Diene-based rubber polymer and graft copolymer, and thermoplastic resin composition comprising same

Abstract

The present invention relates to a diene-based rubber polymer and a graft copolymer, and a thermoplastic resin composition comprising the graft copolymer. According to the present invention, the degree of swelling of a graft copolymer comprising a diene-based rubber polymer can be controlled by controlling the particle size distribution, the average particle size, and the roundness of the diene-based rubber polymer having a specific microstructure. In addition, the present invention can provide a thermoplastic resin composition having an excellent physical property balance between impact resistance and flowability, and capable of providing high gloss or high flowability.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to Korean Patent Applications No. 10-2023-0151820, 10-2023-0151821, 10-2023-0151817, and 10-2023-0151816, filed with the Korean Intellectual Property Office on November 6, 2023, and Korean Patent Applications No. 10-2024-0155234, 10-2024-0155370, 10-2024-0155371, and 10-2024-0155233, refiled on November 5, 2024, based on the aforementioned applications, the disclosures of which are hereby incorporated. Technical Field

[0003] This invention relates to diene rubber polymers and graft copolymers, as well as thermoplastic resin compositions comprising the same. According to the invention, the swelling degree of graft copolymers comprising diene rubber polymers can be controlled by controlling the particle size distribution, average particle size, and roundness of the diene rubber polymer having a predetermined microstructure. Furthermore, the invention can provide a thermoplastic resin composition exhibiting an excellent balance of physical properties between impact resistance and flowability, and capable of providing high gloss or high flowability. Background Technology

[0004] Vinyl cyanide-conjugated diene rubber-aromatic vinyl compound graft copolymers, represented by acrylonitrile-butadiene rubber-styrene resin, possess excellent rigidity and chemical resistance due to the presence of acrylonitrile, and achieve a superior balance of physical properties in terms of processability, mechanical strength, and colorability through the inclusion of butadiene and styrene. Furthermore, these graft copolymers have an attractive appearance. Due to these advantages, graft copolymers are used in various fields, such as electrical / electronic products, toys, and office equipment.

[0005] In vinyl cyanide-conjugated diene rubber-aromatic vinyl compound graft copolymers, the low-gloss properties of the graft copolymer increase with the increase of the conjugated diene rubber particle size. Therefore, acid thickeners are used to coagulate the polymerized conjugated diene rubber. However, this process has some drawbacks, such as the inability to retain all solids after coagulation or the generation of a large amount of byproduct clumps, which reduces impact resistance and flowability.

[0006] Because diene-based rubber polymers are prepared using free radical initiators, it is difficult to artificially control the microstructure and cross-linking structure within these polymers. For example, the microstructure may include 1,4-cis bonds, 1,4-trans bonds, and 1,2-vinyl bonds.

[0007] When diene rubber polymers contain uncontrolled microstructures and cross-linked structures, the impact resistance and processability of graft copolymers and thermoplastic resin compositions containing such diene rubber polymers deteriorate.

[0008] Therefore, there is a need to develop a diene-based rubber polymer and graft copolymer that can solve these problems and provide a balance of physical properties between impact resistance and flowability, as well as high gloss.

[0009] [Patent Literature]

[0010] Japanese Announcement No. 11-130825 Summary of the Invention

[0011] Technical issues

[0012] Therefore, the present invention has been made in view of the above-mentioned problems. One object of the present invention is to provide a diene rubber polymer that has an excellent balance of physical properties between impact resistance and flowability by controlling its microstructure, particle size distribution, average particle size and roundness, and is able to provide high gloss or high flowability. The present invention also provides a graft copolymer comprising the diene rubber polymer, and a thermoplastic resin composition comprising the graft copolymer.

[0013] The above and other objectives can be achieved by the invention described below.

[0014] Technical solution

[0015] I) According to one aspect of the present invention, a diene rubber polymer is provided having a microstructure comprising 20% ​​to 30% cis-1,4-bonds, 55% to 65% trans-1,4-bonds, and the balance 1,2-bonds. The diene-based rubber polymer has a first particle size distribution range of 200 Å to 3000 Å. The average particle size is 3000 Å to 4000 Å or 800 Å to 1800 Å, and The roundness calculated using Equation 1 below is between 1.03 and 1.5. [Equation 1]

[0016] Where Di is the ratio of the major axis length to the minor axis length of the i-th particle in the latex [major axis length / minor axis length].

[0017] II) According to I), the diene rubber polymer may have a second particle size distribution range of 1800 Å to 8000 Å.

[0018] III) According to I) to II), the weight ratio (first:second) of particles contained in the first particle size distribution range to particles contained in the second particle size distribution range can be from 1:0.60 to 1:0.94.

[0019] IV) According to I) to III), in the entire particle size distribution range exhibited by the diene rubber polymer, the first particle size distribution range may exhibit a polydisperse particle size distribution of 15% to 75%, and the second particle size distribution range may exhibit a polydisperse particle size distribution of 25% to 55%.

[0020] V) According to I) to IV), the polydisperse particle size distribution can be a measurement of a diene rubber polymer in latex form or a measurement of its acid-thickened product.

[0021] VI) According to I) to V), in the diene rubber polymer, the first particle size distribution range may have a first particle size distribution range of 200 Å to 1800 Å and a second particle size distribution range of 1800 Å to 8000 Å, the first particle size distribution range may be in the range of 45% to 75%, the second particle size distribution range may be in the range of 25% to 55%, and the average particle size may be in the range of 3000 Å to 4000 Å.

[0022] VII) According to I) to VI), in the diene rubber polymer, the first particle size distribution range may have a first particle size distribution range of 1500 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å, the first particle size distribution range may be in the range of 15% to 40%, the second particle size distribution range may be in the range of 60% to 85%, and the average particle size may be in the range of 3000 Å to 4000 Å.

[0023] VIII) According to I) to VII), in the diene rubber polymer, the first particle size distribution range may have a first particle size distribution range of 1500 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å, the first particle size distribution range may be in the range of 35% to 65%, the second particle size distribution range may be in the range of 35% to 65%, and the average particle size may be in the range of 3000 Å to 4000 Å.

[0024] IX) According to I) to VIII), in the diene rubber polymer, the first particle size distribution range may have a monodisperse particle size distribution range of 300 Å to 600 Å, and the average particle size may be in the range of 800 Å to 1800 Å.

[0025] X) According to another aspect of the present invention, a method for preparing a diene-based rubber polymer is provided, the method comprising: preparing a diene-based rubber polymer latex by emulsion polymerization of a conjugated diene compound; and obtaining the diene-based rubber polymer by acid thickening treatment of the diene-based rubber polymer latex. The acid thickening treatment is carried out using one or more acid thickening agents selected from acetic acid, formic acid, citric acid, phosphoric acid, dihydrogen phosphate, and monohydrogen phosphate.

[0026] XI) According to another aspect of the present invention, a graft copolymer is provided, comprising the diene rubber polymer described above.

[0027] According to XI), the content of the diene rubber polymer in the graft copolymer can be from 3% by weight to 80% by weight.

[0028] According to XIII) to XII), the swelling degree of the graft copolymer can be 8 to 20.

[0029] XIV) According to another aspect of the present invention, a thermoplastic resin composition comprising the graft copolymer described above is provided.

[0030] XV) According to another aspect of the invention, a molding article is provided that comprises the thermoplastic resin composition described above.

[0031] Beneficial effects

[0032] According to the present invention, the advantage of the present invention is that, by controlling its microstructure, particle size distribution and roundness, it provides diene rubber polymers that have an excellent balance of physical properties between impact resistance and flowability and can provide high gloss or high flowability, as well as graft copolymers and thermoplastic resin compositions comprising said diene rubber polymers. Attached Figure Description

[0033] Figure 1 This is a graph showing the particle size distribution of the diene rubber polymer after acid thickening treatment according to Example 1.

[0034] Figure 2 This is a graph showing the particle size distribution of the diene rubber polymer after acid thickening treatment according to Example 2.

[0035] Figure 3 This is a graph showing the particle size distribution of the diene rubber polymer after acid thickening treatment according to Example 3.

[0036] Figure 4 This is a graph showing the particle size distribution of the diene rubber polymer according to Example 4. Detailed Implementation

[0037] The invention is described in more detail below to aid in understanding it. However, the invention is not limited to the embodiments described below.

[0038] In this invention, the "diene rubber polymer" is preferably a polymer obtained by acid thickening of diene rubber polymer latex.

[0039] In this invention, "diene rubber polymer latex" can refer to a polymeric colloidal product comprising a conjugated diene compound dispersed in water.

[0040] In this invention, the “capillary hydrodynamic classification (CHDF) particle size distribution” can be the weight-average particle size distribution analyzed using a CHDF 4000 instrument (Mass Applied Science).

[0041] Weight-average particle size distribution refers to the difference in particle size corresponding to half the maximum particle size in the particle size distribution. As this difference (i.e., the half-width of the particle size) increases, the uniformity of rubber particle size increases. As a specific example, when fmax is the maximum particle size, half of the maximum particle size is fmax / 2, and the particle size range at the corresponding two points is the weight-average particle size distribution.

[0042] In this invention, "polydisperse" refers to a configuration in which the particle size distribution of a diene rubber polymer latex is bimodal, trimodal, or multimodal, and "monodisperse" refers to a configuration in which the particle size distribution of a diene rubber polymer latex is monomodal.

[0043] For reference, when polydisperse diene rubber polymers are included, the size of the diene rubber polymer latex particles is widely distributed from small diameter to large diameter, which may affect the physical properties of the graft copolymer.

[0044] In addition, when monodisperse diene rubber polymers are included, the particle distribution of the diene rubber polymer latex can be uniform, and a relatively narrow particle size distribution is formed due to the presence of only small diameters or only large diameters, which may affect the physical properties of the graft copolymer.

[0045] For example, it can directly affect the impact strength and gloss of thermoplastic resin compositions containing graft copolymers, and can indirectly affect the melt index and swelling degree of graft copolymers.

[0046] The inventors have demonstrated that, prior to the preparation of the graft copolymer, when the microstructure, polydisperse particle size distribution, and roundness of the diene rubber polymer are controlled within a certain range, an excellent balance between impact resistance and flowability is achieved, resulting in high gloss and high flowability. Based on these results, the inventors conducted further research to complete this invention.

[0047] The diene rubber polymer of the present invention comprises 20% to 30% cis-1,4-bonds, 55% to 65% trans-1,4-bonds, and the balance 1,2-bonds, exhibiting a first particle size distribution range of 200 Å to 3000 Å when subjected to capillary hydrodynamic classification, and satisfying a roundness within a predetermined range. In this case, the balance between impact resistance and flowability can be excellent. Furthermore, high gloss or high flowability can be provided, thus the polymer can be usefully used in products requiring impact resistance, high gloss, or high flowability.

[0048] The following is a detailed description of diene rubber polymers.

[0049] Diene-based rubber polymers

[0050] The diene rubber polymer of the present invention may contain 20% to 30% cis-1,4-bonds, 55% to 65% trans-1,4-bonds and the balance 1,2-bonds.

[0051] For example, diene-based rubber polymers may include one or more selected from polybutadiene rubber, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-(ethylene-butadiene)-styrene block copolymer, acrylonitrile-butadiene rubber, acrylonitrile-styrene-butadiene rubber and methyl methacrylate-butadiene rubber, preferably polybutadiene rubber, styrene-butadiene rubber or acrylonitrile-butadiene rubber, more preferably polybutadiene rubber.

[0052] Diene-based rubber polymers can preferably be obtained by emulsion polymerization of conjugated diene compounds followed by acid thickening.

[0053] In this invention, for example, the conjugated diene compound may include one or more selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene, preferably 1,3-butadiene.

[0054] In this invention, cis-1,4-bonds, trans-1,4-bonds, and 1,2-bonds can be collectively referred to as microstructures.

[0055] Microstructure is represented by the results of 13C 1D normal NMR analysis, and for example, microstructure can be a value measured during the pre-crosslinking step.

[0056] Microstructure can also be measured using IR, but NMR is preferred for accuracy due to the possibility of overlapping areas.

[0057] For example, the microstructure may have 20% to 27% cis-1,4-bonds, 57% to 63% trans-1,4-bonds, and the balance 1,2-bonds. In this case, thermoplastic resin compositions comprising graft copolymers containing diene rubber polymers can be endowed with a physical balance between impact resistance and flowability, as well as high gloss.

[0058] As a specific example, the microstructure may have 20% to 25% by weight of cis-1,4-bonds, 57% to 62% by weight of trans-1,4-bonds, and 15% to 20% by weight of 1,2-vinyl bonds; as a preferred example, the microstructure may have 22% to 24.5% by weight of cis-1,4-bonds, 59% to 61% by weight of trans-1,4-bonds, and 15% to 18% by weight of 1,2-vinyl bonds.

[0059] Diene rubber polymers can have a particle size distribution measured by capillary hydrodynamic classification (CHDF) (hereinafter referred to as "CHDF particle size distribution") that exhibits not only a monodisperse particle size distribution but also a polydisperse particle size distribution with a range of particle size distributions.

[0060] In this invention, polydisperse particle size distribution refers to the distribution range that includes one peak. Here, particle size distribution range refers to the range of particle size distribution of diene rubber polymers, and polydisperse particle size distribution refers to the distribution range that includes two or more peaks.

[0061] For reference, when polydisperse diene polymers are included, the diene polymer latex particles have a wide range of sizes from small to large diameters, which may affect the physical properties of the graft copolymer. When monodisperse diene polymers are included, the diene polymer latex particle distribution can be uniform, and due to the presence of only small or only large diameters, a relatively narrow particle size distribution is formed, which can affect the physical properties of the graft copolymer.

[0062] For example, a polydisperse particle size distribution may include one or more peaks in a first particle size distribution range of 200 Å to 1800 Å and a second particle size distribution range of 1800 Å to 8000 Å, respectively. In the case of the particle size distribution of conventional diene rubber polymers, the particle size distribution range is narrow, resulting in graft copolymers with poor flowability. On the other hand, according to the present invention, since the particle size distribution range is wide and a polydisperse particle size distribution is present, the problem of poor flowability can be solved, and the productivity of graft copolymers can be improved.

