 2 to 18 parts by weight, with respect to 100 parts by weight of the total of the aromatic vinyl compound and the unsaturated nitrile compound. When the above ranges are satisfied, the reaction stability can be maintained, and a dense crosslinking network can be formed in the core layer and the inside of the shell layer and between the layers, and thus the above ranges are preferred.

[0075] In addition, the first and second polymerizable compositions can further contain a crosslinking agent. The crosslinking agent can be used without limitation as long as it has two or more crosslinkable functional groups, and as non-limiting examples, 1,2-ethanediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutanediol di(meth)acrylate, allyl (meth)acrylate, divinylbenzene, trivinylbenzene, and trialkyl isocyanurate, or the like can be used. The crosslinking agent can be used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 3 parts by weight, with respect to 100 parts by weight of the aromatic vinyl compound, but is not limited thereto.

[0076] In addition, the first and second polymerizable compositions can further contain a molecular weight adjusting agent for adjusting the molecular weight. The molecular weight adjusting agent can be used in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, with respect to 100 parts by weight of the aromatic vinyl compound, but is not limited thereto, and n-dodecyl mercaptan, n-pentyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-nonyl mercaptan, or the like can be used.

[0077] According to an embodiment of the present application, the step of manufacturing the core layer can include the steps of (a) adding the first polymerizable composition, deionized water, an emulsifier, and an acid compound to a reactor and stirring to thereby manufacture a pre-emulsion; and (b) introducing a water-soluble initiator, initiating a reaction, and performing emulsion polymerization.

[0078] Specifically, the above-mentioned (a) step is a step of preparing a pre-emulsion by stirring the first polymerizable composition, deionized water, an emulsifier, and an acid compound at room temperature, and emulsification can be performed for a sufficient time and stirring speed. The better the emulsification state of the above-mentioned pre-emulsion, the better the reaction stability. Therefore, the time and stirring speed are not substantially limited, and as an example, when the reactor size is 2 L, it is preferable to maintain the stirring speed at 200 rpm or more for 10 minutes or more. At this time, a commonly used or well-known emulsifying aid, a buffer (pH adjuster), a molecular weight adjuster, or the like can also be included.

[0079] In the above-mentioned (a) step, the above-mentioned first polymerizable composition forms a dispersed phase in a medium of deionized water (an aqueous phase), and stirring can be performed sufficiently so that the droplets of the dispersed phase can be small and uniformly dispersed. In addition, the above-mentioned emulsifier and acid compound can be located at the interface between the aqueous phase and the dispersed phase, and the polymerization of the above-mentioned polymerizable composition can be completed at the interface.

[0080] The above-mentioned (b) step is a step of raising the temperature inside the reactor to 50 to 70°C and then adding a water-soluble initiator to initiate the reaction. As the reaction proceeds, exothermic heat can occur, and it is preferable to use a cooler to stably maintain the reactor temperature at 65 to 75°C. The reaction time can be 10 to 200 minutes, and the above-mentioned (b) step can further include a further polymerization step, which can be further polymerization at a temperature of 60 to 75°C for 30 to 120 minutes, but is not limited thereto. Through the above-mentioned (a) and (b) steps, a core layer of emulsion polymer particles can be manufactured, and the polymerization conversion rate can be 70 to 99% at this time.

[0081] Next, the above-mentioned shell layer can be manufactured by the following steps: a step of slowly dropping the above-mentioned second polymerizable composition in the presence of the above-mentioned core layer and performing emulsion polymerization to thereby manufacture an emulsion polymer particle dispersion liquid. Specifically, the above-mentioned second polymerizable composition can be dropped at a constant flow rate into the above-mentioned core layer for 30 minutes to 5 hours, and it is preferable to stably maintain the reaction temperature at 60 to 80°C. In addition, the above-mentioned second polymerizable composition can further include an emulsifying aid, a buffer (pH adjuster), a molecular weight adjuster, or the like. After the reaction is completed, a step of cooling to 40°C or less can also be included. Through the above-mentioned steps, a dispersion liquid in which first emulsion polymer particles including a core layer and a shell layer are dispersed can be obtained, the final polymerization conversion rate is 95 to 99.9%, and the above-mentioned dispersion liquid can include 20 to 45 wt% of the first emulsion polymer particles. In addition, the above-mentioned first emulsion polymer particles can include 5 to 60 wt% of the core layer and 40 to 95 wt% of the shell layer. The specific description of the above-mentioned manufactured first emulsion polymer particles is the same as described above.

