Matting agent comprising 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 polymer particles, a matting polymer composition comprising the matting agent, and a method for producing the same, the above polymer particles being produced by a simple process such as a suspension polymerization method, and having the advantage that the crosslinking degree can be easily adjusted. In addition, when a matting polymer composition is produced using a matting agent comprising the above polymer particles, a molded product having excellent matting effects 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, excellent matting effects that have been difficult to achieve in the past in extrusion processing can be achieved.

Description

Technical Field

[0001] This invention relates to a matting agent comprising polymer particles, a matting polymer composition comprising the matting agent, and a method for manufacturing the same. Background Technology

[0002] With the increasing popularity of electric vehicles, the issue of lightweighting in the automotive industry has become more important, and various efforts have been made to address it. Representative examples include replacing the metal materials of the car body with lightweight, high-strength engineering plastics, or removing metal materials from parts joined by existing bolts and nuts using adhesives.

[0003] In addition, in terms of using paint to depict various colors and textures in automotive interior and exterior materials, there is an increasing preference for products with low-gloss or matte textures due to issues such as lightweighting, environmental concerns, driver problems caused by light reflection from painted surfaces, and the increasing sophistication of interior decoration.

[0004] As a method to reduce gloss, resin can be injected into the etched mold, but it cannot produce a sufficient matting effect. Alternatively, inorganic fillers can be added, but an excessive amount must be used to achieve a sufficient matting effect, and the mechanical strength is weakened when used in excess, thus its use is very limited.

[0005] In US patent US5580924A, in order to reduce the gloss of PC, a styrene-acrylonitrile copolymer is synthesized and mixed with 3,4-epoxycyclohexyl-3,4-epoxycyclohexylcarboxylic acid ester. The cross-linked SAN is then manufactured through a reactive extruder. However, the above-mentioned prior art has limitations in manufacturing high-quality molded products. For example, surface foreign matter such as black spots will be generated during reactive extrusion, making it difficult to improve the color, difficult to adjust the cross-linking point, and insoluble during processing, resulting in poor appearance.

[0006] Therefore, there is an urgent need to develop matting additives that have excellent matting effects, do not degrade mechanical properties, and can exhibit superior appearance quality. Summary of the Invention

[0007] In order to solve the problems of the prior art as described above, the object of the present invention is to provide a matting agent comprising polymer particles manufactured by suspension polymerization.

[0008] Another object of the present invention is to provide a matting polymer composition comprising the above-mentioned matting agent, wherein by extruding or injection molding the above composition, a molded article having excellent matting effect, mechanical properties and excellent appearance quality is provided.

[0009] To address the aforementioned problems, the inventors of this invention employed a suspension polymerization method, previously unexplored, to manufacture polymer particles from a polymerizable composition comprising aromatic vinyl compounds, unsaturated nitrile compounds, and alicyclic epoxy compounds. These polymer particles exhibit easily adjustable crosslinking levels. Surprisingly, when using matting agents and matting polymer compositions containing these particles, it was discovered that molded articles with excellent appearance quality, exhibiting superior matting effects with only small amounts, could be produced without compromising the physical properties of existing thermoplastic polymers, thus completing this invention.

[0010] The present invention provides polymer particles manufactured from a polymerizable composition comprising an aromatic vinyl compound, an unsaturated nitrile compound and an alicyclic epoxy compound, having an average particle size of 1 to 5000 μm, wherein the epoxy groups of the aforementioned alicyclic epoxy compound are ring-opening.

[0011] According to one embodiment of the present invention, the polymer particles may be manufactured by suspension polymerization.

[0012] According to an embodiment of the present invention, the above-mentioned alicyclic epoxy compound may have two or more epoxy groups, and the above-mentioned alicyclic epoxy compound may be selected from 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-epoxy-6-methylcyclohexane-carboxylate), and 3-methyl-1,5-pentanediol bis(3,4-epoxy-6-methylcyclohexane-carboxylate). One or more of the following: (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-diepoxylimonene.

[0013] According to an embodiment of the present invention, the above-described polymerizable composition may be manufactured by comprising 20 to 45 parts by weight of an unsaturated nitrile compound and 2.5 to 25 parts by weight of an alicyclic epoxy compound relative to 100 parts by weight of an aromatic vinyl compound.