[0063] As a specific example, polydisperse particle size distributions can exhibit a first particle size distribution range of 200 Å to 1500 Å and a second particle size distribution range of 1800 Å to 8000 Å. Within this range, flowability can be improved.

[0064] For example, the weight ratio (first:second) of particles contained in the first particle size distribution range to particles contained in the second particle size distribution range can be from 1:0.60 to 1:0.90. In this case, flowability can be improved.

[0065] As a preferred example, the weight ratio (first:second) of particles contained in the first particle size distribution range to particles contained in the second particle size distribution range can be from 1:0.65 to 1:0.85. In this case, flowability can be improved.

[0066] As a preferred example, the weight ratio (first:second) of particles contained in the first particle size distribution range to particles contained in the second particle size distribution range can be from 1:0.69 to 1:0.82. In this case, flowability can be improved.

[0067] For example, within the entire particle size distribution range exhibited by diene rubber polymers, a first particle size distribution range may be included, comprising 45% to 75% by weight, 45% to 65% by weight, and preferably 50% to 65% by weight. Within this range, flowability can be improved.

[0068] For example, within the entire particle size distribution range exhibited by diene rubber polymers, a second particle size distribution range may be included, comprising 25% to 55% by weight, 35% to 55% by weight, and preferably 35% to 45% by weight. Within this range, flowability can be improved.

[0069] For example, a polydisperse particle size distribution may include one or more peaks in a first particle size distribution range of 1500 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å. In the case of the particle size distribution of conventional diene rubber polymers, graft copolymers with poor flowability are provided due to the narrow particle size distribution range. On the other hand, according to the present invention, since a polydisperse particle size distribution is present in addition to a wide particle size distribution range, the problem of poor flowability can be solved, and the productivity of graft copolymers can be improved.

[0070] As a specific example, polydisperse particle size distributions can exhibit a first particle size distribution range of 1500 Å to 3000 Å or 1800 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å. Within this range, flowability can be improved.

[0071] For example, the weight ratio (first:second) of particles contained in the first particle size distribution range to particles contained in the second particle size distribution range can be from 1:0.60 to 1:0.90. In this case, flowability can be improved.

[0072] As a preferred example, the weight ratio of particles contained in the first particle size distribution range to particles contained in the second particle size distribution range can be from 1:0.65 to 1:0.85. In this case, flowability can be improved.

[0073] As a preferred example, the weight ratio of particles contained in the first particle size distribution range to particles contained in the second particle size distribution range can be from 1:0.69 to 1:0.82. In this case, flowability can be improved.

[0074] For example, within the entire particle size distribution range exhibited by diene rubber polymers, a first particle size distribution range may be included, comprising 15 to 40 wt%, 20.0 to 32.9 wt%, or 20.0 to 30.0 wt%, preferably 22.0 to 28.0 wt%. Within this range, flowability can be improved.

[0075] For example, within the entire particle size distribution range exhibited by diene rubber polymers, a second particle size distribution range may be included, comprising 60 wt% to 85 wt%, 67.1 wt% to 80.0 wt%, or 70.0 wt% to 80.0 wt%, preferably 72.0 wt% to 78.0 wt%. Within this range, flowability can be improved.

[0076] For example, a polydisperse particle size distribution may include one or more peaks in a first particle size distribution range of 1500 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å. In the case of the particle size distribution of conventional diene rubber polymers, graft copolymers with poor flowability are provided due to the narrow particle size distribution range. On the other hand, according to the present invention, since a polydisperse particle size distribution is present in addition to a wide particle size distribution range, the problem of poor flowability can be solved, and the productivity of graft copolymers can be improved.

[0077] As a specific example, polydisperse particle size distributions can exhibit a first particle size distribution range of 1500 Å to 3000 Å or 1800 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å. Within this range, flowability can be improved.

[0078] For example, the weight ratio (first:second) of particles contained in the first particle size distribution range to particles contained in the second particle size distribution range can be from 1:0.84 to 1:0.94. In this case, flowability can be improved.

[0079] As a preferred example, the weight ratio (first:second) of particles contained in the first particle size distribution range to particles contained in the second particle size distribution range can be from 1:0.91 to 1:0.93. In this case, flowability can be improved.

[0080] As a more preferred example, the weight ratio (first:second) of particles contained in the first particle size distribution range to particles contained in the second particle size distribution range can be from 1:0.92 to 1:0.93. In this case, flowability can be improved.

[0081] For example, within the entire particle size distribution range exhibited by diene rubber polymers, a first particle size distribution range can be included within 35% to 65%, preferably within 45% to 65%, and more preferably within 45% to 55%. Within this range, flowability can be improved.

[0082] For example, within the entire particle size distribution range exhibited by diene rubber polymers, the second particle size distribution range can be included within 35% to 65%, preferably within 45% to 65%, and more preferably within 45% to 55%. Within this range, flowability can be improved.

[0083] As a specific example, monodisperse particle size distributions can exhibit a particle size range of 350 Å to 550 Å. Within this range, flowability can be improved.

[0084] Unless otherwise specified, particle size distribution is based on weight ratio.

[0085] Diene-based rubber polymers can have a roundness of 1.03 to 1.5, preferably 1.05 to 1.08, as calculated by Equation 1 below. In this case, uniform spherical particles can be provided.

[0086] [Equation 1]

[0087] In Equation 1, Di is the ratio of the major axis length to the minor axis length of the i-th particle in the latex [major axis length / minor axis length].

[0088] Roundness is an indicator of the sphericity of particles in latex, also known as sphericity. For 50 particles in a latex, the length of the major axis passing through the center of the particle and the length of the minor axis passing through the center of the particle and perpendicular to the major axis are measured. The ratio of the major axis length to the minor axis length in each particle (major axis length / minor axis length) is calculated. Roundness is defined as the average ratio of the major axis length to the minor axis length of each particle. When the above value is close to 1, the lengths of the major and minor axes of each particle become closer, which may mean that the particles that make up the latex are closer to being spheres.

[0089] Diene-based rubber polymers can have an average particle size of 3000 Å to 4000 Å or 800 Å to 1800 Å. In this case, impact resistance can be improved.

[0090] For example, the average particle size of the diene rubber polymer can preferably be from 3000 Å to 3700 Å, more preferably from 3200 Å to 3600 Å.

[0091] As another example, the average particle size of the diene rubber polymer can preferably be from 952 Å to 1510 Å, more preferably from 1000 Å to 1400 Å.

[0092] In this invention, the average particle size can be measured by dynamic light scattering, and specifically, using a Nicomp 380 particle size analyzer (manufacturer: PSS) in Gaussian mode. As a specific measurement example, a sample is prepared by diluting 0.1 g of latex (TSC: 35 to 50 wt%) with distilled water by a factor of 1000 to 5000; that is, the sample is appropriately diluted to not significantly deviate from the 300 kHz intensity setting and placed in a glass tube. Then, in the measurement mode of dynamic light scattering / intensity 300 kHz / intensity-weight Gaussian analysis, the average particle size of the sample is measured using a flow cell in auto-dilution. The settings are as follows: temperature: 23°C; measurement wavelength: 632.8 nm; and channel width: 10 μsec.

[0093] Methods for controlling the microstructure and swelling degree of diene rubber polymers include changing the type and content of polymerization initiators, using free radical catalysts or alkali metal catalysts, changing the polymerization temperature, and / or changing the type and content of chain transfer agents. Among these factors, the effect of polymerization temperature is significant; therefore, the proportion of cis-1,4- bonds varies greatly with polymerization temperature, and the swelling degree also varies greatly with the proportion of cis-1,4- bonds.

[0094] For example, the degree of swelling can be measured in the following ways.

[0095] First, diene rubber polymer latex was dropwise added to a mixture containing a 1:1 volume ratio of ethanol-water solution and 1% by weight of sulfuric acid to obtain a solid, which was then completely dried. Approximately 1 g of the obtained solid was immersed in 100 ml of toluene in a dark room at room temperature for 24 hours, and then filtered through a 100-mesh wire mesh to obtain the toluene-insoluble contents. After the toluene-insoluble material was completely dried, the degree of swelling was calculated by dividing the weight before complete drying by the weight after complete drying.

[0096] In this invention, complete drying means the weight when there is no further weight change under vacuum drying conditions.

[0097] For example, the degree of swelling can be 4 to 12, preferably 5.8 to 10.1, and more preferably 6 to 9. Within this range, impact resistance can be improved.

[0098] As another example, in diene-based rubber polymers, a first particle size distribution range can be 200 Å to 1800 Å, and a second particle size distribution range can be 1800 Å to 8000 Å. The first particle size distribution range can be in the range of 45% to 75%, the second particle size distribution range can be in the range of 25% to 55%, and the average particle size can be in the range of 3000 Å to 4000 Å. In this case, the swelling degree of the graft copolymer containing the diene-based rubber polymer can be controlled, and therefore the thermoplastic resin composition containing this graft copolymer can have an excellent balance of physical properties between impact resistance and flowability.

[0099] As another example, diene rubber polymers can be rubber latexes in which the particle size distribution measured by capillary hydrodynamic classification (CHDF) (hereinafter referred to as "CHDF particle size distribution") is a polydisperse particle size distribution.

[0100] For example, the polydisperse particle size distribution of CHDF can exhibit a first particle size distribution range of 1500 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å. In this case, the problem of providing graft copolymers with poor processability in the past can be solved. In addition, the productivity of graft copolymers can be ensured.

[0101] As another example, the diene rubber polymer can be a diene rubber polymer containing 20% ​​to 30% cis-1,4-bonds, 55% to 65% trans-1,4-bonds and the balance 1,2-bonds, and can have a polydisperse particle size distribution when performing capillary hydrodynamic classification, said polydisperse particle size distribution including one or more peaks in a first particle size distribution range of 1500 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å.

[0102] Within the entire particle size distribution range exhibited by the diene rubber polymer, the first particle size distribution range can account for 15% to 40%, and the second particle size distribution range can account for 60% to 85%. In this case, the swelling degree of the graft copolymer containing the diene rubber polymer can be controlled, and thus the thermoplastic resin composition containing the graft copolymer can have an excellent balance of physical properties between impact resistance and flowability.

[0103] Diene-based rubber polymers can be rubber latexes in which the particle size distribution measured by capillary hydrodynamic classification (CHDF) (hereinafter referred to as "CHDF particle size distribution") is a polydisperse particle size distribution.

[0104] For example, the polydisperse particle size distribution of CHDF can exhibit a first particle size distribution range of 1500 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å. In this case, the problem of providing graft copolymers with poor processability in the past can be solved. In addition, the productivity of graft copolymers can be ensured.

[0105] As another example, the diene rubber polymer can be a diene rubber polymer containing 20 to 30% cis-1,4-bonds, 55 to 65% trans-1,4-bonds, and the balance 1,2-bonds, and can have a polydisperse particle size distribution when subjected to capillary hydrodynamic classification, said polydisperse particle size distribution including one or more peaks in a first particle size distribution range of 1500 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å. In the entire particle size distribution range exhibited by the diene rubber polymer, the first particle size distribution range can account for 35% to 65%, and the second particle size distribution range can account for 35% to 65%. In this case, the swelling degree of the graft copolymer containing the diene rubber polymer can be controlled, so the thermoplastic resin composition containing the graft copolymer can have an excellent balance of physical properties between impact resistance and flowability.

[0106] As another example, the diene rubber polymer can be a diene rubber polymer containing 20% ​​to 30% cis-1,4-bonds, 55% to 65% trans-1,4-bonds, and the balance 1,2-bonds, which can have a monodisperse particle size distribution of 300 Å to 600 Å when subjected to capillary hydrodynamic fractionation, and can have a swelling degree of 4 to 12. In this case, the thermoplastic resin composition containing the diene rubber polymer can achieve an excellent balance of physical properties between impact resistance and flowability.

[0107] Diene-based rubber polymers may include linear structures that appear in the pre-crosslinking step.

[0108] For example, diene rubber polymers can be prepared by various methods, and can be prepared by the following methods.

[0109] Preparation methods of diene rubber polymers

[0110] For example, the diene-based rubber polymer according to the present invention can be obtained by emulsion polymerization of a conjugated diene compound to prepare a diene-based rubber polymer latex and acid thickening treatment of the diene-based rubber polymer latex.

[0111] For example, diene-based rubber polymer latex can be prepared by including the following steps: a first step of polymerizing 20 to 40 parts by weight of a total of 100 parts by weight of a conjugated diene compound, 0.1 to 2 parts by weight of an emulsifier, a molecular weight regulator, and an electrolyte; and a second step of adding the remaining conjugated diene compound and molecular weight regulator and polymerizing to obtain a diene-based rubber polymer latex.

[0112] For example, the emulsifier can be a polymer of unsaturated fatty acids or their metal salts. In this case, the latex stability can be excellent.

[0113] For example, based on 100 parts by weight of the conjugated diene compound, the emulsifier content can be 0.3 to 1.7 parts by weight, preferably 0.5 to 1.5 parts by weight, and more preferably 0.13 to 0.2 parts by weight. Within this range, the impact resistance can be excellent, productivity can be increased during injection molding, and the appearance quality can be improved.

[0114] For example, the molecular weight regulator can be a thiol molecular weight regulator, preferably tert-dodecyl thiol.

[0115] For example, based on 100 parts by weight of the conjugated diene compound, a molecular weight regulator may be included in an amount of 0.05 to 0.3 parts by weight, preferably 0.1 to 0.25 parts by weight, more preferably 0.13 to 0.2 parts by weight. Within this range, impact resistance can be improved.

[0116] For example, in the first step, the polymerization reaction can be carried out at 50°C to 60°C for 50 to 70 minutes, preferably at 53°C to 57°C for 55 to 65 minutes. In this case, the half-width of the diene rubber polymer particle size can be controlled to significantly improve impact resistance and flowability.