[0082] Further, the dispersion liquid containing the above first emulsion polymer particles can be further subjected to a coagulation step. In the coagulation step, the above first emulsion polymer particles are coagulated using an acid solution or a salt solution to separate from the medium (water), and after the particle surface is solidified (cured) by raising the temperature, the particles are subjected to a dehydration and drying process, thereby obtaining second emulsion polymer particles in the form of white powder having a water content of 0.5 wt% or less. At this time, as the coagulant, a publicly known or generally used coagulant can be used, and as an example, sulfuric acid, phosphoric acid, magnesium sulfate, or the like can be used. The specific description of the above produced second emulsion polymer particles is the same as that described above.

[0083] According to an embodiment of the present application, the above emulsifier reduces the interfacial energy between the above dispersed phase of the polymerizable composition and the aqueous phase of the deionized water, and thus a more uniform dispersed phase is maintained, so that stable emulsion polymerization can be performed. The above emulsifier can be one or more selected from cationic, anionic, and nonionic surfactants, and as non-limiting examples, cationic surfactants such as octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, didodecyldimethylammonium hydroxide, dioctadecyl dimethylammonium hydroxide, and the like can be used alone or in combination; alkali metal soaps of higher fatty acids, alkyl aryl sulfonates such as sodium dodecylbenzenesulfonate, potassium abietate, potassium fatty acid, potassium alkenyl dicarboxylate, sodium laurylsulfate, sodium dodecylsulfate, sodium lauryl ether sulfate sodium dodecylbenzenesulfate, alkyl sulfates, alkyl ether sulfates , alkyl phenyl ether sulfates alkylbenzenesulfonates, alkyl sulfonates, and dialkyl sulfosuccinates, and the like anionic surfactants; and condensates of ethylene oxide with long-chain fatty alcohols or C 12-16 alcohols, condensates of ethylene oxide with amines or amides, condensation products of ethylene with propylene oxide, glycerol, sucrose, sorbitol, fatty acid alkylol amides, sucrose esters, oxidized fatty amines, polyoxyalkylene sorbitan esters, ethylene glycol-propylene glycol copolymers, alkyl polysaccharides, polyvinyl alcohol (PVA), polyvinyl methyl ether, and the like nonionic surfactants. Preferably, potassium abietate and dodecylbenzenesulfonic acid are used, and can be contained in an amount of 0.1 to 5 parts by weight, preferably 1 to 3 parts by weight, with respect to 100 parts by weight of the above polymerizable composition, but are not limited thereto.

[0084] According to an embodiment of the present application, the above acid compound is any one or a combination of two or more selected from R1COOH, R2SO3H, and salts thereof, and the above R1and R2, each independently, can be C6-30 alkyl, C 6-30 aryl, or C 6-30 aryl C 6-30 alkyl, the description of the above acid compound and the example of the specific compound are the same as those described above.

[0085] In addition, in the above first polymerizable composition, the weight ratio of the above alicyclic epoxy compound and the above acid compound can be 1:0.005 to 0.5, preferably 1:0.01 to 0.2. When the above range is satisfied, the reaction stability can be maintained, the emulsion polymer particle can be manufactured to have uniform particle diameter and particle size distribution, and thus it is preferred that, when the matting agent containing the above emulsion polymer particle is used, a molded product having improved matting effect and appearance quality can be manufactured by adding a small amount, without a decrease in mechanical properties.

[0086] According to an embodiment of the present application, the above water-soluble initiator can be used without particular limitation as long as it is an initiator generally used for emulsion polymerization or a well-known compound, and as non-limiting examples, peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate can be used. With respect to 100 parts by weight of the above polymerizable composition, 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight, can be contained, but it is not limited thereto.

[0087] Hereinafter, the present application will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are only an example for describing the present application in more detail, and the present application is not limited to the following examples and comparative examples.

[0088] [Physical property measurement method]

[0089] 1) Average particle diameter: Measured using a particle size analyzer (Malvern Mastersizer 3000).

[0090] 2) Surface gloss (GLOSS): Measured according to AS T M D523 at 60° and 85°.

[0091] 3) IZOD impact strength (Noched IZOD Impact strength): Impact strength was measured according to ASTM D256 at 1 / 4" and 1 / 8".

[0092] 4) Tensile strength: Tensile strength was measured according to ASTM D638.

[0093] 5) Yellow Index (YI): A 3.2 mm-thick injection-molded product was produced, and the yellow index was measured in accordance with ASTM D1925.