[0014] According to one embodiment of the present invention, the polymerizable composition may further comprise one or more acid compounds selected from R1COOH, R2SO3H and their salts, wherein R1 and R2 are each independently C 6-30 Alkyl, C 6-30 Aryl, or C 6-30 Aryl C 6-30 alkyl.

[0015] According to one embodiment of the present invention, the polymerizable composition may contain 0.05 to 1 part by weight of the acid compound relative to 100 parts by weight of the aromatic vinyl compound.

[0016] According to one embodiment of the present invention, the polymer particles may contain divalent -SO3-.

[0017] The present invention can provide a matting agent comprising the above-mentioned polymer particles.

[0018] The present invention can provide masterbatch fragments containing the above-mentioned matting agent.

[0019] The present invention can provide a matting polymer composition comprising the above-mentioned matting agent and thermoplastic polymer.

[0020] According to one embodiment of the present invention, the above-mentioned thermoplastic polymer may be one or more selected from 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.

[0021] The present invention can provide molded articles manufactured by extruding or injection molding the above-mentioned matte polymer composition.

[0022] The present invention can provide a method for manufacturing polymer particles, comprising the following steps: dispersing a polymeric composition comprising an aromatic vinyl compound, an unsaturated nitrile compound and an alicyclic epoxy compound in an aqueous solution comprising a suspension stabilizer; and suspending polymerizing the above-dispersed polymeric composition.

[0023] In a method for manufacturing polymer particles according to an embodiment of the present invention, the polymeric composition may contain 20 to 45 parts by weight of an unsaturated nitrile compound and 2.5 to 25 parts by weight of an alicyclic epoxy compound relative to 100 parts by weight of an aromatic vinyl compound.

[0024] In a method for manufacturing polymer particles according to an embodiment of the present invention, the polymeric composition may further comprise one or more acid compounds selected from R1COOH, R2SO3H and their salts, wherein R1 and R2 are each independently C 6-30 Alkyl, C 6-30 Aryl, or C 6-30 Aryl C 6-30 alkyl.

[0025] In a method for manufacturing polymer particles according to an embodiment of the present invention, the polymeric composition may contain 0.05 to 1 part by weight of the acid compound relative to 100 parts by weight of the aromatic vinyl compound.

[0026] The polymer particles according to the present invention can be manufactured through a simple process such as suspension polymerization, which has the advantage of making it relatively easy to adjust the degree of crosslinking. Furthermore, when using a matting agent containing the above-mentioned polymer particles to manufacture a matting polymer composition, the matting properties can be effectively exerted without reducing other physical properties, and therefore this method is preferred.

[0027] Furthermore, when using the above-mentioned matte polymer composition, it is possible to manufacture molded articles with a beautiful appearance and excellent matte effect without reducing the mechanical properties such as impact strength and tensile strength of existing thermoplastic polymers. In particular, it can achieve an excellent matte effect that is difficult to achieve in extrusion processing in the past, and is therefore highly preferred.

[0028] The matting agent of the present invention and the matting polymer composition containing the same can be applied to a variety of products, such as automotive interior / exterior trim materials, interior decoration materials, and household appliances. Detailed Implementation

[0029] The present invention will now be described in more detail by way of specific examples or embodiments. However, the specific examples or embodiments described below are merely for reference in providing a detailed description of the present invention, and the present invention is not limited thereto and can be implemented in various forms.

[0030] Furthermore, unless otherwise defined, all technical and scientific terms shall have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terms used in this invention for illustrative purposes are merely for the effective description of specific examples and are not intended to limit the scope of the invention.

[0031] In addition, the singular form used in the specification and the appended claims may also be intended to include the plural form unless otherwise indicated in the context.

[0032] Furthermore, when it is stated that a part "contains / includes" a certain constituent element, unless there is a particularly contrary statement, it means that other constituent elements may be included, rather than excluding other constituent elements.

[0033] The term "dullness" as used in this specification refers to the property of reducing gloss by utilizing the diffuse reflection effect through differences in shrinkage and refractive index or surface processing between polymers in an incompatible polymer composition and between polymers and additives.

[0034] The term "dispersed phase" as used in this specification refers to a discontinuous phase distributed throughout the dispersion medium. Specifically, it can refer to a discontinuous phase in which the polymerizable composition is distributed in the form of droplets in an aqueous medium.

[0035] The preferred embodiments and methods for measuring physical properties of the present invention, including the matting agent containing polymer particles, the matting polymer composition containing the matting agent, and the manufacturing method thereof, are described in detail below.