[0117] For example, in the first step, polymerization can be carried out using a mixture comprising 0.01 to 0.5 parts by weight of a redox catalyst, 0.01 to 0.7 parts by weight of a lipophilic polymerization initiator, and 80 to 120 parts by weight of deionized water, preferably 0.05 to 0.3 parts by weight of the redox catalyst, 0.1 to 0.5 parts by weight of the lipophilic polymerization initiator, and 90 to 110 parts by weight of deionized water. Within this range, productivity can be increased due to the reduction of unreacted monomers, and the physical properties of the graft copolymer comprising the polymer can be improved.

[0118] For example, redox catalysts may include one or more selected from sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, ferrous sulfate, dextrose, sodium pyrrole phosphate, and sodium sulfite. Within this range, the productivity and physical properties of graft copolymers can be improved by reducing unreacted monomers.

[0119] For example, the lipid-soluble polymerization initiator may include one or more selected from alkyl peroxides, aryl peroxides and azonitrs, particularly one or more selected from cumene hydroperoxide, diisopropylbenzene hydroperoxide, azobisisobutyronitrile, tert-butyl hydroperoxide, p-methane hydroperoxide and benzoyl peroxide, preferably tert-butyl hydroperoxide.

[0120] For example, the electrolyte may include one or more selected from K2CO3, Na2SO4, Na3PO4, NaH2PO4 and Na2HPO4, preferably K2CO3.

[0121] For example, based on 100 parts by weight of the conjugated diene compound, an electrolyte may be included in an amount of 0.1 to 0.5 parts by weight, preferably 0.2 to 0.4 parts by weight. Within this range, impact resistance can be excellent, productivity can be increased during injection molding, and appearance quality can be improved.

[0122] For example, after the first step, in the second step, preferably, the temperature can be raised to 73°C to 83°C while the remaining conjugated diene compound and molecular weight regulator are continuously added for 9 to 11 hours, and the temperature can be maintained for 8 to 10 hours. More preferably, the temperature can be raised to 75°C to 80°C while the remaining conjugated diene compound and molecular weight regulator are continuously added for 9.5 to 10.5 hours, and the temperature can be maintained for 8.5 to 9.5 hours. In this case, due to the increase in the half-maximum width of the conjugated diene rubber particle size, the impact resistance can be increased and the flowability can be excellent.

[0123] In this invention, "continuous feeding" means that the components are not fed in batches.

[0124] For example, depending on continuous feeding, the components can be fed dropwise, stepwise or continuously for more than 10 minutes, more than 30 minutes, more than 1 hour, preferably more than 2 hours, for example less than 12 hours, less than 11 hours or less than 10 hours within the polymerization time range.

[0125] The second step may preferably include the following steps 2-1): continuously adding the remaining conjugated diene compound and molecular weight regulator for 9 to 11 hours, raising the temperature to 73°C to 83°C and maintaining it for 8 to 10 hours, and carrying out the polymerization reaction while maintaining the temperature; step 2-2): adding 0.05 to 0.2 parts by weight of a water-soluble initiator and 0.05 to 0.3 parts by weight of an emulsifier at a polymerization conversion rate of 30% to 40% by weight, and carrying out the polymerization reaction; and step 2-3): terminating the polymerization reaction at a polymerization conversion rate of 98% to 209% by weight.

[0126] In this invention, polymerization conversion can be defined as the weight (wt%) of monomers converted into polymer based on 100% of the total weight of monomers introduced before the end of polymerization. Methods for measuring polymerization conversion according to these definitions can be used in this invention without any particular limitation. As a specific example, 1.5 g of the prepared latex is dried in a hot air dryer at 150°C for 15 minutes, its weight is measured, the total solids content (TSC) is calculated using Equation 2 below, and the polymerization conversion is calculated using the total solids content using Equation 3 below.

[0127] Equation 3 is based on the assumption that the total weight of the introduced monomers is 100 parts by weight.

[0128] [Equation 2]

[0129] Total solids content (%) = [weight after drying / weight before drying] × 100

[0130] [Equation 3]

[0131] Polymerization conversion rate (%) = [Total solids content × (total weight of added monomers, ion-exchange water, and auxiliary materials) / 100] - (weight of added auxiliary materials excluding monomers and ion-exchange water)

[0132] In Equation 3, the auxiliary materials include initiators, emulsifiers, electrolytes, and molecular weight regulators.

[0133] The introduced monomer refers to a conjugated diene compound.

[0134] For example, in step 2-2), one or more of hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate can be used as water-soluble initiators.

[0135] For example, based on 100 parts by weight of the conjugated diene compound, a water-soluble initiator may be included in an amount of 0.07 to 0.15 parts by weight, preferably 0.09 to 0.13 parts by weight. Within this range, productivity can be increased and physical properties can be improved by reducing unreacted monomers.

[0136] For example, in step 2-2), the emulsifier may be selected from the emulsifier described in step 1).

[0137] For example, based on 100 parts by weight of the conjugated diene compound, the emulsifier of step 2-2) may be included in an amount of 0.1 to 0.25 parts by weight, preferably 0.1 to 0.2 parts by weight. Within this range, by reducing the gel content, impact resistance can be improved, and residues during the injection molding process can be reduced.

[0138] For example, the diene rubber polymer latex obtained in steps 2-3) can have an average particle size of 3000 Å to 4000 Å, preferably 3000 Å to 3600 Å, and more preferably 3200 Å to 3700 Å. Within this range, the impact resistance can be significantly increased due to the increased effective surface area of ​​the rubber, and physical properties such as flowability can be excellent.

[0139] For example, the diene rubber polymer latex obtained in steps 2-3) can have an average particle size of 800 Å to 1800 Å, preferably 952 Å to 1510 Å, and more preferably 1000 Å to 1400 Å. Within this range, as the half-width of the particle size increases, the impact resistance can increase significantly, and physical properties such as flowability can be excellent.

[0140] Diene-based rubber polymer latexes can have polydisperse particle size distributions.

[0141] According to the polymerization method of the present invention, the particle size distribution is selectively broadened, making it easy to control the balance between processability and physical properties. However, due to the narrow polydisperse particle size distribution, although the tensile and viscoelastic properties are excellent, the processability may be poor and the productivity may be reduced.

[0142] Diene-based rubber polymer latexes are preferably latexes that have undergone acid thickening treatment.

[0143] The acid may be an acid commonly used in thickening treatments of diene rubber polymers, and may preferably include one or more selected from acetic acid, formic acid, citric acid, phosphoric acid, dihydrophosphoric acid, and monohydrophosphoric acid.

[0144] Based on 100 parts by weight (based on solids) of diene rubber polymer latex, the acid may be contained in an amount of 0.1 to 10 parts by weight or 0.5 to 5 parts by weight.

[0145] Furthermore, the diene rubber polymer latex obtained in steps 2-3) can have an average particle size of 800 Å to 1800 Å, preferably 952 Å to 1510 Å, and more preferably 1000 Å to 1400 Å. Within this range, the impact resistance can be significantly increased due to the increased half-width of the particle size, the balance between impact resistance and flowability can be excellent, and high gloss can be provided.

[0146] graft copolymer

[0147] The graft copolymer includes the aforementioned diene rubber polymers. In this case, the swelling degree of the graft copolymer can also be controlled, so the graft copolymer and the thermoplastic resin composition containing the graft copolymer can have an excellent balance of physical properties between impact resistance and flowability, and also have excellent high gloss.

[0148] For example, the graft copolymer can be a graft copolymer obtained by grafting 5 to 80 parts by weight of the above-mentioned diene rubber polymer and 20 to 95 parts by weight of one or more selected from aromatic vinyl compounds and vinyl cyanide compounds.

[0149] In this invention, for example, the aromatic vinyl compound may include one or more selected from the group consisting of 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, preferably one or more selected from the group consisting of styrene and α-methylstyrene, more preferably styrene. In this case, due to suitable flowability, processability and mechanical properties such as impact resistance can be excellent.

[0150] In this invention, for example, the vinyl cyanide compound may include one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, preferably acrylonitrile.

[0151] Furthermore, the graft copolymer may further include comonomers that can be copolymerized with aromatic vinyl compounds and vinyl cyanide compounds.

[0152] For example, the comonomer may include one or more selected from (meth)acrylate monomers, maleimide monomers, and amide monomers.

[0153] For example, (meth)acrylate monomers may include one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl acrylate, phenyl (meth)acrylate, 4-tert-butylphenyl (meth)acrylate, (di)bromophenyl (meth)acrylate, and chlorophenyl (meth)acrylate.

[0154] For example, the maleimide monomer can be N-phenylmaleimide, N-cyclohexylmaleimide, or a mixture thereof.

[0155] For example, the amide monomer can be acrylamide, methacrylamide, or a mixture thereof.

[0156] There are no particular limitations on the composition ratio of the aromatic vinyl compound, the vinyl cyanide compound, and the comonomer, and it can be, for example, 60% to 90% by weight of the aromatic vinyl compound, 10% to 40% by weight of the vinyl cyanide compound, and 0% to 30% by weight of the copolymerizable comonomer. Within this range, the degree of swelling can be easily controlled.

[0157] As another example, the composition can preferably be 20% to 70% by weight of an aromatic vinyl compound, 10% to 60% by weight of a vinyl cyanide compound, and 0% to 30% by weight of a copolymerizable comonomer.

[0158] For example, the ratio of diene rubber polymer latex (based on solids) to other compounds (including comonomers) can be from 5% to 80% by weight of diene rubber polymer latex and from 20% to 95% by weight of other compounds, preferably from 30% to 70% by weight of diene rubber polymer latex and from 30% to 70% by weight of other compounds. Within this range, the balance of physical properties can be excellent.

[0159] There are no particular limitations on the grafting degree of the grafted copolymer, but when the grafting degree is too low, the impact resistance tends to decrease, while when the grafting degree is too high, the flowability tends to decrease. Therefore, the grafting degree is preferably 25% to 85% by weight, more preferably 30% to 60% by weight.

[0160] Here, when measuring the grafting degree, acetone is used as a solvent to separate the grafted copolymer into soluble and insoluble components, and the grafting degree can be calculated using Equation 4 below.

[0161] [Equation 4]

[0162] Grafting degree (wt%) = [(Weight of acetone-insoluble matter - Weight of rubber polymer in the graft copolymer) / Weight of rubber polymer in the graft copolymer] × 100

[0163] As another example, the graft copolymer can be a graft copolymer obtained by grafting 5% to 80% (based on solids) of the aforementioned diene rubber polymer, 10% to 75% of an aromatic vinyl compound and 5% to 25% of a vinyl cyanide compound.

[0164] The swelling degree of graft copolymers can be measured in the following ways.

[0165] First, the graft copolymer was impregnated in acetone to extract the insoluble matter, and then completely dried. The obtained completely dried material was then immersed in toluene solvent in a dark room at room temperature for 48 hours and filtered to obtain the toluene-insoluble substance. The obtained toluene-insoluble substance was completely dried, and the degree of swelling was calculated by dividing the weight before complete drying by the weight after complete drying.

[0166] For example, the degree of swelling can be 8 to 20, preferably 10 to 18. Within this range, impact resistance can be improved.

[0167] There are no particular restrictions on the methods used to polymerize graft copolymers, and emulsion polymerization, suspension polymerization, bulk polymerization, etc., can be used.

[0168] Graft copolymers can be used alone, but can also be blended with other thermoplastic resins as needed. Other thermoplastic resins may include styrene-acrylonitrile resin, α-methylstyrene-acrylonitrile resin, styrene-acrylonitrile-methyl methacrylate resin, N-phenylmaleimide-styrene resin, N-phenylmaleimide-styrene-acrylonitrile resin, polycarbonate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyamide resin, rubber-reinforced polystyrene resin, acrylonitrile-butadiene rubber-styrene resin, acrylonitrile-ethylene propylene rubber-styrene resin, methyl methacrylate-butadiene rubber-styrene resin, and / or acrylonitrile-propylene rubber-styrene resin.

[0169] Preparation method of graft copolymer

[0170] When preparing graft copolymers, 40% to 70% (based on solids) of diene rubber polymer, 15% to 45% of aromatic vinyl compounds and 5% to 25% of vinyl cyanide compounds can be subjected to graft polymerization to obtain vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymers.

[0171] According to the method for preparing the graft copolymer, preferably, 45 wt% to 65 wt% (based on solids) of a diene rubber polymer, 20 wt% to 40 wt% of an aromatic vinyl compound, and 10 wt% to 20 wt% of a vinyl cyanide compound can be subjected to a graft polymerization reaction to obtain a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer. More preferably, 50 wt% to 60 wt% (based on solids) of a diene rubber polymer, 25 wt% to 35 wt% of an aromatic vinyl compound, and 12 wt% to 17 wt% of a vinyl cyanide compound can be subjected to a graft polymerization reaction to obtain a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound graft copolymer. Within this range, both flowability and impact resistance can be excellent.

[0172] The method for preparing the graft copolymer may preferably include: a first graft polymerization step a) based on a total of 100 parts by weight of a diene rubber polymer (based on solids), an aromatic vinyl compound, and a vinyl cyanide compound, continuously adding to 40 to 70 parts by weight (based on solids) of a diene rubber polymer latex and 80 to 120 parts by weight of deionized water a mixture containing 15 to 45 parts by weight of an aromatic vinyl compound, 5 to 25 parts by weight of a vinyl cyanide compound, 10 to 30 parts by weight of deionized water, 0.01 to 2 parts by weight of an emulsifier, and 0.01 to 2 parts by weight of a molecular weight regulator. The first graft polymerization step involves adding 2 parts by weight of a lipophilic polymerization initiator and 0.001 to 0.4 parts by weight of a redox catalyst, reacting at 65°C to 75°C for 2 to 4 hours; step b): after the first graft polymerization step, adding 0.001 to 0.6 parts by weight of a redox catalyst and 0.001 to 0.5 parts by weight of the lipophilic polymerization initiator; second graft polymerization step c): after adding the redox catalyst and the lipophilic polymerization initiator, raising the temperature to 75°C to 85°C and reacting for 50 to 70 minutes; and step d): terminating the polymerization reaction at a polymerization conversion rate of 90% to 99%. In this case, the flowability and impact resistance can be excellent.