[0094] [Example 1] Production of emulsion polymer particles

[0095] (A) Core layer production step

[0096] Styrene 23 g, acrylonitrile 9 g, 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexyl carboxylate (CEL-2021, Dicel Chemical) 3 g, and dodecylbenzenesulfonic acid (95 wt%, Mikuni Chemical) 0.35 g were put into a reactor, and stirring was performed. Then, after further putting deionized water 200 g and potassium abietate 2.0 g, stirring was performed at a stirring speed of 200 rpm or more for 30 minutes or more. After confirming that the composition in the reactor became a milky white pre-emulsion state, the temperature was raised to 60°C. Potassium persulfate 0.15 g was put into the reactor, and the reaction was initiated, and then, the exothermic reaction was adjusted, and the temperature inside the reactor was maintained at 70°C, and emulsion polymerization was performed for 2 hours, whereby the core layer of the emulsion polymer particles was produced. (Polymerization conversion rate 97%)

[0097] (B) Shell layer production step

[0098] After the above (A) step, a composition in which styrene 43 g, acrylonitrile 16 g, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate 6 g were mixed was continuously dropped into the reactor at an internal temperature of 70°C for 2 hours, and then, the exothermic reaction was adjusted, and the temperature was maintained at 70°C, and emulsion polymerization was performed for 2 hours. After the reaction was completed, the temperature inside the reactor was cooled to 40°C or less, and a dispersion liquid (emulsion) containing the emulsion polymer particles was obtained. (Polymerization conversion rate 98%, solid content 33%)

[0099] After the above emulsion was coagulated using magnesium sulfate, the washing, dewatering, and drying steps were performed, and finally, the emulsion polymer particles described in Example 1 were obtained in the form of a white powder. The average particle diameter of the above emulsion polymer particles was measured to be 195 nm.

[0100] [Example 2]

[0101] In the above (A) step of Example 1, styrene 32 g was put in without putting acrylonitrile, and otherwise, the same method as Example 1 was performed. The average particle diameter of the above emulsion polymer particles was measured to be 160 nm.

[0102] [Example 3]

[0103] In the above (A) step of Example 1, styrene 24 g and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate 2 g were charged, and in the above (B) step, styrene 44 g, acrylonitrile 17 g and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate 4 g were charged, and otherwise, the same method as Example 1 was performed. The average particle diameter of the emulsion polymer particles was measured as 180 nm.

[0104] [Example 4]

[0105] In the above (A) step of Example 1, acrylonitrile 8 g and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate 4 g were charged, and in the above (B) step, styrene 42 g, acrylonitrile 15 g and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate 8 g were charged, and otherwise, the same method as Example 1 was performed. The average particle diameter of the emulsion polymer particles was measured as 215 nm.

[0106] [Example 5]

[0107] In the above (A) step of Example 1, styrene was charged while divinylbenzene 0.1 g was additionally charged, and in the above (B) step, styrene was charged while divinylbenzene 0.3 g was additionally charged, and otherwise, the same method as Example 1 was performed. The average particle diameter of the emulsion polymer particles was measured as 140 nm.

[0108] [Comparative Example 1]

[0109] In the above (A) step of Example 1, no dodecylbenzenesulfonic acid was charged, and divinylbenzene 3 g was charged instead of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate, and in the above (B) step, divinylbenzene 6 g was charged instead of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate, and otherwise, the same method as Example 1 was performed, and the polymerization conversion rate of the obtained emulsion was 97%, and the solid content was 36%. The subsequent processes were also performed by the same method as Example 1. The average particle diameter of the emulsion polymer particles was measured as 118 nm.

[0110] - Manufacture of injection-molded products and extruded sheets

[0111] [Examples 6 to 10 and Comparative Examples 2 to 4]

[0112] After mixing PC (3020PJ) 65.5 wt%, ABS (IM-601) 11.4 wt%, SAN (92HR) 18 wt% and antioxidant 0.3 wt% with the emulsion polymer particles 4.7 wt% described in Examples 1 to 5 and Comparative Example 1 described above, particles of the matting polymer composition were obtained by an extruder, and the particles were dried, and a sample having a width, length and thickness of 70 mm x 75 mm x 3.0 mm was manufactured using an injection molding machine, and a sheet-shaped sample having a width, length and thickness of 100 mm x 75 mm x 2.0 mm was manufactured using a single sheet extruder. The physical properties of the injection-molded product and the extruded sheet were measured and are shown in Table 1 below.