[0036] The invention can be better understood through the following embodiments, which are for illustrative purposes only and are not intended to limit the scope of protection defined by the appended claims.

[0037] The following is a more detailed description of one embodiment of the present invention.

[0038] The present invention provides polymer particles manufactured from a polymerizable composition comprising an aromatic vinyl compound, an unsaturated nitrile compound and an alicyclic epoxy compound, having an average particle size of 1 to 5000 μm, wherein the epoxy groups of the aforementioned alicyclic epoxy compound are ring-opening.

[0039] The average particle size of the aforementioned polymer particles can be represented by D50, which refers to the particle diameter at which the cumulative volume of small-diameter particles reaches 50% in a particle size distribution determination using laser scattering. Here, D50 can be obtained by collecting particles according to the KS AISO 13320-1 standard and determining the particle size distribution of the polymer particles using a Malvern Mastersizer 3000. Specifically, water can be used as the dispersion medium, and an ultrasonic disperser can be used if necessary. After dispersion, the volume density is measured, but the invention is not limited to this. Conventional or known methods can be used to determine the average particle size.

[0040] Specifically, the average particle size of the polymer particles can be 1 to 5000 μm, 5 to 2000 μm, or 10 to 1500 μm, and is preferably 50 to 1000 μm. When using polymer particles with an average particle size within the above range, excellent matting effects can be achieved with only a small amount added without reducing other physical properties, and therefore this is preferred. Furthermore, the polymer particles can have a relatively spherical shape, which allows for the manufacture of molded articles with good appearance quality, and is therefore preferred.

[0041] The epoxy groups of the alicyclic epoxy compounds contained in the polymer particles may be in an open-ring state. Specifically, the open-ring epoxy groups may be formed by reaction with other compounds contained in the polymeric composition. More specifically, the alicyclic epoxy compounds may be chemically bonded to the polymer and contained within the polymer particles, but this is not necessarily the case.

[0042] According to one embodiment of the present invention, the polymer particles described above can be manufactured by suspension polymerization. To address the problems arising in the prior art, suspension polymerization can be used to manufacture suspension polymer particles. When using these suspension polymer particles, the degree of crosslinking is easily adjusted, and molded articles with excellent appearance quality can be manufactured. Excellent matting effects can be achieved with only a small amount of addition, therefore this method is preferred.

[0043] According to one embodiment of the present invention, as a non-limiting example, the above-mentioned aromatic vinyl compound may be one or more selected from styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, tert-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, with styrene being preferred.

[0044] As a non-limiting example, the aforementioned unsaturated nitrile compound may be one or more selected from acrylonitrile, methacrylonitrile, ethylacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile being preferred.

[0045] Preferably, the above-mentioned alicyclic epoxy compounds may have two or more epoxy groups. Specifically, the above-mentioned alicyclic epoxy compounds may be selected from 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, One or more of the following are preferred: 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-diepoxylimonene. 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate is also preferred. As another example, commercially available products such as CEL-2021, CEL-3000, and CEL-2081 from Daicel Chemicals can be used.

[0046] According to one embodiment of the present invention, the polymerizable composition may contain 1 to 90 parts by weight of an unsaturated nitrile compound, preferably 10 to 70 parts by weight, more preferably 20 to 45 parts by weight, relative to 100 parts by weight of the aromatic vinyl compound, and may contain 0.1 to 50 parts by weight of the aforementioned alicyclic epoxy compound, preferably 1 to 40 parts by weight, more preferably 2.5 to 25 parts by weight or 5 to 20 parts by weight. When the above ranges are satisfied, reaction stability can be maintained, and polymer particles having the target properties of the present invention can be produced. Therefore, it is preferable that even a small amount of matting agent containing it can effectively exert a matting effect, and even more preferable.

[0047] Furthermore, based on the total weight of the polymerizable composition described above, it may contain 50 to 90 wt% of the aromatic vinyl compound, preferably 65 to 80 wt%, and may contain 10 to 50 wt% of the unsaturated nitrile compound, preferably 20 to 35 wt%. When the above ranges are met, the matting effect can be more effectively exerted, yellowing can be suppressed, and color reproduction performance can be improved, which is therefore preferred, but it is not limited thereto as long as the target physical properties of the present invention are not impaired.