[0173] For example, the emulsifier may be included in an amount of 0.01 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, more preferably 0.1 to 1 part by weight, and even more preferably 0.2 to 0.7 parts by weight. Within this range, the latex stability can be excellent, and the amount of coagulation can be reduced.

[0174] In step a), the emulsifier can be, for example, a polymer of unsaturated fatty acids (polyacids) or a metal salt thereof. In this case, the latex stability can be excellent, and coagulation can be reduced.

[0175] For example, the unsaturated fatty acid can be a straight-chain, branched, or cyclic unsaturated fatty acid with 8 to 22 carbon atoms. In this case, latex coagulation can be reduced, and residues in the injection mold can be reduced during the injection molding process.

[0176] In step a), the content of the molecular weight regulator is preferably 0.05 to 1.5 parts by weight, more preferably 0.1 to 1 part by weight, and even more preferably 0.2 to 0.7 parts by weight.

[0177] In step a), the content of the redox catalyst is preferably 0.001 to 0.3 parts by weight, more preferably 0.005 to 0.1 parts by weight.

[0178] In step a), preferably, the reaction can be carried out by continuously adding the mixture solution (diene rubber polymer) and the fat-soluble polymerization initiator at 67°C to 73°C for 2.5 to 3.5 hours. Within this range, grafting efficiency can be excellent, and latex coagulation can be reduced.

[0179] In step b), the content of the redox catalyst is preferably 0.001 to 0.6 parts by weight, more preferably 0.01 to 0.3 parts by weight.

[0180] In step b), the content of the molecular weight regulator is preferably 0.01 to 0.3 parts by weight, more preferably 0.03 to 0.1 parts by weight.

[0181] In step c), after adding the redox catalyst and the lipophilic polymerization initiator, the temperature can be raised to 77°C to 82°C, and the reaction can proceed for 55 to 65 minutes. Within this range, the reaction efficiency can be excellent, and condensation can be reduced.

[0182] In step d), the polymerization reaction can preferably be terminated at a polymerization conversion rate of 98% to 99%.

[0183] The vinyl cyanide-conjugated diene rubber-aromatic vinyl compound graft copolymer obtained in step d) can be subjected to conventional methods including coagulation, washing and drying to obtain the graft copolymer in powder form.

[0184] For example, 100 parts by weight (based on solids) of graft copolymer latex can be coagulated by adding an acid coagulant in an amount of 0.1 to 2 parts by weight, preferably 0.5 to 1.5 parts by weight.

[0185] For example, the acid coagulant may include one or more selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid, and acetic acid, with sulfuric acid being preferred. In this case, the coagulation efficiency can be excellent.

[0186] In this invention, when the electrolyte and coagulant are contained in a solvent such as water, their weight refers to the weight excluding the solvent.

[0187] Thermoplastic resin composition

[0188] In this invention, the thermoplastic resin composition may comprise a graft copolymer. As a specific example, the thermoplastic resin composition may comprise graft copolymers and other thermoplastic resins.

[0189] Here, other thermoplastic resins may be selected from one or more types of other thermoplastic resins described in the above-mentioned graft copolymers.

[0190] Where necessary, the thermoplastic resin composition may include hindered phenolic antioxidants, sulfur-containing organic compound antioxidants, and phosphorus-containing organic compound antioxidants; phenolic and acrylate heat stabilizers; benzotriazole, benzophenone, and salicylates as UV absorbers; lubricants, such as higher fatty acid amides; plasticizers, such as phosphate esters; halogen compounds, such as polybrominated phenyl ethers, tetrabromobisphenol A, brominated epoxy oligomers, and brominated compounds; phosphorus compounds; flame retardants, such as antimony trioxide; flame retardant additives; masking agents; carbon black, titanium dioxide; pigments; and / or dyes.

[0191] In addition, the thermoplastic resin composition may further include reinforcing agents or fillers, such as talc, calcium carbonate, aluminum hydroxide, glass fiber, glass sheet, glass bead, carbon fiber and / or metal fiber.

[0192] Thermoplastic resin composition can be obtained by mixing the above components using a mixing device.

[0193] For example, known mixing devices such as extruders, rollers, Banbury mixers, and kneaders can be used as mixing devices.

[0194] For example, when the impact strength is measured using a 1 / 4" thick sample according to ASTM D256, the impact strength of the thermoplastic resin composition can be 20 kgf·cm / cm or more, preferably 20 kgf·cm / cm to 30 kgf·cm / cm, and more preferably 23 to 30 kgf·cm / cm. In this case, molded articles with excellent mechanical strength can be provided.

[0195] For example, the thermoplastic resin composition may have a melt index of 26 g / 10 min to 35 g / 10 min, preferably 29 g / 10 min to 33 g / 10 min, more preferably 29 g / 10 min to 33 g / 10 min, as measured at 220°C and 10 kg according to ASTM D648. In this case, the balance of physical properties between impact resistance and flowability can be excellent, and high gloss or high flowability can be provided.

[0196] For example, according to ASTM D528 measurements, the thermoplastic resin composition can have a gloss (45°) of 95 or higher, preferably 95 to 99, more preferably 96 to 99. In this case, the balance of physical properties between impact resistance and flowability can be excellent, and high gloss or high flowability can be provided.

[0197] Preparation method of thermoplastic resin composition

[0198] In this invention, for example, a method for preparing a thermoplastic resin composition may include the following steps: preparing a vinyl cyanide-conjugated diene rubber-aromatic vinyl compound graft copolymer; and adding 15% to 35% by weight of the prepared graft copolymer and 65% to 85% by weight of the aromatic vinyl compound-vinyl cyanide copolymer to an extruder, performing melt kneading and extrusion. In this case, the flowability, gloss, and impact resistance can be excellent.

[0199] Preferably, the method for preparing the thermoplastic resin composition may include the following steps: preparing a vinyl cyanide-conjugated diene rubber-aromatic vinyl compound graft copolymer; and adding 20% ​​to 30% by weight of the prepared graft copolymer and 70% to 80% by weight of the aromatic vinyl compound-vinyl cyanide copolymer to an extruder, performing melt mixing and extrusion. In this case, the flowability, gloss, and impact resistance can be excellent.

[0200] For example, the melt kneading and extrusion steps can be carried out at a barrel temperature of 200°C to 330°C, preferably 210°C to 300°C, more preferably 210°C to 280°C, and even more preferably 220°C to 250°C. In this case, the production rate per unit time can be suitable, and melt kneading can be sufficiently achieved. Furthermore, thermal decomposition of the resin components can be prevented.

[0201] For example, the melt kneading and extrusion steps can be carried out at screw speeds of 100 rpm to 500 rpm, preferably 150 rpm to 400 rpm, more preferably 100 rpm to 350 rpm, even more preferably 200 rpm to 310 rpm, and most preferably 250 rpm to 350 rpm. In this case, due to the appropriate production volume per unit time, the process efficiency can be excellent, and over-cutting of the glass fibers can be suppressed.

[0202] For example, a Banbury internal mixer, a single-screw extruder, a twin-screw extruder, or a kneader can be used for melt kneading, but the invention is not particularly limited thereto.

[0203] For example, during melt kneading, based on 100 parts by weight of the thermoplastic resin composition (graft copolymer + other thermoplastic resin), one or more additives selected from the group consisting of colorants, heat stabilizers, light stabilizers, reinforcing agents, fillers, flame retardants, lubricants, plasticizers, antistatic agents and processing aids may be added in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

[0204] For example, an aromatic vinyl compound-vinyl cyanide compound copolymer may comprise 65% to 85% by weight of an aromatic vinyl compound and 15% to 35% by weight of a vinyl cyanide compound, preferably 70% to 80% by weight of an aromatic vinyl compound and 20% to 30% by weight of a vinyl cyanide compound. Within this range, due to suitable flowability, processability and impact resistance can be excellent.

[0205] In this invention, a polymer comprising a certain compound refers to a polymer prepared by polymerizing the compound, and the units in the polymer are derived from the compound.

[0206] For example, aromatic vinyl compound-vinyl cyanide compound copolymers can be prepared by solution polymerization or bulk polymerization, preferably bulk polymerization. In this case, heat resistance and flowability can be excellent.

[0207] Solution polymerization and bulk polymerization, which are commonly practiced in the field to which this invention pertain, may be used in this invention without particular limitation.

[0208] Molded products

[0209] Molded articles with excellent impact resistance can be manufactured using graft copolymers or thermoplastic resin compositions.

[0210] The molded articles may preferably comprise a thermoplastic resin composition. In this case, flowability and high gloss can be excellent. Furthermore, compared to conventional ABS resin, impact resistance can be greatly improved, and productivity and appearance can be superior.

[0211] Example

[0212] The present invention will now be described in detail with reference to embodiments, but the invention is not limited thereto. Furthermore, the terms "parts" and "%" shown in the embodiments are based on weight.

[0213] Example 1

[0214] <Preparation of Diene Rubber Polymers>

[0215] 90 parts by weight of ion-exchanged water, 30 parts by weight of 1,3-butadiene, 1 part by weight of oleic acid saponification, 0.4 parts by weight of potassium carbonate, 0.15 parts by weight of tert-dodecyl mercaptan, 0.15 parts by weight of tert-butyl hydroperoxide, 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrrolidate and 0.0025 parts by weight of ferrous sulfate were added in batches to a nitrogen-purged polymerization reactor.

[0216] Polymerization was carried out in the reactor at 55°C for 5 hours.

[0217] Then, polymerization was carried out by continuously feeding 70 parts by weight of 1,3-butadiene and 0.3 parts by weight of tert-dodecyl mercaptan at a constant rate while raising the temperature to 78°C. The continuous feeding process lasted for 9 hours.

[0218] Then, when the polymerization conversion rate reaches 30% to 40%, 0.1 parts by weight of potassium persulfate and 0.15 parts by weight of rosin acid emulsifier are added in batches.

[0219] Then, when the polymerization conversion rate reaches 95%, the polymerization is terminated to prepare diene rubber polymer latex.

[0220] Thickening of diene-based rubber polymer latex

[0221] 0.9 parts by weight of acetic acid were added to 100 parts by weight (based on solids) of diene rubber polymer latex to thicken the diene rubber polymer latex.

[0222] The average particle size of the thickened diene rubber polymer latex is 3450 Å.

[0223] <Preparation of Graft Copolymers>

[0224] A first mixture containing 15 parts by weight of acrylonitrile, 30 parts by weight of styrene, 0.4 parts by weight of dimer acid saponification, 0.35 parts by weight of tert-dodecyl mercaptan and 20 parts by weight of ion-exchanged water is prepared.

[0225] A second mixture containing 0.12 parts by weight of tert-butyl hydroperoxide, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrrolidone and 0.002 parts by weight of ferrous sulfate was prepared.

[0226] 55 parts by weight (based on solids) of thickened diene rubber polymer latex and 100 parts by weight of ion-exchanged water are fed in batches into a nitrogen-purged polymerization reactor.

[0227] Then, polymerization was carried out while the first and second mixtures were continuously fed into the reactor at a constant rate at 70°C for 3 hours.

[0228] Then, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrrolidone, 0.001 parts by weight of ferrous sulfate and 0.05 parts by weight of tert-butyl hydroperoxide were fed into the reactor, the temperature of the reactor was raised to 80°C at a constant rate for 1 hour, and the polymerization was terminated to obtain the graft copolymer latex.

[0229] The graft copolymer latex is coagulated, matured, washed, dehydrated and dried to obtain graft copolymer powder.

[0230] <Preparation of Thermoplastic Resin Compositions>

[0231] A thermoplastic resin composition was prepared by mixing 30 parts by weight of graft copolymer powder and 70 parts by weight of a styrene-acrylonitrile polymer (LG Chemical Co., Ltd., weight average molecular weight: 120,000 g / mol) containing 73% by weight of styrene and 28% by weight of acrylonitrile.

[0232] Comparative Example 1

[0233] <Preparation of Diene Rubber Polymers>

[0234] 75 parts by weight of ion-exchanged water, 90 parts by weight of 1,3-butadiene, 1.6 parts by weight of oleic acid saponification, 0.1 parts by weight of potassium carbonate, 0.1 parts by weight of tert-dodecyl mercaptan, 0.15 parts by weight of tert-butyl hydroperoxide, 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrrolidate, and 0.0025 parts by weight of ferrous sulfate were added in batches to a nitrogen-purged polymerization reactor.

[0235] Polymerization was carried out in a reactor at 55°C. When the polymerization conversion reached 30% to 40%, 0.3 parts by weight of potassium persulfate were added in batches.

[0236] Then, the reactor is heated to 72°C. When the polymerization conversion reaches 60% to 70%, 10 parts by weight of 1,3-butadiene are added in batches.

[0237] Then, when the polymerization conversion rate reaches 95%, the polymerization is terminated to prepare diene polymer latex.

[0238] The average particle size of the resulting diene-based rubber polymer latex was 1155 Å.

[0239] Thickening of diene-based rubber polymer latex

[0240] 1.5 parts by weight of acetic acid were added to 100 parts by weight (based on solids) of diene rubber polymer latex to thicken the diene rubber polymer latex.

[0241] The average particle size of the thickened diene rubber polymer latex is 3020 Å.

[0242] <Preparation of Graft Copolymers> and <Preparation of Thermoplastic Resin Compositions>

[0243] Perform each procedure as in Example 1.

[0244] Comparative Example 2

[0245] Except for the addition of 0.4 parts by weight of oleic acid saponifier in the <Preparation of Diene Rubber Polymers> of Example 1, the same procedure as in Example 1 was performed. The average particle size of the thickened diene rubber polymer latex was 3255 Å.