[0113] [Comparative Example 5]

[0114] In Example 6 described above, instead of the emulsion polymer particles, an equal amount of SAN Gel-1 described in US Patent Publication No. 5580924A was added, and otherwise, the same method as in Example 6 was performed. The physical properties of the injection-molded product and the extruded sheet were measured and are shown in Table 1 below.

[0115] [Examples 11 to 15 and Comparative Examples 6 to 8]

[0116] In Example 6 described above, instead of ABS (IM-601), an equal amount of ASA (XC-500A) was added, and otherwise, the same method as in Example 6 was performed. The physical properties of the injection-molded product and the extruded sheet were measured and are shown in Table 2 below.

[0117] [Table 1]

[0118]

[0119] [Table 2]

[0120]

[0121] -BLENDEX BMAT: styrene-acrylonitrile copolymer

[0122] -XPHERE-NGR: styrene-acrylonitrile copolymer

[0123] As shown in Tables 1 to 2 above, the surface gloss of the sheet (molded product) manufactured by extrusion or injection molding of the matting polymer composition containing the emulsion polymer particles of the present application was effectively reduced, and specifically, in Examples 6 to 10 in which the emulsion polymer particles of the present application were applied to PC / ABS, it was confirmed that the mechanical properties such as impact strength and tensile strength did not greatly change, and at the same time, compared to Comparative Examples 3 and 4 in which commercial products were applied, excellent matting effects and a lower yellow index were exhibited.

[0124] In particular, it is seen that the surface gloss at 85° in Comparative Examples 2 to 4 and Comparative Examples 6 to 8 are all 40 or more, in contrast, in Examples 6 to 15, they are all 30 or less, and thus it is confirmed that when the matting agent (emulsion polymer particles) according to the present application is used, a matting effect that is difficult to achieve in conventional extrusion processing can be very effectively exhibited. Furthermore, the appearance of the sheet according to Example 6 is good, in contrast, the surface of the sheet of the above-mentioned Comparative Example 5 is very uneven, and moreover, a plurality of black spots are generated, and thus it is determined to be poor.

[0125] Comparing Examples 6, 8 and 9 using the emulsion polymer particles of Examples 1, 3 and 4, it is confirmed that when 3 to 25 parts by weight of the alicyclic epoxy compound is used with respect to 100 parts by weight of the aromatic vinyl compound, particularly 5 to 15 parts by weight, a more excellent matting effect is exhibited.

[0126] As described above, in the present application, specific matters and limited examples are described, but this is provided only to help more fully understand the present application, and the present application is not limited to the above-described examples, and as long as a person skilled in the art in the field to which the present application belongs, various modifications and alterations can be made based on such description.

[0127] Therefore, the idea of the present application is not limited to the described examples, and not only the scope of the present application claimed, but also all the scope of the modifications equivalent or equivalent to the scope of the present application claimed belong to the category of the idea of the present application.

Claims

1. An emulsion polymer particle produced from a first polymerizable composition for producing a core layer comprising an aromatic vinyl compound, an acid compound, and an alicyclic epoxy compound, of which an epoxy group is ring-opened, wherein the alicyclic epoxy compound has two or more epoxy groups, and a second polymerizable composition for producing a shell layer comprising an aromatic vinyl compound, an unsaturated nitrile compound, and an alicyclic epoxy compound, wherein the emulsion polymer particle comprises a core layer and a shell layer, the first polymerizable composition contains 1 to 30 parts by weight of the alicyclic epoxy compound with respect to 100 parts by weight of the aromatic vinyl compound, the weight ratio of the alicyclic epoxy compound to the acid compound in the first polymerizable composition is 1 : 0.005 to 0.5, the second polymerizable composition contains 5 to 80 parts by weight of the unsaturated nitrile compound with respect to 100 parts by weight of the aromatic vinyl compound, and the second polymerizable composition contains 0.5 to 50 parts by weight of the alicyclic epoxy compound with respect to 100 parts by weight of the total of the aromatic vinyl compound and the unsaturated nitrile compound, wherein the average particle diameter of the emulsion polymer particle is 70 to 500 nm, and wherein the surface of the emulsion polymer particle is negatively charged.