[0048] According to an embodiment of the present invention, the polymerizable composition may further comprise one or more acid compounds selected from R1COOH, R2SO3H and their salts, wherein R1 and R2 may each independently be C 6-30 Alkyl, C 6-30 Aryl, or C 6-30 Aryl C 6-30 Alkyl groups; furthermore, the salt compounds of the above-mentioned acid compounds may be represented by R1COOM and R2SO3M, where R1 and R2 are the same as described above, and M may be a cation. M may be an alkali metal cation or an ammonium cation. As a non-limiting example, M may be selected from one or more of sodium ions, potassium ions, and lithium ions, but is not limited thereto.

[0049] Preferably, the acid compound is R2SO3H, where R2 can be C. 6-12 Aryl C 6-18 Alkyl groups, as an example, may be selected from butylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, and pentadecylbenzenesulfonic acid, but are not limited thereto. The acid compound may contain 0.005 to 5 parts by weight, preferably 0.05 to 1 part by weight, relative to 100 parts by weight of the aromatic vinyl compound in the polymerizable composition.

[0050] Furthermore, the aforementioned polymer particles may contain divalent -SO3- or -CO3- substituents, specifically -SO3- substituents. These divalent substituents may be formed by the reaction of an acid compound and an alicyclic epoxy compound contained in the polymeric composition, and each divalent substituent may be bonded to a hydrocarbon group. The divalent substituents may be included through bonding with the polymer chain. Moreover, the divalent substituents are primarily present on the surface of the polymer particles, resulting in a concentration gradient where the concentration of the divalent substituents decreases from the surface of the polymer particles towards the interior of the polymer. This concentration gradient may originate from a suspension polymerization mechanism. Specifically, since the acid compound is located at the interface of the dispersed phase, the divalent substituents may exist at a high concentration on the surface of the polymer particles through the reaction between the acid compound and the alicyclic epoxy compound at the interface. Polymer particles with the above structure can exhibit a significant extinction effect and are therefore more preferable.

[0051] Specifically, the polymerizable composition described above can be mixed with water (medium) to form a dispersed phase, and the acid compound or its salt compound can be located at the interface between the dispersed phase and the aqueous phase, whereby the polymerizable composition polymerizes. When the acid compound is further added to the polymerizable composition for suspension polymerization, the reaction rate can be effectively increased, and polymer particles forming a robust cross-linked network can be produced, which is therefore highly preferred.

[0052] The present invention can provide a matting agent comprising the above-described polymer particles. This can be achieved by obtaining the above-described polymer particles in bead form after suspension polymerization, then dehydrating and drying them for use as a matting agent.

[0053] This invention provides masterbatch chips containing the aforementioned matting agent. The masterbatch chips may contain a thermoplastic polymer and a matting agent, and further may contain one or more additives selected from antioxidants, UV absorbers, UV stabilizers, lubricants, and mixtures thereof. The additives can be used without limitation as long as they are commonly used or known. Based on the total weight of the masterbatch chips, the matting agent may be contained in 0.1 to 50 wt%, preferably 5 to 30 wt%. When using masterbatch chips within the above range, the dispersibility and uniformity of the matting agent and additives are improved, thereby enabling the manufacture of high-quality products (molded articles), which is therefore preferred.

[0054] This invention provides a matting polymer composition comprising the aforementioned matting agent and a thermoplastic polymer. The aforementioned matting agent, added in small amounts, effectively exhibits matting properties without reducing the physical properties of existing thermoplastic polymers, possesses a high degree of cross-linking, and demonstrates excellent dispersibility with the aforementioned thermoplastic polymer. Therefore, the problems of the prior art can be solved, and the aforementioned matting polymer composition can be extruded and injection molded to manufacture low-gloss or matte products with excellent mechanical strength.

[0055] According to one embodiment of the present invention, the above-mentioned thermoplastic polymer may be one or more selected from 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. Specifically, mixtures of PC and SAN, mixtures of PC and ABS, or mixtures of PC and ASA may be used, but it is not limited thereto.

[0056] According to one embodiment of the present invention, the above-mentioned matting polymer composition may contain 0.1 to 30 wt% of the above-mentioned matting agent and 70 to 99.9 wt% of the above-mentioned thermoplastic polymer, but is not limited thereto. The amount of the above-mentioned matting agent can be adjusted according to the surface gloss of the product to be manufactured.