[0246] Comparative Example 3

[0247] Except for the polymerization being carried out at a reaction temperature of 51°C and then raised to 69°C in Example 1, the same procedure as in Example 1 was performed.

[0248] Comparative Example 4

[0249] Except for the polymerization being carried out at a reaction temperature of 60°C and then raised to 80°C in Example 1, the same procedure as in Example 1 was performed.

[0250] Comparative Example 5

[0251] Except for the addition of 1.4 parts by weight of acetic acid in <Thickening of Diene Rubber Polymer Latex> in Example 1, the same procedure as in Example 1 was performed.

[0252] Comparative Example 6

[0253] Except for the addition of 2.3 parts by weight of acetic acid in <Thickening of Diene Rubber Polymer Latex> in Example 1, the same procedure as in Example 1 was performed.

[0254] Comparative Example 7

[0255] Except for the addition of 2.5 parts by weight of acetic acid in <Thickening of Diene Rubber Polymer Latex> in Example 1, the same procedure as in Example 1 was performed.

[0256] <Experimental Example 1-1>

[0257] The physical properties of the diene rubber polymers of Example 1 and Comparative Examples 1 to 7 were measured as follows.

[0258] 1) Microstructure: The ratio (%) of cis-1,4-, trans-1,4-, and 1,2- bonds in the thickened diene rubber polymer latex was analyzed using 13C 1D normal NMR, and the results are shown in Table 1 below.

[0259] 2) Polydisperse particle size distribution: For thickened diene rubber polymer latex, the capillary hydrodynamic classification (CHDF) particle size distribution was measured using a MATEC CHDF 4000 instrument (Mass Applied Science). The first particle size distribution range was confirmed to be 200 Å to 1800 Å and the second particle size distribution range was confirmed to be 1800 Å to 8000 Å. The results are shown in Table 1.

[0260] 3) Weight ratio of the first and second diene rubber polymers: For the thickened diene rubber polymer latex, the weight ratio values ​​for each particle size distribution range (first and second) provided by the CHDF instrument were read, and the results are shown in Table 1. For reference, the particle size distribution ranges measured by the CHDF instrument are shown below. Figure 1 middle.

[0261] Here, the first particle size rubber polymer refers to the analytical value calculated within the first particle size distribution range of 200 Å to 1800 Å, and the second particle size rubber polymer refers to the analytical value calculated within the second particle size distribution range of 1800 Å to 8000 Å.

[0262] 4) Particle roundness measurement: For thickened diene rubber polymer latex, the ratio of the major axis length to the minor axis length of the particles was measured, and the roundness of the particles was calculated based on their average value. Specifically, after analyzing each latex using a TEM instrument (JEM-1400, Jeol), the major axis length and minor axis length of each of 50 particles were measured, and the particle roundness was calculated using Equation 1 below. The results are shown in Table 1 below.

[0263] [Equation 1]

[0264] In Equation 1, Di represents the ratio of the major axis length to the minor axis length of the i-th particle [major axis length / minor axis length].

[0265] Specifically, each latex was analyzed using a TEM instrument (JEM-1400, Jeol, 40K), and at least 50 to 100 particles were identified. In the images where 50 particles were identified, the major and minor axis lengths of each particle were measured, and roundness was calculated. For reference, more than 200 particles were identified using a TEM instrument (JEM-1400, Jeol, 25K), fewer than 50 particles were identified using a TEM instrument (JEM-1400, Jeol, 50K), and fewer than 10 particles were identified using a TEM instrument (JEM-1400, Jeol, 100K).

[0266] 5) Average particle size (Å): 0.1 g of thickened diene rubber polymer latex was mixed with 100 g of distilled water using a Nicomp 380 apparatus (manufacturer: PSS), and the results are shown in Table 1 below.

[0267] <Experimental Example 1-2>

[0268] The physical properties of the graft copolymer powders of Example 1 and Comparative Examples 1 to 7 were measured as follows.

[0269] 1) Swelling degree: Immerse 2g of graft copolymer powder in 300ml of acetone and stir for 24 hours. Extract the insoluble matter from the solution.

[0270] The insoluble substance was soaked in 100 ml of toluene for 48 hours. The weight of the toluene-insoluble substance (weight a) and the weight of the vacuum-dried toluene-insoluble substance (weight b) were measured after filtration through a 100-mesh metal wire mesh. The degree of swelling was calculated using Equation 5 below, and the results are shown in Table 1.

[0271] [Equation 5]

[0272] Swelling degree = Weight of toluene-insoluble matter (weight a) / Weight after vacuum drying (weight b)

[0273] <Experimental Examples 1-3>

[0274] 100 parts by weight of the thermoplastic resin composition of Example 1 and Comparative Examples 1 to 7 were mixed with 1 part by weight of lubricant and 0.1 part by weight of heat stabilizer, and kneaded and extruded at 210°C and 160 rpm to obtain granules.

[0275] The obtained granules were injected using an injection molding machine (injection temperature: 230°C, injection pressure: 80 bar, Engel ES 200 / 45HL-Pro Series), and then dried at 25°C and 50±5°C relative humidity for 12 hours to produce samples.

[0276] The physical properties of the sample are measured using the methods described below.

[0277] 1) Impact strength: For the obtained samples, the Izod impact strength (unit: kgf·cm / cm) was measured according to ASTM D256 using a Tinius Olsen (product name: Model Impact 104, manufacturer: Tinius Olsen Testing Machine Company) at a thickness of 1 / 4”, and the results are listed in Table 1.

[0278] 2) Melt index: For the obtained samples, the melt index (unit: g / 10min) was measured according to ASTM 648 at 220°C under a load of 10kg, and the results are shown in Table 1 below.

[0279] 3) Gloss: For the obtained samples, the gloss was measured at 45° using a gloss meter according to ASTM D528, and the results are shown in Table 1 below. As this value increases, the surface gloss improves.

[0280] [Table 1]

[0281] As shown in Table 1, in the case of diene rubber polymers in which the roundness of latex particles follows that of Example 1 of the present invention, the impact strength is greatly improved compared with Comparative Examples 1 to 7, which are outside the scope of the present invention, and the melt index and gloss are significantly improved.

[0282] Furthermore, in Comparative Examples 3 and 4, where the microstructure is outside the scope of this invention, the impact strength was significantly reduced compared to Example 1, and the melt index and gloss were also reduced.

[0283] Furthermore, in Comparative Examples 5 to 7, where the average particle size was outside the scope of the present invention, the impact strength was significantly reduced compared to Example 1, and the melt index and gloss were also reduced.

[0284] In addition, the following Figure 1 This is a graph showing the polydisperse particle size distribution according to Example 1. As shown below... Figure 1 As shown, a bimodal distribution is presented.

[0285] Specifically, as follows Figure 1 As shown, a bimodal distribution according to the present invention is observed. The first particle size distribution range of 200 Å to 1800 Å accounts for 47.7% by weight, and the second particle size distribution range of 1800 Å to 8000 Å accounts for 52.3% by weight. Here, the small diameter region can directly affect the gloss of the thermoplastic resin composition containing the graft copolymer, and the large diameter region can directly affect its impact strength.

[0286] In particular, it has been confirmed that the thermoplastic resin composition according to the invention exhibits an excellent balance of physical properties between impact resistance and flowability due to its superior impact strength and melt index. Furthermore, the thermoplastic resin composition displays a gloss of 95% or higher at 45°, making it suitable for products requiring high gloss. Additionally, the thermoplastic resin composition displays a uniform spherical shape with a roundness of 1.06.

[0287] <Experimental Examples 1-4>

[0288] Additional Comparative Example 1

[0289] Except for the addition of 3.0 parts by weight of oleic acid saponifier in the <Preparation of Diene Rubber Polymers> of Example 1, the same procedure as in Example 1 was performed. The average particle size of the thickened diene rubber polymer latex was 3020 Å.

[0290] Additional Comparative Example 2

[0291] Except for the addition of 1.8 parts by weight of acetic acid in <Thickening of Diene Rubber Polymer Latex> in Example 1, the same procedure as in Example 1 was performed. The average particle size of the thickened diene rubber polymer latex was 3970 Å.

[0292] Additional Comparative Example 3

[0293] Except for the process described in Example 1, "Preparation of Diene Rubber Polymers", in which the reaction was terminated at a polymerization conversion rate of 99%, the same procedure as in Example 1 was performed.

[0294] Additional Comparative Example 4

[0295] Except for terminating the reaction at a polymerization conversion rate of 90% in Example 1, the same procedure as in Example 1 was performed.

[0296] As described above, samples were manufactured and their physical properties were measured. The results are shown in Table 2 below.

[0297] [Table 2]

[0298] As shown in Table 2, in the case of diene rubber polymers in which the roundness of latex particles follows that of Example 1 of the present invention, the impact strength is greatly improved compared with the additional comparative examples 1 to 4 which are outside the scope of the present invention, and the melt index and gloss are significantly improved.

[0299] Furthermore, in Additional Comparative Examples 1 and 2, where the weight ratio of particles contained in the polydisperse particle size distribution range is outside the scope of the present invention, the impact strength is significantly reduced compared to Example 1, and the melt index and gloss are also reduced.

[0300] Furthermore, in the cases of Additional Comparative Examples 3 and 4, where the degree of swelling is outside the scope of the present invention, the impact strength was significantly reduced compared to Example 1, and the melt index and gloss were also reduced.

[0301] Example 2

[0302] <Preparation of Diene Rubber Polymers>

[0303] 90 parts by weight of ion-exchanged water, 30 parts by weight of 1,3-butadiene, 1 part by weight of oleic acid saponification, 0.4 parts by weight of potassium carbonate, 0.15 parts by weight of tert-dodecyl mercaptan, 0.15 parts by weight of tert-butyl hydroperoxide, 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrrolidate and 0.0025 parts by weight of ferrous sulfate were added in batches to a nitrogen-purged polymerization reactor.

[0304] Polymerization was carried out in the reactor at 55°C for 5 hours.

[0305] Then, polymerization was carried out by continuously feeding 70 parts by weight of 1,3-butadiene and 0.3 parts by weight of tert-dodecyl mercaptan at a constant rate while raising the temperature to 78°C. The continuous feeding process lasted for 9 hours.

[0306] Then, when the polymerization conversion rate reaches 30% to 40%, 0.1 parts by weight of potassium persulfate and 0.15 parts by weight of rosin acid emulsifier are added in batches.

[0307] Then, when the polymerization conversion reached 95%, the polymerization was terminated to prepare a diene-based rubber polymer latex. At this point, the average particle size of the diene-based rubber polymer latex was 1180 Å.

[0308] Thickening of diene-based rubber polymer latex

[0309] 0.9 parts by weight of acetic acid were added to 100 parts by weight (based on solids) of diene rubber polymer latex to thicken the diene rubber polymer latex.

[0310] The average particle size of the thickened diene rubber polymer latex is 3350 Å.

[0311] <Preparation of Graft Copolymers>

[0312] A first mixture containing 15 parts by weight of acrylonitrile, 30 parts by weight of styrene, 0.4 parts by weight of dimer acid saponification, 0.35 parts by weight of tert-dodecyl mercaptan and 20 parts by weight of ion-exchanged water is prepared.

[0313] A second mixture containing 0.12 parts by weight of tert-butyl hydroperoxide, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrrolidone and 0.002 parts by weight of ferrous sulfate was prepared.

[0314] 55 parts by weight (based on solids) of thickened diene rubber polymer latex and 100 parts by weight of ion-exchanged water are fed in batches into a nitrogen-purged polymerization reactor.

[0315] Then, polymerization was carried out while the first and second mixtures were continuously fed into the reactor at a constant rate at 70°C for 3 hours.

[0316] Then, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrrolidone, 0.001 parts by weight of ferrous sulfate and 0.05 parts by weight of tert-butyl hydroperoxide were fed into the reactor, the temperature of the reactor was raised to 80°C at a constant rate for 1 hour, and the polymerization was terminated to obtain the graft copolymer latex.

[0317] The graft copolymer latex is coagulated, matured, washed, dehydrated and dried to obtain graft copolymer powder.

[0318] <Preparation of Thermoplastic Resin Compositions>

[0319] A thermoplastic resin composition was prepared by mixing 30 parts by weight of graft copolymer powder and 70 parts by weight of a styrene-acrylonitrile polymer (LG Chemical Co., Ltd., weight average molecular weight: 120,000 g / mol) containing 73% by weight of styrene and 28% by weight of acrylonitrile.

[0320] Comparative Example 8

[0321] <Preparation of Diene Rubber Polymers>

[0322] 75 parts by weight of ion-exchanged water, 90 parts by weight of 1,3-butadiene, 1.6 parts by weight of oleic acid saponification, 0.1 parts by weight of potassium carbonate, 0.1 parts by weight of tert-dodecyl mercaptan, 0.15 parts by weight of tert-butyl hydroperoxide, 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrrolidate, and 0.0025 parts by weight of ferrous sulfate were added in batches to a nitrogen-purged polymerization reactor.

[0323] Polymerization was carried out in a reactor at 55°C. When the polymerization conversion reached 30% to 40%, 0.3 parts by weight of potassium persulfate were added in batches.

[0324] Then, the reactor is heated to 72°C. When the polymerization conversion reaches 60% to 70%, 10 parts by weight of 1,3-butadiene are added in batches.

[0325] Then, when the polymerization conversion rate reaches 95%, the polymerization is terminated to prepare diene polymer latex.

[0326] Thickening of diene-based rubber polymer latex

[0327] 1.5 parts by weight of acetic acid were added to 100 parts by weight (based on solids) of diene rubber polymer latex to thicken the diene rubber polymer latex.

[0328] The average particle size of the thickened diene rubber polymer latex is 3365 Å.

[0329] <Preparation of Graft Copolymers> and <Preparation of Thermoplastic Resin Compositions>

[0330] Perform each procedure in the same manner as in Example 2.

[0331] Comparative Example 9

[0332] Except for the addition of 0.4 parts by weight of oleic acid saponifier in the <Preparation of Diene Rubber Polymers> section of Example 2, the same steps as in Example 2 were performed. The average particle size of the thickened diene rubber polymer latex was 3280 Å.