2. The emulsion polymer particles of claim 1, wherein, The alicyclic epoxy compound is one or more selected from the group consisting of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate, diethylene glycol bis(3,4-epoxycyclohexane-carboxylate), 2-ethyl-1,3-hexanediol bis(3,4-epoxycyclohexane-carboxylate), diethylene glycol bis(3,4-epoxy-6-methylcyclohexane-carboxylate), 3-methyl-1,5-pentanediol bis(3,4-epoxycyclohexane-carboxylate), 1,5-pentanediol bis(3,4-epoxycyclohexane-carboxylate), ethylene glycol bis(3,4-epoxycyclohexane-carboxylate), ethylene glycol bis(3,4-epoxy-6-methylcyclohexane-carboxylate), bis(3,4-epoxycyclohexylmethyl)oxalate, bis(3,4-epoxycyclohexylmethyl)succinate, bis(3,4-epoxycyclohexylmethyl)adipate, and 1,2,8,9-diepoxy limonene.

3. The emulsion polymer particles of claim 1, wherein, The acid compound is any one or a combination of two selected from the group consisting of R1COOH and R2SO3H, R1and R2are each independently C 6-30 alkyl, C 6-30 aryl, or C 6-30 aryl C 6-30 alkyl.

4. The emulsion polymer particles of claim 1, wherein, The emulsion polymer particle contains a divalent -SO3- or -CO3- substituent.

5. The emulsion polymer particles of claim 1, wherein, The average particle diameter of the emulsion polymer particle is 90 to 250 nm.

6. A matting agent comprising the emulsion polymer particle according to any one of claims 1 to 5.

7. A master batch chip comprising the matting agent according to claim 6.

8. A matting polymer composition comprising the matting agent according to claim 6 and a thermoplastic polymer.

9. The composition of claim 8, wherein, The thermoplastic polymer is one or more selected from the group consisting of polypropylene (PP), polyacrylate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamide, styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylate (ASA), and mixtures thereof.

10. A molded article produced by extrusion or injection molding the matting polymer composition of claim 8.

11. A method for producing emulsion polymer particles, comprising the steps of: producing a core layer by emulsion polymerization of a first polymerizable composition comprising an aromatic vinyl compound and an alicyclic epoxy compound in an aqueous phase; and producing a shell layer by emulsion polymerization of a second polymerizable composition comprising an aromatic vinyl compound, an unsaturated nitrile compound, and an alicyclic epoxy compound in the presence of the core layer. the step of producing the core layer includes the steps of: (a) adding the first polymerizable composition, deionized water, an emulsifier, and an acid compound in a reactor and stirring to produce a pre-emulsion; and wherein (b) adding a water-soluble initiator to initiate the reaction and perform emulsion polymerization, wherein the alicyclic epoxy compound has two or more epoxy groups, wherein the emulsion polymer particles comprise a core layer and a shell layer, the first polymerizable composition contains 1 to 30 parts by weight of the alicyclic epoxy compound per 100 parts by weight of the aromatic vinyl compound, the second polymerizable composition contains 5 to 80 parts by weight of the unsaturated nitrile compound per 100 parts by weight of the aromatic vinyl compound, the second polymerizable composition contains 0.5 to 50 parts by weight of the alicyclic epoxy compound per 100 parts by weight of the sum of the aromatic vinyl compound and the unsaturated nitrile compound, wherein the average particle diameter of the emulsion polymer particles is 70 to 500 nm, wherein the surface of the emulsion polymer particles is negatively charged. the first polymerizable composition contains 1 to 20 parts by weight of the alicyclic epoxy compound per 100 parts by weight of the aromatic vinyl compound, the second polymerizable composition contains 2 to 18 parts by weight of the alicyclic epoxy compound per 100 parts by weight of the sum of the aromatic vinyl compound and the unsaturated nitrile compound.

12. The method for producing emulsion polymer particles according to claim 11, wherein the acid compound is either one or a combination of both selected from the group consisting of R1COOH and R2SO3H, the step of producing the shell layer includes the step of:

13. The method for producing emulsion polymer particles according to claim 12, wherein dropping the second polymerizable composition in the presence of the core layer to perform emulsion polymerization and thereby produce an emulsion polymer particle dispersion. R1and R2are each independently C 6-30 alkyl, C 6-30 aryl, or C 6-30 aryl C 6-30 alkyl.

14. The method for producing emulsion polymer particles according to claim 11, wherein The emulsion polymer particles contain 5 to 60 wt% of the core layer and 40 to 95 wt% of the shell layer. The solid content of the emulsion polymer particle dispersion is 20 to 45 wt%.

15. The method for producing emulsion polymer particles according to claim 11, wherein ​ 16. The method for producing emulsion polymer particles according to claim 14, wherein ​

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