[0057] According to one embodiment of the present invention, the above-described matting polymer composition may further include additives commonly used in the art, depending on the purpose and use. For example, it may also include antioxidants, UV absorbers, UV stabilizers, lubricants, etc. In this case, the above-described additives may be included in appropriate amounts without reducing the target properties of the present invention.

[0058] According to one embodiment of the present invention, after the above-mentioned matting agent, comprising a thermoplastic polymer, is manufactured into masterbatch fragments, it can be mixed again with the thermoplastic polymer. The masterbatch fragments may also contain additives. Based on the total weight of the above-mentioned matting polymer composition, the masterbatch fragments may be included in an amount of 0.1 to 50 wt%, preferably 1 to 30 wt%. The amount of the masterbatch fragments can be adjusted to determine the content of the matting agent in the final manufactured product.

[0059] This invention provides molded articles manufactured by extruding or injection molding the above-mentioned matte polymer composition. Conventionally, it has been very difficult to manufacture molded articles with excellent matte finish during extrusion processing. However, when using a matte polymer composition incorporating a matte agent containing polymer particles of this invention, not only can undesirable appearance phenomena caused by particle protrusion, especially during extrusion processing, be effectively suppressed, but molded articles with excellent matte finish and superior appearance quality can also be manufactured without reducing the mechanical properties of existing polymers. Therefore, this invention is highly preferred.

[0060] The method for manufacturing polymer particles according to the present invention will now be described in detail.

[0061] The present invention can provide a method for manufacturing polymer particles, comprising the following steps: dispersing a polymeric composition comprising an aromatic vinyl compound, an unsaturated nitrile compound and an alicyclic epoxy compound in an aqueous solution comprising a suspension stabilizer; and suspending polymerizing the above-dispersed polymeric composition.

[0062] The suspension polymerization described above can be performed without limitation using methods including those known or commonly used, as long as it can produce the target polymer particles of the present invention. Furthermore, the specific examples and contents of the polymerizable compositions, aromatic vinyl compounds, unsaturated nitrile compounds, and alicyclic epoxy compounds described above are the same as those described above.

[0063] In a method for manufacturing polymer particles according to an embodiment of the present invention, the polymeric composition may further contain one or more acid compounds selected from R1COOH, R2SO3H and their salt compounds, and the detailed description of the acid compounds and examples of specific compounds are the same as those described above.

[0064] In addition, the polymerizable composition described above may also contain a crosslinking agent. The crosslinking agent can be used with virtually no restriction as long as it has two or more crosslinkable functional groups, and the detailed description of the crosslinking agent and examples of specific compounds are the same as described above.

[0065] In addition, the above-mentioned polymerizable composition may also contain a molecular weight regulator for adjusting the molecular weight. The molecular weight regulator may be n-dodecyl mercaptan, n-pentyl mercaptan, tert-butyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-nonyl mercaptan, etc., and may be used in amounts of 0.001 to 10 parts by weight relative to 100 parts by weight of the above-mentioned aromatic vinyl compound, preferably 0.01 to 5 parts by weight, but is not limited thereto.

[0066] According to one embodiment of the present invention, the step of dispersing the above-mentioned polymeric composition in an aqueous solution containing a suspension stabilizer involves adding the polymeric composition, acid compound, and initiator to an aqueous solution formed by dissolving the suspension stabilizer in deionized water, and stirring and dispersing at room temperature to produce a polymeric suspension. It is preferable to disperse the polymeric composition for a sufficient time and at a sufficient stirring speed. The more stable the dispersion of the polymeric suspension, the better the reaction stability. Therefore, the time and stirring speed are generally not limited. As an example, when the reactor size is 2L, it is preferable to maintain a stirring time of 500 rpm or higher for at least 10 minutes. In this case, the polymeric suspension may also contain commonly used or known suspension stabilizers, buffers (pH adjusters), and molecular weight adjusters, etc.

[0067] Furthermore, in the above-described dispersion step, the polymerizable composition is dispersed in deionized water (aqueous phase) as a medium, and can be thoroughly stirred to allow the droplets of the dispersed phase to diffuse uniformly. Additionally, the suspension stabilizer and acid compound or their salt compound can be located at the interface between the aqueous phase and the dispersed phase, and the initiator present within the dispersed phase initiates polymerization according to external temperature conditions, thereby enabling polymerization of the polymerizable composition to occur both within the dispersed phase and at the interface.