[0333] <Experimental Example 2-1>

[0334] The physical properties of the diene rubber polymers of Examples 2 and Comparative Examples 8 and 9 were measured as follows.

[0335] 1) Microstructure: The ratio (%) of cis-1,4-, trans-1,4-, and 1,2- bonds in the thickened diene rubber polymer latex was analyzed using 13C 1D normal NMR, and the results are shown in Table 3 below.

[0336] 2) Polydisperse particle size distribution: For thickened diene rubber polymer latex, capillary hydrodynamic classification (CHDF) particle size distribution was measured using a MATEC CHDF 4000 instrument (Mass Applied Science), confirming a first particle size distribution range of 1500 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å. The results are shown in Table 3 below.

[0337] 3) Weight ratio of the first and second diene rubber polymers: For the thickened diene rubber polymer latex, the weight ratio values ​​for each particle size distribution range (first and second) were read from the CHDF instrument, and the results are shown in Table 3. For reference, the particle size distribution ranges measured by the CHDF instrument are shown below. Figure 2 middle.

[0338] Here, the first particle size rubber polymer refers to the analytical value calculated within the first particle size distribution range of 1500 Å to 3000 Å, and the second particle size rubber polymer refers to the analytical value calculated within the second particle size distribution range of 3000 Å to 8000 Å.

[0339] 4) Particle roundness measurement: For thickened diene rubber polymer latex, the ratio of the major axis length to the minor axis length of the particles was measured, and the roundness of the particles was calculated based on their average value. Specifically, after analyzing each latex using a TEM instrument (JEM-1400, Jeol), the major axis length and minor axis length of each of 50 particles were measured, and the particle roundness was calculated using Equation 1 below. The results are shown in Table 3 below.

[0340] [Equation 1]

[0341] In Equation 1, Di represents the ratio of the major axis length to the minor axis length of the i-th particle [major axis length / minor axis length].

[0342] Specifically, each latex was analyzed using a TEM instrument (JEM-1400, Jeol, 40K), and at least 50 to 100 particles were identified. In the images of the 50 identified particles, the lengths of the major and minor axes of each particle were measured, and roundness was calculated.

[0343] 5) Average particle size (Å): 0.1 g of thickened diene rubber polymer latex was mixed with 100 g of distilled water using a Nicomp 380 apparatus (manufacturer: PSS), and the results are shown in Table 3 below.

[0344] 6) Swelling degree measurement: Thickened diene rubber polymer latex is dropped into a mixture obtained by mixing an aqueous ethanol solution with a volume ratio of 1:1 and sulfuric acid based on 1% by weight of the aqueous ethanol solution to obtain a solid, and the solid is completely dried.

[0345] Approximately 1g of the obtained solid was immersed in 100ml of toluene in a dark room at room temperature for 24 hours, and then filtered through a 100-mesh metal wire mesh to obtain a toluene-insoluble substance.

[0346] The toluene-insoluble substance was completely dried, and the weight before complete drying was divided by the weight after complete drying. The values ​​are shown in Table 3 below.

[0347] <Experimental Example 2-2>

[0348] The physical properties of the graft copolymer powders of Example 2 and Comparative Examples 8 and 9 were measured as follows.

[0349] 1) Swelling degree: Immerse 2g of graft copolymer powder in 300ml of acetone and stir for 24 hours. Extract the insoluble matter from the solution.

[0350] The insoluble substance was soaked in 100 ml of toluene for 48 hours. The weight of the toluene-insoluble substance (weight a) and the weight of the vacuum-dried toluene-insoluble substance (weight b) were measured after filtration through a 100-mesh metal wire mesh. The degree of swelling was calculated using Equation 5 below, and the results are shown in Table 3.

[0351] [Equation 5]

[0352] Swelling degree = Weight of toluene-insoluble matter (weight a) / Weight after vacuum drying (weight b)

[0353] <Experimental Example 2-3>

[0354] 100 parts by weight of the thermoplastic resin compositions of Examples 2 and Comparative Examples 8 and 9 were mixed with 1 part by weight of lubricant and 0.1 part by weight of heat stabilizer, and kneaded and extruded at 210°C and 160 rpm to obtain granules.

[0355] The obtained granules were injected using an injection molding machine (injection temperature: 230°C, injection pressure: 80 bar, Engel ES 200 / 45HL-Pro Series), and then dried at 25°C and 50±5°C relative humidity for 12 hours to produce samples.

[0356] The physical properties of the sample are measured using the methods described below.

[0357] 1) Impact strength: For the obtained samples, the Izod impact strength (unit: kgf·cm / cm) was determined according to ASTM D256 using a Tinius Olsen (product name: Model Impact 104, manufacturer: Tinius Olsen Testing Machine Company) at a thickness of 1 / 4”, and the results are shown in Table 3 below.

[0358] 2) Melt index: For the obtained samples, the melt index (unit: g / 10min) was measured according to ASTM 648 at 220°C under a load of 10kg, and the results are shown in Table 3 below.

[0359] [Table 3]

[0360] As shown in Table 2, in the case of diene rubber polymers in which the roundness of latex particles follows that of Example 2 of the present invention, the impact strength and melt index are significantly improved compared with Comparative Examples 8 and 9, which are outside the scope of the present invention.

[0361] In particular, in Comparative Examples 8 and 9, where the roundness is outside the scope of the present invention, the impact strength is significantly reduced and the melt index is also reduced compared to Example 2.

[0362] also, Figure 2 This is a graph showing the polydisperse particle size distribution according to Example 2. As shown below... Figure 2 As shown, this confirms the bimodal or trimodal (corresponding to multimodal) distribution.

[0363] Specifically, as follows Figure 2 As shown, several peaks were observed. The first particle size distribution range of 1500 Å to 3000 Å accounted for 32.9% by weight, and the second particle size distribution range of 3000 Å to 8000 Å accounted for 67.1% by weight. Here, the small diameter region can affect the physical properties of the thermoplastic resin composition containing the graft copolymer, such as the melt index, and the large diameter region can directly affect its impact strength.

[0364] In particular, it has been confirmed that the thermoplastic resin composition according to the invention exhibits an excellent balance of physical properties between impact resistance and flowability due to its superior impact strength and melt index, and is suitable for products requiring high flowability. Furthermore, the thermoplastic resin composition displays a uniform spherical shape with a roundness of 1.06.

[0365] <Experimental Example 2-4>

[0366] Additional Comparative Example 5

[0367] Except for the addition of 1.0 part by weight of oleic acid saponifier in the <Preparation of Diene Rubber Polymers> section of Example 2, the same procedure as in Example 2 was performed. The average particle size of the thickened diene rubber polymer latex was 3272 Å.

[0368] Additional Comparative Example 6

[0369] Except for terminating the reaction at 91% polymerization conversion in Example 2's <Thickening of Diene Rubber Polymer Latex>, the same procedure as in Example 2 was performed. The thickened diene rubber polymer latex had an average particle size of 3360 Å.

[0370] Additional Comparative Example 7

[0371] Except for the use of 0.7 parts by weight of acetic acid in <Thickening of Diene Rubber Polymer Latex> in Example 2, the same procedure as in Example 2 was performed. The average particle size of the thickened diene rubber polymer latex was 3070 Å.

[0372] Additional Comparative Example 8

[0373] Except for the use of 1.5 parts by weight of acetic acid in <Thickening of Diene Rubber Polymer Latex> in Example 2, the same procedure as in Example 2 was performed. The average particle size of the thickened diene rubber polymer latex was 3860 Å.

[0374] Additional Comparative Example 9

[0375] Except for the use of 0.05 parts by weight of tert-dodecyl mercaptan in the <Preparation of Diene Rubber Polymers> section of Example 2, the same procedure as in Example 2 was performed. The average particle size of the thickened diene rubber polymer latex was 3275 Å.

[0376] Additional Comparative Example 10

[0377] Except for the use of 0.3 parts by weight of tert-dodecyl mercaptan in the <Preparation of Diene Rubber Polymers> section of Example 2, the same procedure as in Example 2 was performed. The average particle size of the thickened diene rubber polymer latex was 3365 Å.

[0378] As described above, samples were manufactured and their physical properties were measured. The results are shown in Table 4 below.

[0379] [Table 4]

[0380] As shown in Table 4, in the cases of Additional Comparative Examples 5 and 6, where the degree of swelling is outside the scope of the present invention, the impact strength is significantly reduced compared to Example 2, and the melt index is also reduced.

[0381] In addition, in the cases of Additional Comparative Examples 7 and 8, where the content of particles contained in the polydisperse particle size distribution range is outside the scope of the present invention, the impact strength is significantly reduced and the melt index is also reduced compared to Example 2.

[0382] Furthermore, in the cases of Additional Comparative Examples 9 and 10, in which the swelling degree of the rubber particles was outside the scope of the present invention, the impact strength was significantly reduced and the melt index was also reduced compared to Example 2.

[0383] Example 3

[0384] <Preparation of Diene Rubber Polymers>

[0385] 85 parts by weight of ion-exchanged water, 30 parts by weight of 1,3-butadiene, 3 parts by weight of oleic acid saponification, 0.35 parts by weight of potassium carbonate, 0.1 parts by weight of tert-dodecyl mercaptan, 0.15 parts by weight of tert-butyl hydroperoxide, 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrrolidate and 0.0025 parts by weight of ferrous sulfate were added in batches to a nitrogen-purged polymerization reactor.

[0386] Polymerization was carried out in a reactor at 55°C.

[0387] Then, when the polymerization conversion rate reaches 35%, 0.3 parts by weight of potassium persulfate are added, the temperature is raised to 72°C, and polymerization continues until the polymerization conversion rate reaches 65%.

[0388] Then, 15 parts by weight of 1,3-butadiene, 0.1 parts by weight of potassium persulfate and 0.3 parts by weight of oleic acid saponifier are added in batches.

[0389] Then, when the polymerization conversion reached 95%, the polymerization was terminated to prepare a diene-based rubber polymer latex. At this point, the average particle size of the diene-based rubber polymer latex was 1150 Å.

[0390] Thickening of diene-based rubber polymer latex

[0391] 0.95 parts by weight of acetic acid were added to 100 parts by weight (based on solids) of diene rubber polymer latex to thicken the diene rubber polymer latex.

[0392] The average particle size of the thickened diene rubber polymer latex is 3350 Å.

[0393] <Preparation of Graft Copolymers>

[0394] A first mixture containing 15 parts by weight of acrylonitrile, 30 parts by weight of styrene, 0.4 parts by weight of dimer acid saponification, 0.35 parts by weight of tert-dodecyl mercaptan and 20 parts by weight of ion-exchanged water is prepared.

[0395] A second mixture containing 0.12 parts by weight of tert-butyl hydroperoxide, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrrolidone and 0.002 parts by weight of ferrous sulfate was prepared.

[0396] 55 parts by weight (based on solids) of thickened diene rubber polymer latex and 100 parts by weight of ion-exchanged water are fed in batches into a nitrogen-purged polymerization reactor.

[0397] Then, polymerization was carried out while the first and second mixtures were continuously fed into the reactor at a constant rate at 70°C for 3 hours.

[0398] Then, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrrolidone, 0.001 parts by weight of ferrous sulfate and 0.05 parts by weight of tert-butyl hydroperoxide were fed into the reactor, the temperature of the reactor was raised to 80°C at a constant rate for 1 hour, and the polymerization was terminated to obtain the graft copolymer latex.

[0399] The graft copolymer latex is coagulated, matured, washed, dehydrated and dried to obtain graft copolymer powder.

[0400] <Preparation of Thermoplastic Resin Compositions>

[0401] A thermoplastic resin composition was prepared by mixing 30 parts by weight of graft copolymer powder and 70 parts by weight of a styrene-acrylonitrile polymer (LG Chemical Co., Ltd., weight average molecular weight: 120,000 g / mol) containing 73% by weight of styrene and 28% by weight of acrylonitrile.

[0402] Comparative Example 10

[0403] Except for the addition of 1.6 parts by weight of oleic acid saponifier in the <Preparation of Diene Rubber Polymers> section of Example 3, the same procedure as in Example 3 was performed. The average particle size of the thickened diene rubber polymer latex was 3335 Å.

[0404] Comparative Example 11

[0405] Except for the addition of 0.4 parts by weight of oleic acid saponifier in the <Preparation of Diene Rubber Polymers> section of Example 3, the same procedure as in Example 3 was performed. The average particle size of the thickened diene rubber polymer latex was 3315 Å.

[0406] Comparative Example 12

[0407] Except for increasing the reaction temperature from 51°C to 69°C in Example 3's <Preparation of Diene Rubber Polymers>, the procedure was the same as in Example 3. The average particle size of the thickened diene rubber polymer latex was 3310 Å.

[0408] Comparative Example 13

[0409] Except for increasing the reaction temperature from 60°C to 80°C in Example 3, <Preparation of Diene Rubber Polymers>, the same procedure as in Example 3 was performed. The average particle size of the thickened diene rubber polymer latex was 3330 Å.

[0410] Comparative Example 14

[0411] Except for the inclusion of 1.0 part by weight of acetic acid in Comparative Example 3 (<Thickening of Diene Rubber Polymer Latex>), the same procedure as in Example 3 was performed. The average particle size of the thickened diene rubber polymer latex was 2680 Å.

[0412] Comparative Example 15

[0413] Except for the inclusion of 2.0 parts by weight of acetic acid in Comparative Example 3 (<Thickening of Diene Rubber Polymer Latex>), the same procedure as in Example 3 was performed. The average particle size of the thickened diene rubber polymer latex was 4470 Å.

[0414] <Experimental Example 3-1>

[0415] The physical properties of the diene rubber polymers of Examples 3 and Comparative Examples 10 to 15 were measured as follows.

[0416] 1) Microstructure: The ratio (%) of cis-1,4-, trans-1,4-, and 1,2- bonds in the thickened diene rubber polymer latex was analyzed using 13C 1D normal NMR, and the results are shown in Table 5 below.

[0417] 2) Polydisperse particle size distribution: For thickened diene rubber polymer latex, capillary hydrodynamic classification (CHDF) particle size distribution was measured using a MATEC CHDF4000 instrument (Mass Applied Science), confirming a first particle size distribution range of 1500 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å. The results are shown in Table 5 below.

[0418] 3) Weight ratio of the first and second diene rubber polymers: For the thickened diene rubber polymer latex, the weight ratio values ​​for each particle size distribution range (first and second) provided by the CHDF instrument were read, and the results are shown in Table 5. For reference, the particle size distribution ranges measured by the CHDF instrument are shown below. Figure 3 middle.

[0419] Here, the first particle size rubber polymer refers to the analytical value calculated within the first particle size distribution range of 1500 Å to 3000 Å, and the second particle size rubber polymer refers to the analytical value calculated within the second particle size distribution range of 3000 Å to 8000 Å.

[0420] 4) Particle roundness measurement: For thickened diene rubber polymer latex, the ratio of the major axis length to the minor axis length of the particles was measured, and the roundness of the particles was calculated based on the average value. Specifically, after analyzing each latex using a TEM instrument (JEM-1400, Jeol), the major axis length and minor axis length of each of 50 particles were measured, and the particle roundness was calculated using Equation 1 below. The results are shown in Table 5 below.

[0421] [Equation 1]

[0422] In Equation 1, Di represents the ratio of the major axis length to the minor axis length of the i-th particle [major axis length / minor axis length].

[0423] Specifically, each latex was analyzed using a TEM instrument (JEM-1400, Jeol, 40K), and at least 50 to 100 particles were identified. In the images of the 50 identified particles, the lengths of the major and minor axes of each particle were measured, and roundness was calculated.

[0424] 5) Average particle size (Å): 0.1 g of thickened diene rubber polymer latex was mixed with 100 g of distilled water using a Nicomp 380 apparatus (manufacturer: PSS), and the results are shown in Table 5 below.

[0425] 6) Swelling degree measurement: Thickened diene rubber polymer latex is dropped into a mixture obtained by mixing an aqueous ethanol solution with a volume ratio of 1:1 and sulfuric acid based on 1% by weight of the aqueous ethanol solution to obtain a solid, and the solid is completely dried.

[0426] Approximately 1g of the obtained solid was immersed in 100ml of toluene in a dark room at room temperature for 24 hours, and then filtered through a 100-mesh metal wire mesh to obtain a toluene-insoluble substance.

[0427] The toluene-insoluble substance was completely dried, and the values ​​obtained by dividing the weight before complete drying by the weight after complete drying are shown in Table 5 below.

[0428] <Experimental Example 3-2>

[0429] The physical properties of the graft copolymer powders of Examples 3 and Comparative Examples 10 to 15 were measured as follows.

[0430] 1) Swelling degree: Immerse 2g of graft copolymer powder in 300ml of acetone and stir for 24 hours. Extract the insoluble matter from the solution.

[0431] The insoluble substance was soaked in 100 ml of toluene for 48 hours. The weight of the toluene-insoluble substance (weight a) and the weight of the vacuum-dried toluene-insoluble substance (weight b) were measured after filtration through a 100-mesh metal wire mesh. The degree of swelling was calculated using Equation 5 below, and the results are shown in Table 5.

[0432] [Equation 5]

[0433] Swelling degree = Weight of toluene-insoluble matter (weight a) / Weight after vacuum drying (weight b)

[0434] <Experimental Example 3>

[0435] 100 parts by weight of the thermoplastic resin composition of Example 3 and Comparative Examples 10 to 15 were mixed with 1 part by weight of lubricant and 0.1 part by weight of heat stabilizer, and kneaded and extruded at 210°C and 160 rpm to obtain granules.

[0436] The obtained granules were injected using an injection molding machine (injection temperature: 230°C, injection pressure: 80 bar, Engel ES 200 / 45 HL-ProSeries) and then dried at 25°C and 50±5°C relative humidity for 12 hours to produce samples.

[0437] The physical properties of the sample are measured using the methods described below.

[0438] 1) Impact strength: For the obtained samples, the Izod impact strength (unit: kgf·cm / cm) was determined according to ASTM D256 using a Tinius Olsen (product name: Model Impact 104, manufacturer: Tinius Olsen Testing Machine Company) at a thickness of 1 / 4”, and the results are listed in Table 5.

[0439] 2) Melt index: For the obtained samples, the melt index (unit: g / 10min) was measured according to ASTM 648 at 220°C under a load of 10kg, and the results are shown in Table 5 below.

[0440] [Table 5]

[0441] As shown in Table 5, in the case of diene rubber polymers in which the roundness of latex particles follows that of Example 3 of the present invention, the impact strength and melt index are significantly improved compared to Comparative Examples 10 to 15, which are outside the scope of the present invention.

[0442] In particular, in Comparative Examples 10 and 11, where the roundness is outside the scope of the present invention, the impact strength is significantly reduced and the melt index is also reduced compared to Example 3.

[0443] In addition, in Comparative Examples 12 and 13, where the microstructure of the rubber particles is outside the scope of the present invention, the impact strength was significantly reduced and the melt index was also reduced compared to Example 3.

[0444] In addition, in Comparative Examples 14 and 15, where the average particle size of the rubber particles was outside the scope of the present invention, the impact strength was significantly reduced and the melt index was also reduced compared to Example 3.

[0445] In addition, the following Figure 3 This is a graph showing the polydisperse particle size distribution according to Example 3. As shown below... Figure 3 As shown, a bimodal distribution was observed.

[0446] Specifically, as follows: Figure 3 As shown, a bimodal distribution according to the present invention is observed, with the first particle size distribution range of 500 Å to 3000 Å accounting for 38.1% by weight and the second particle size distribution range of 3000 Å to 8000 Å accounting for 61.9% by weight. Here, the small diameter region can affect the physical properties of the thermoplastic resin composition containing the graft copolymer, such as the melt index, and the large diameter region can directly affect its impact strength.

[0447] In particular, it has been confirmed that the thermoplastic resin composition according to the invention exhibits an excellent balance of physical properties between impact resistance and flowability due to its superior impact strength and melt index, and is suitable for products requiring impact resistance. Furthermore, the thermoplastic resin composition displays a uniform spherical shape with a roundness of 1.06.

[0448] <Experimental Example 3-4>

[0449] Additional Comparative Example 11

[0450] <Preparation of Diene Rubber Polymer Latex>

[0451] 70 parts by weight of 1,3-butadiene, 75 parts by weight of ion-exchanged water, 3 parts by weight of oleic acid saponification, 0.1 parts by weight of potassium carbonate, 0.1 parts by weight of tert-dodecyl mercaptan, 0.15 parts by weight of tert-butyl hydroperoxide, 0.06 parts by weight of dextrose, 0.005 parts by weight of tetrasodium pyrophosphate, and 0.0025 parts by weight of ferrous sulfate are fed into a nitrogen-purged polymerization reactor. The temperature is raised to 55°C to initiate polymerization, and polymerization continues until the polymerization conversion reaches 35%.

[0452] Then, add 0.3 parts by weight of potassium persulfate, raise the temperature to 72°C, and polymerize until the polymerization conversion reaches 65%.

[0453] Then, 30 parts by weight of 1,3-butadiene, 0.1 parts by weight of potassium persulfate, and 0.3 parts by weight of oleic acid saponification were added, and the reaction was terminated at a polymerization conversion rate of 95%. At this point, the average particle size of the diene rubber polymer latex was 1145 Å.

[0454] Thickening of diene-based rubber polymer latex

[0455] An aqueous solution containing 1.45 parts by weight of acetic acid as an acid thickener was added to 100 parts by weight (based on solids) of a diene rubber polymer latex to thicken the diene rubber polymer latex. At this point, the average particle size of the thickened diene rubber polymer latex was 3272 Å.

[0456] Preparation of Vinyl Cyanide-Conjugated Diene Rubber-Aromatic Vinyl Compound Graft Copolymers

[0457] Perform the same procedure as in Example 3.

[0458] <Preparation of Thermoplastic Resin Compositions and Samples for Physical Property Measurement>

[0459] Perform the same procedure as in Example 3.

[0460] Additional Comparative Example 12

[0461] Except for terminating the reaction at a polymerization conversion rate of 91% in Example 3 (<Thickening of Diene Rubber Polymer Latex>), the same procedure as in Example 3 was performed. The thickened diene rubber polymer latex had an average particle size of 3360 Å.

[0462] Additional Comparative Example 13

[0463] Except for the use of 1.3 parts by weight of acetic acid in <Thickening of Diene Rubber Polymer Latex> in Example 3, the same procedure as in Example 3 was performed. The average particle size of the thickened diene rubber polymer latex was 3070 Å.

[0464] Additional Comparative Example 14

[0465] Except for the use of 1.7 parts by weight of acetic acid in <Thickening of Diene Rubber Polymer Latex> in Example 3, the same procedure as in Example 3 was performed. The average particle size of the thickened diene rubber polymer latex was 3860 Å.

[0466] As described above, samples were manufactured and their physical properties were measured. The results are shown in Table 6 below.

[0467] [Table 6]

[0468] As shown in Table 6, in the case of diene rubber polymers in which the roundness of latex particles follows that of Example 3 of the present invention, both impact strength and melt index are significantly improved compared to the additional comparative examples 11 to 14 which are outside the scope of the present invention.

[0469] Furthermore, in Comparative Examples 11 and 12, where the swelling degree of the graft copolymer is outside the scope of the present invention, the impact strength is significantly reduced and the melt index is also reduced compared to Example 3.

[0470] In addition, in Comparative Examples 13 and 14, where the weight ratio of particles present in each distribution range of rubber particles is outside the scope of the present invention, the impact strength is significantly reduced and the melt index is also reduced compared to Example 3.

[0471] Example 4

[0472] <Preparation of Diene Rubber Polymers>

[0473] 90 parts by weight of ion-exchanged water, 30 parts by weight of 1,3-butadiene, 1 part by weight of oleic acid saponification, 0.4 parts by weight of potassium carbonate, 0.15 parts by weight of tert-dodecyl mercaptan, 0.15 parts by weight of tert-butyl hydroperoxide, 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrrolidate and 0.0025 parts by weight of ferrous sulfate were added in batches to a nitrogen-purged polymerization reactor.

[0474] Polymerization was carried out in the reactor at 55°C for 5 hours.

[0475] Then, polymerization was carried out by continuously feeding 70 parts by weight of 1,3-butadiene and 0.3 parts by weight of tert-dodecyl mercaptan at a constant rate while raising the temperature to 78°C. The continuous feeding process lasted for 9 hours.

[0476] Then, when the polymerization conversion rate reaches 30% to 40%, 0.1 parts by weight of potassium persulfate and 0.15 parts by weight of rosin acid emulsifier are added in batches.

[0477] Then, when the polymerization conversion reached 95%, the polymerization was terminated to prepare a diene-based rubber polymer latex. At this point, the average particle size of the diene-based rubber polymer latex was 1180 Å, and the half-width was 450 Å.

[0478] <Preparation of Graft Copolymers>

[0479] A first mixture containing 15 parts by weight of acrylonitrile, 30 parts by weight of styrene, 0.4 parts by weight of dimer acid saponification, 0.35 parts by weight of tert-dodecyl mercaptan and 20 parts by weight of ion-exchanged water is prepared.

[0480] A second mixture containing 0.12 parts by weight of tert-butyl hydroperoxide, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrrolidone and 0.002 parts by weight of ferrous sulfate was prepared.

[0481] 55 parts by weight (based on solids) of diene rubber polymer latex and 100 parts by weight of ion-exchanged water are fed in batches into a nitrogen-purged polymerization reactor.

[0482] Then, polymerization was carried out while the first and second mixtures were continuously fed into the reactor at a constant rate at 70°C for 3 hours.

[0483] Then, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrrolidone, 0.001 parts by weight of ferrous sulfate and 0.05 parts by weight of tert-butyl hydroperoxide were fed into the reactor, the temperature of the reactor was raised to 80°C at a constant rate for 1 hour, and the polymerization was terminated to obtain the graft copolymer latex.

[0484] The graft copolymer latex is coagulated, matured, washed, dehydrated and dried to obtain graft copolymer powder.

[0485] <Preparation of Thermoplastic Resin Compositions>

[0486] A thermoplastic resin composition was prepared by mixing 30 parts by weight of graft copolymer powder and 70 parts by weight of a styrene-acrylonitrile polymer (LG Chemical Co., Ltd., weight average molecular weight: 120,000 g / mol) containing 73% by weight of styrene and 28% by weight of acrylonitrile.

[0487] Comparative Example 16

[0488] Except for the addition of 1.6 parts by weight of oleic acid saponifier in the <Preparation of Diene Rubber Polymers> of Example 4, the same procedure as in Example 4 was performed. At this time, the average particle size of the resulting diene rubber polymer latex was 1650 Å, and the half-width at half-maximum (WWHM) was 560 Å.

[0489] Comparative Example 17

[0490] Except for the addition of 0.4 parts by weight of oleic acid saponifier in the <Preparation of Diene Rubber Polymers> of Example 4, the same procedure as in Example 4 was performed. At this time, the average particle size of the obtained diene rubber polymer latex was 1170 Å, and the half-width at half-maximum (WWHM) was 463 Å.

[0491] Comparative Example 18

[0492] Except for the addition of 0.05 parts by weight of potassium carbonate in the <Preparation of Diene Rubber Polymers> section of Example 4, the same procedure as in Example 4 was performed. At this time, the average particle size of the resulting diene rubber polymer latex was 955 Å, and the half-width at half-maximum (WWHM) was 296 Å.

[0493] Comparative Example 19

[0494] Except for the addition of 0.2 parts by weight of potassium carbonate in the <Preparation of Diene Rubber Polymers> of Example 4, the same procedure as in Example 4 was performed. At this time, the average particle size of the resulting diene rubber polymer latex was 1355 Å, and the half-width at half-maximum (WWHM) was 612 Å.