[0068] The suspension polymerization step of the above-mentioned dispersed polymerizable composition involves raising the internal temperature of the reactor to 50 to 70°C to initiate the reaction. As the reaction proceeds, exothermic reactions may occur; therefore, a cooler is preferably used to stabilize the reactor temperature at 65 to 75°C. The reaction time can be 1 to 5 hours. Furthermore, the polymerization step may include one or more further polymerization steps, for example, further polymerization at 60 to 75°C for 30 minutes to 5 hours, followed by further polymerization at 80 to 95°C for 30 minutes to 6 hours, but is not limited to this.

[0069] Furthermore, after the reaction is complete, a dehydration and drying process yields polymer particles in a white powder state with a moisture content of less than 0.5 wt%. Specific details regarding the polymer particles manufactured as described above are the same as those described above.

[0070] The aforementioned suspension stabilizer reduces the interfacial energy between the polymerizable composition of the dispersed phase and the aqueous phase of deionized water, thus maintaining a more uniform dispersed phase and enabling the production of a stable polymerizable suspension. Therefore, suspension polymerization can proceed stably. The choice of suspension stabilizer is largely unrestricted as long as it can produce the target polymer particles of this invention.

[0071] The aforementioned suspension stabilizer can be either organic or inorganic. As a non-limiting example, examples of such suspension stabilizers include monomers or copolymers of acrylic acid or methacrylic acid, alkyl polyacrylate-(meth)acrylic acid (ethyl polyacrylate-acrylic acid, ethyl polyacrylate-methacrylic acid, and ethylhexyl polyacrylate-acrylic acid, etc.), polyolefin-maleic acid, polyvinyl alcohol, cellulose, etc.; inorganic suspension stabilizers including tricalcium phosphate, etc.; mixtures thereof, etc., but are not limited thereto. The aforementioned (meth)acrylic acid can be in the form of sodium, potassium, or ammonium salts. Furthermore, relative to 100 parts by weight of the aforementioned polymerizable composition, it may contain 0.01 to 3 parts by weight, preferably 0.05 to 0.5 parts by weight, but is not limited thereto.

[0072] As the aforementioned suspension stabilizers, disodium hydrogen phosphate and sodium dihydrogen phosphate can be used, or sodium sulfate can be added to control the solubility characteristics of water-soluble polymers or monomers, but this is not a limitation.

[0073] The descriptions of the acid compounds and the examples of specific compounds are the same as those described above.

[0074] Furthermore, in the above-described polymerizable composition, the weight ratio of the alicyclic epoxy compound to the acid compound can be from 1:0.001 to 0.5, preferably from 1:0.005 to 0.2, and more preferably from 1:0.01 to 0.1. When the above range is met, the reaction stability can be maintained, and the polymer particles can be manufactured into relatively spherical shapes. Therefore, it is preferable that when the above-described suspended polymer particles are used as a matting agent, only a small amount needs to be added to manufacture molded articles with improved matting effect and appearance quality without any decrease in mechanical properties.

[0075] According to one embodiment of the present invention, the initiator may be an oil-soluble initiator dissolved in the polymerizable composition, but it may be used without particular limitation as long as it is an initiator commonly used for suspension polymerization or a known compound. For example, it may be a free radical polymerization initiator. As non-limiting examples, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, monochlorobenzoyl peroxide, dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, tert-butyl perbenzoate, azobisisobutyronitrile, and azobis(2,4-dimethyl)pentanonitrile may be used, but it is not limited thereto. Relative to 100 parts by weight of the polymerizable composition, it may contain 0.01 to 5 parts by weight, preferably 0.05 to 0.5 parts by weight, but it is not limited thereto.

[0076] The present invention will now be described in more detail based on embodiments and comparative examples. However, the embodiments and comparative examples described below are merely illustrative examples for illustrating the present invention in more detail, and the present invention is not limited to the embodiments and comparative examples described below.

[0077] [Methods for determining physical properties]

[0078] 1) Average particle size: The average particle size was determined using a particle size analyzer (Malvern Mastersizer 3000).

[0079] 2) Surface gloss (GLOSS): Measured at 60° and 85° according to ASTM D523.

[0080] 3) Noched IZOD Impact Strength: The impact strength was measured at 1 / 4” and 1 / 8” according to ASTM D256.

[0081] 4) Tensile strength: The tensile strength was determined according to ASTM D638.