[0495] Comparative Example 20

[0496] Except for increasing the reaction temperature from 51°C to 69°C in Example 4, the procedure was the same as in Example 4. At this time, the average particle size of the obtained diene rubber polymer latex was 1210 Å, and the half-width at half-maximum (WWHM) was 460 Å.

[0497] Comparative Example 21

[0498] Except for increasing the reaction temperature from 60°C to 80°C in Example 4, the procedure was the same as in Example 4. At this time, the resulting diene rubber polymer latex had an average particle size of 1170 Å and a half-width of 455 Å.

[0499] Comparative Example 22

[0500] Except for the addition of 0.25 parts by weight of tert-butyl hydrogen peroxide in the <Preparation of Diene Rubber Polymer Latex> of Example 4, the same procedure as in Example 4 was performed. At this time, the average particle size of the obtained diene rubber polymer latex was 785 Å, and the half-width at half-maximum (WWHM) was 326 Å.

[0501] Comparative Example 23

[0502] Except for the addition of 0.05 parts by weight of tert-butyl hydrogen peroxide in the <Preparation of Diene Rubber Polymer Latex> of Example 4, the same procedure as in Example 4 was performed. At this time, the average particle size of the obtained diene rubber polymer latex was 1812 Å, and the half-width at half-maximum (WWHM) was 565 Å.

[0503] <Experimental Example 4-1>

[0504] The physical properties of the diene rubber polymers of Example 4 and Comparative Examples 16 to 23 were measured as follows.

[0505] 1) Microstructure: The ratio (%) of cis-1,4-, trans-1,4-, and 1,2- bonds in diene rubber polymer latex was analyzed using 13C 1D normal NMR, and the results are shown in Table 7 below.

[0506] 2) Monodisperse particle size distribution: For diene rubber polymer latexes, capillary hydrodynamic classification (CHDF) particle size distribution was measured using a MATEC CHDF 4000 instrument (Mass Applied Science). The half-width at half-maximum (WHH) of the measured distribution range was measured using a CHDF 400 instrument (Mass Applied Science), and the results are shown in the FWHH section of Table 7 below.

[0507] The particle size half-width refers to the difference between particle sizes corresponding to half the maximum particle size in the particle size distribution. As the difference, or particle size half-width, increases, the uniformity of rubber particle size increases. As a specific example, when fmax is the maximum particle size, half the maximum particle size is fmax / 2, and the range of particle sizes between these two points is the particle size half-width.

[0508] 3) Particle roundness measurement: For diene rubber polymer latex, the ratio of the major axis length to the minor axis length of the particles was measured, and the roundness of the particles was calculated based on their average value. Specifically, after analyzing each latex using a TEM instrument (JEM-1400, Jeol), the major axis length and minor axis length of each of 50 particles were measured, and the particle roundness was calculated using Equation 1 below. The results are shown in Table 7 below.

[0509] [Equation 1]

[0510] In Equation 1, Di represents the ratio of the major axis length to the minor axis length of the i-th particle [major axis length / minor axis length].

[0511] Specifically, each latex was analyzed using a TEM instrument (JEM-1400, Jeol, 40K), and at least 50 to 100 particles were identified. In the images of the 50 identified particles, the lengths of the major and minor axes of each particle were measured, and roundness was calculated.

[0512] 4) Average particle size (Å): 0.1 g of diene rubber polymer latex was mixed with 100 g of distilled water using a Nicomp 380 apparatus (manufacturer: PSS), and the results are shown in Table 7 below.

[0513] 5) Swelling degree of rubber granules: 1 g of solid rubber polymer was immersed in 100 ml of toluene for 48 hours. When filtered through a 100-mesh metal wire mesh, the weight of the toluene-insoluble substance (weight a) and the weight of the vacuum-dried toluene-insoluble substance (weight b) were measured. The swelling degree was calculated using Equation 5 below, and the results are shown in Table 7 below.

[0514] [Equation 5]

[0515] Swelling degree = Weight of toluene-insoluble matter (weight a) / Weight after vacuum drying (weight b)

[0516] <Experimental Example 4-2>

[0517] The physical properties of the graft copolymer powders of Examples 4 and Comparative Examples 16 to 23 were measured as follows.

[0518] 1) Swelling degree: Immerse 2g of graft copolymer powder in 300ml of acetone and stir for 24 hours. Extract the insoluble matter from the solution.

[0519] The insoluble substance was soaked in 100 ml of toluene for 48 hours. The weight of the toluene-insoluble substance (weight a) and the weight of the vacuum-dried toluene-insoluble substance (weight b) were measured after filtration through a 100-mesh metal wire mesh. The degree of swelling was calculated using Equation 5 below, and the results are shown in Table 7.

[0520] [Equation 5]

[0521] Swelling degree = Weight of toluene-insoluble matter (weight a) / Weight after vacuum drying (weight b)

[0522] <Experimental Example 4-3>

[0523] 100 parts by weight of the thermoplastic resin compositions of Examples 4 and Comparative Examples 16 to 23 were mixed with 1 part by weight of lubricant and 0.1 part by weight of heat stabilizer, and kneaded and extruded at 210°C and 160 rpm to obtain granules.

[0524] The obtained granules were injected using an injection molding machine (injection temperature: 230°C, injection pressure: 80 bar, Engel ES 200 / 45 HL-ProSeries) and then dried at 25°C and 50±5°C relative humidity for 12 hours to produce samples.

[0525] The physical properties of the sample are measured using the methods described below.

[0526] 1) Impact strength: For the obtained samples, the Izod impact strength (unit: kgf·cm / cm) was measured according to ASTM D256 using a Tinius Olsen (product name: Model Impact 104, manufacturer: Tinius Olsen Testing Machine Company) at a thickness of 1 / 4”, and the results are shown in Table 7 below.

[0527] 2) Melt index: For the obtained samples, the melt index (unit: g / 10min) was measured according to ASTM 648 at 220°C under a load of 10kg, and the results are shown in Table 7 below.

[0528] 3) Gloss: For the obtained samples, the gloss was measured at 45° using a gloss meter according to ASTM D528, and the results are shown in Table 7 below. As this value increases, the surface gloss improves.

[0529] [Table 7]

[0530] As shown in Table 4, in the case of diene rubber polymers in which the roundness of latex particles follows that of Example 4 of the present invention, the impact strength is greatly improved compared with Comparative Examples 16 to 23, which are outside the scope of the present invention, and the melt index and gloss are significantly improved.

[0531] In addition, in Comparative Examples 16 and 17, where the roundness is outside the scope of the present invention, the impact strength is significantly reduced compared to Example 4, and the melt index and gloss are also reduced.

[0532] Furthermore, in Comparative Examples 18 and 19, where the average particle size is outside the scope of the present invention, the impact strength was significantly reduced compared to Example 4, and the melt index and gloss were also reduced.

[0533] Furthermore, in Comparative Examples 20 and 21, where the microstructure is outside the scope of this invention, the impact strength was significantly reduced compared to Example 4, and the melt index and gloss were also reduced.

[0534] Furthermore, in Comparative Examples 22 and 23, where the average particle size is outside the scope of the present invention, the impact strength was significantly reduced, and the melt index and gloss were reduced compared to Example 4.

[0535] In particular, it has been confirmed that the thermoplastic resin composition according to the invention exhibits an excellent balance of physical properties between impact resistance and flowability due to its superior impact strength and melt index. Furthermore, the thermoplastic resin composition displays a gloss of 95% or higher at 45°, making it suitable for products requiring high gloss. Additionally, the thermoplastic resin composition displays a uniform spherical shape with a roundness of 1.06.

[0536] Additionally, the following Figure 4 This is a graph showing the particle size distribution. See below. Figure 4 As shown, a monodisperse dispersion was observed.

[0537] <Experimental Example 4-4>

[0538] Additional Comparative Example 15

[0539] <Preparation of Diene Rubber Polymer Latex>

[0540] 75 parts by weight of deionized water, 90 parts by weight of 1,3-butadiene as a conjugated diene compound, 3 parts by weight of dimer acid saponifiables as emulsifiers, 0.1 parts by weight of potassium carbonate (K2CO3) as an electrolyte, 0.1 parts by weight of tert-dodecyl mercaptan (TDDM) as a molecular weight regulator, 0.15 parts by weight of tert-butyl hydroperoxide as an initiator, 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrrolidone, and 0.0025 parts by weight of ferrous sulfate were added in batches to a nitrogen-purged polymerization reactor (autoclave). The reaction was carried out at a reaction temperature of 55°C until the polymerization conversion reached 30% to 40%. 0.3% by weight of potassium persulfate was added in batches, and the temperature was raised to 72°C. When the polymerization conversion reached 60% to 70%, 10 parts by weight of the remaining 1,3-butadiene were added in batches. The reaction was terminated at a polymerization conversion of 95%. At this point, the average particle size of the diene rubber polymer latex obtained is 1155 Å, and the half-width of the particle size is 447 Å.

[0541] <Preparation of Graft Copolymers> and <Preparation of Thermoplastic Resin Compositions>

[0542] Perform each procedure in the same manner as in Example 4.

[0543] Additional Comparative Example 16

[0544] Except for terminating the reaction at 90% polymerization conversion in Example 4 (Preparation of Diene Rubber Polymer Latex), the same procedure as in Example 4 was performed. At this time, the resulting diene rubber polymer latex had an average particle size of 1120 Å and a particle size half-width of 452 Å.

[0545] As described above, samples were manufactured and their physical properties were measured. The results are shown in Table 8 below.

[0546] [Table 8]

[0547] As shown in Table 8, in the case where the roundness of the latex particles follows that of the diene rubber polymer of Example 4 of the present invention, the impact strength is greatly improved compared with the additional comparative examples 15 and 16 which are outside the scope of the present invention, and the melt index and gloss are significantly improved.

[0548] For reference, in Comparative Examples 15 and 16, where the degree of swelling is outside the scope of the present invention, the impact strength was significantly reduced compared to Example 4, and the melt index and gloss were also reduced.

[0549] In summary, the diene-based rubber polymers according to the present invention have a predetermined polydisperse particle size distribution. The microstructure, average particle size, and roundness of the diene-based rubber polymers, as well as the swelling degree of the graft copolymers, can be easily controlled, thereby providing an excellent balance of physical properties between impact resistance and flowability. Furthermore, the diene-based rubber polymers can be applied to products requiring impact resistance, high gloss, or high flowability.

Claims

1. A diene-based rubber polymer having a microstructure comprising 20% ​​to 30% cis-1,4-bonds, 55% to 65% trans-1,4-bonds, and the balance 1,2-bonds, said diene-based rubber polymer having a first particle size distribution range of 200 Å to 3000 Å, an average particle size of 3000 Å to 4000 Å or 800 Å to 1800 Å, and a roundness of 1.03 to 1.5 calculated by Equation 1 below. [Equation 1] in, Di is the ratio of the major axis length to the minor axis length of the i-th particle in the latex [major axis length / minor axis length].

2. The diene-based rubber polymer according to claim 1, wherein, The diene-based rubber polymer has a second particle size distribution range of 1800 Å to 8000 Å.

3. The diene-based rubber polymer according to claim 1, wherein, The weight ratio (first:second) of particles contained in the first particle size distribution range to particles contained in the second particle size distribution range is 1:0.60 to 1:0.

97.

4. The diene-based rubber polymer according to claim 1, wherein, In the entire particle size distribution range exhibited by the diene rubber polymer, the first particle size distribution range exhibits a polydisperse particle size distribution of 15% to 75%, and the second particle size distribution range exhibits a polydisperse particle size distribution of 25% to 85%.

5. The diene-based rubber polymer according to claim 1, wherein, The polydisperse particle size distribution is a measurement of diene rubber polymers in latex form or of their acid-thickened products.

6. The diene rubber polymer according to claim 1, wherein, The first particle size distribution range has a first particle size distribution range of 200 Å to 1800 Å and a second particle size distribution range of 1800 Å to 8000 Å, the first particle size distribution range is in the range of 45% to 75%, the second particle size distribution range is in the range of 25% to 55%, and the average particle size is in the range of 3000 Å to 4000 Å.

7. The diene rubber polymer according to claim 1, wherein, The first particle size distribution range has a first particle size distribution range of 1500 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å, the first particle size distribution range is in the range of 15% to 40%, the second particle size distribution range is in the range of 60% to 85%, and the average particle size is in the range of 3000 Å to 4000 Å.

8. The diene-based rubber polymer according to claim 1, wherein, The first particle size distribution range has a first particle size distribution range of 1500 Å to 3000 Å and a second particle size distribution range of 3000 Å to 8000 Å, the first particle size distribution range is in the range of 35% to 65%, the second particle size distribution range is in the range of 35% to 65%, and the average particle size is in the range of 3000 Å to 4000 Å.

9. The diene rubber polymer according to claim 1, wherein, The first particle size distribution range has a monodisperse particle size distribution range of 300 Å to 600 Å, an average particle size in the range of 800 Å to 1800 Å, and a swelling degree in the range of 4 to 12.

10. A method for preparing diene-based rubber polymers, comprising: Diene-based rubber polymer latex is prepared by emulsion polymerization of conjugated diene compounds; and diene-based rubber polymer is obtained by acid thickening treatment of the diene-based rubber polymer latex. The acid thickening treatment is carried out using one or more acid thickening agents selected from acetic acid, formic acid, citric acid, phosphoric acid, dihydrogen phosphate, and monohydrogen phosphate.

11. A graft copolymer comprising the diene rubber polymer of claim 1.

12. The graft copolymer according to claim 10, wherein, The content of the diene rubber polymer in the graft copolymer is from 3% to 80% by weight.

13. The graft copolymer according to claim 10, wherein, The swelling degree of the graft copolymer is 8 to 20.

14. A thermoplastic resin composition comprising the graft copolymer of claim 10.

15. A molded article comprising the thermoplastic resin composition of claim 14.

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