[0082] - Manufacturing of polymer particles

[0083] [Example 1]

[0084] 150g of deionized water and 2.0g of tricalcium phosphate were added to the reactor and stirred until dissolved. Then, a polymerizable composition containing 65g of styrene, 26g of acrylonitrile, 9g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 0.25g of dodecylbenzenesulfonic acid, and 0.15g of azobisisobutyronitrile was added to the reactor and stirred at a speed of 500 rpm or higher for at least 30 minutes. After confirming the dispersion stability of the above suspension, suspension polymerization was carried out at 65°C under a nitrogen atmosphere with stirring for 3 hours. Then, the temperature was increased to 70°C for 1 hour and reacted again for 3 hours, followed by a 1-hour increase to 90°C and reacted for 4 hours to complete the suspension polymerization. After the reaction, the polymer particles described in Example 1 were obtained as a white powder after washing, dehydration, and drying. The polymer was obtained in bead form, and the average particle size was measured to be 220 μm.

[0085] [Example 2]

[0086] In Example 1 above, 5 g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate was added, and otherwise the process was carried out using the same method as in Example 1. The average particle size of the polymer beads was determined to be 250 μm.

[0087] [Example 3]

[0088] In Example 1 above, 12 g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate was added, and otherwise the process was carried out using the same method as in Example 1. The average particle size of the polymer beads was determined to be 170 μm.

[0089] [Example 4]

[0090] In Example 1 above, ethyl polyacrylate-methacrylic acid was used instead of tricalcium phosphate as a suspension stabilizer; otherwise, the same method as in Example 1 was used. The average particle size of the polymer beads was measured to be 190 μm.

[0091] [Example 5]

[0092] In Example 1 above, 86g of styrene and 14g of acrylonitrile were added when manufacturing the polymeric composition, and otherwise the process was carried out in the same manner as in Example 1. The average particle size of the polymer beads was measured to be 210μm.

[0093] [Example 6]

[0094] In Example 5 above, 2 g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate was added when manufacturing the polymeric composition, and otherwise the process was carried out in the same manner as in Example 5. The average particle size of the polymer beads was measured to be 270 μm.

[0095] [Comparative Example 1]

[0096] In Example 1 above, dodecylbenzenesulfonic acid was not added; instead of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, an equal amount of divinylbenzene was added. Otherwise, the process was carried out using the same method as in Example 1. The average particle size of the polymer beads was determined to be 200 μm.

[0097] Manufacturing of injection molded products and extruded sheets

[0098] [Examples 7 to 12 and Comparative Examples 2 to 4]

[0099] 65.5 wt% PC (3020PJ), 11.4 wt% ABS (IM-601), 18 wt% SAN (92HR), and 0.3 wt% antioxidant were mixed with 4.7 wt% of the polymer particles described in Examples 1 to 6 and Comparative Example 1. The mixture was then extruded to obtain matte polymer composition particles. These particles were dried, and samples with a width, length, and thickness of 70 mm x 75 mm x 3.0 mm were manufactured using an injection molding machine. Sheet samples with a width, length, and thickness of 100 mm x 75 mm x 2.0 mm were also manufactured using a single-sheet extruder. The physical properties of the manufactured injection-molded articles and extruded sheets were measured and are shown in Table 1 below.

[0100] [Comparative Example 5]

[0101] In Example 7 above, an equal amount of SAN Gel-1 as described in U.S. Patent Publication US5580924A was used instead of the polymer particles described above, and the process was otherwise carried out using the same method as in Example 7. The physical properties of the manufactured injection-molded articles and extruded sheets were measured and are shown in Table 1 below.

[0102] Table 1

[0103]

[0104] -BLENDEX BMAT: Styrene-acrylonitrile copolymer -XPHERE-NGR: Styrene-acrylonitrile copolymer

[0105] As shown in Table 1 above, the surface gloss of sheets (molded articles) manufactured by extruding or injection molding the matting polymer composition containing the polymer particles of the present invention is effectively reduced. Specifically, it was confirmed that when the polymer particles of the present invention are applied to PC / ABS, the mechanical properties such as impact strength and tensile strength are not significantly changed, and the matting effect is excellent compared with Comparative Examples 3 and 4, which are applied to commercially available products.

[0106] In particular, it was observed that the surface gloss of Comparative Examples 2 to 5 at 85° was all above 45, while that of Examples 7 to 11 was below 25. This confirms that when using the matting agent (polymer particles) according to the present invention, a matting effect that is difficult to achieve in conventional extrusion processing can be very effectively exhibited. Furthermore, the sheet described in Example 7, which used polymer particles with appropriately adjusted crosslinking degree, had a good appearance; conversely, the surface of the sheet in Comparative Example 5 was very uneven and had multiple black spots, thus it was deemed defective.

[0107] Comparing Examples 11 and 12, which used the polymer particles of Examples 5 and 6, with Example 7, it can be confirmed that the polymer particles manufactured by comprising 20 to 45 parts by weight of unsaturated nitrile compound and 2.5 to 25 parts by weight of alicyclic epoxy compound relative to 100 parts by weight of aromatic vinyl compound exhibit superior matting effect.

[0108] Furthermore, comparing Examples 7 to 9, which used the polymer particles of Examples 1 to 3 described above, it can be confirmed that when the alicyclic epoxy compound and acid compound are contained in a weight ratio of 1:0.005 to 0.2, a superior matting effect is exhibited.

[0109] As described above, the present invention has been illustrated with specific details and limited embodiments, but this is only provided to help to understand the invention more fully. The present invention is not limited to the above embodiments, and those skilled in the art to which this invention pertains can make various modifications and variations based on such description.

[0110] Therefore, the concept of the present invention is not limited to the illustrated embodiments, but is not only within the scope of protection claimed by the present invention, but also includes all scopes with modifications that are equivalent to or equivalent to the scope of protection claimed by the present invention.

Claims

1. Polymer particles produced from a polymerizable composition comprising an aromatic vinyl compound, an unsaturated nitrile compound, and an alicyclic epoxy compound, wherein the alicyclic epoxy compound has 2 or more epoxy groups, wherein the alicyclic epoxy compound has an average particle diameter of 1 to 5,000 μm, and wherein the epoxy groups of the alicyclic epoxy compound are ring-opened, wherein the polymer particles are produced by suspension polymerization, and wherein the polymerizable composition is produced so as to contain the unsaturated nitrile compound at 20 to 45 parts by weight and the alicyclic epoxy compound at 2.5 to 25 parts by weight, relative to 100 parts by weight of the aromatic vinyl compound.

2. The polymer particles according to claim 1, wherein the polymerizable composition contains any one or two or more of the compounds selected from the group consisting of R1COOH, R2SO3H, and salts thereof, at 0.05 to 1 part by weight, relative to 100 parts by weight of the aromatic vinyl compound.

3. The polymer particles according to claim 1 or 2, 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.

4. A matting agent comprising the polymer particles according to any one of claims 1 to 3.

5. A master batch comprising the matting agent according to claim 4. wherein the polymerizable composition further comprises any one or two or more selected from the group consisting of R1COOH, R2SO3H, and salts thereof, wherein R1and R2are each independently a C 6-30 alkyl, C 6-30 aryl, or C 6-30 aryl C 6-30 alkyl, 6. A matting polymer composition comprising the matting agent according to claim 4 and a thermoplastic polymer.

2. The polymeric particles according to claim 1, wherein, 7. The matting polymer composition according to claim 6, 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.

3. The polymeric particle of claim 1, wherein, 8. A molded article produced by extrusion or injection molding the matting polymer composition according to claim 6.

9. A method for producing polymer particles, comprising the steps of: dispersing a polymerizable composition comprising an aromatic vinyl compound, an unsaturated nitrile compound, and an alicyclic epoxy compound in an aqueous solution comprising a suspension stabilizer, and suspension polymerizing the dispersed polymerizable composition, wherein the alicyclic epoxy compound has 2 or more epoxy groups.

10. The method according to claim 9, wherein the polymerizable composition is produced so as to contain the unsaturated nitrile compound at 20 to 45 parts by weight and the alicyclic epoxy compound at 2.5 to 25 parts by weight, relative to 100 parts by weight of the aromatic vinyl compound. ​ 7. The composition of claim 6, wherein, ​ ​ ​ ​ ​ ​ wherein the polymerizable composition contains 20 to 45 parts by weight of the unsaturated nitrile compound and 2.5 to 25 parts by weight of the alicyclic epoxy compound with respect to 100 parts by weight of the aromatic vinyl compound, wherein the polymerizable composition further comprises any one or two or more 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, wherein the polymerizable composition contains 0.05 to 1 parts by weight of any one or two or more of the compounds selected from R1COOH, R2SO3H and salts thereof with respect to 100 parts by weight of the aromatic vinyl compound.

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