Vinyl chloride-based resin composition

Abstract

The present invention relates to a vinyl chloride-based resin composition, wherein the vinyl chloride-based resin composition comprises: 100 parts by weight of a vinyl chloride-based polymer having a degree of polymerization of 3,700 to 5,000 and a polydispersity index of 3.5 or more; and 40 to 100 parts by weight of a partially crosslinked diene-based rubber polymer comprising vinyl cyanide-based monomer units and diene-based monomer units.

Description

Vinyl chloride-based resin composition

[0001] [Cross-reference with related applications]

[0002] The present invention claims the benefit of priority based on Korean patent applications No. 10-2024-00159242, No. 10-2024-00159244, No. 10-2024-00159245, No. 10-2024-00159246, and No. 10-2024-00159247 filed on November 11, 2024, and includes all contents disclosed in the documents of said Korean patent applications as part of this specification.

[0003] [Technology Field]

[0004] The present invention relates to a vinyl chloride-based resin composition.

[0005] Vinyl chloride polymers are inexpensive and possess excellent mechanical strength, weather resistance, insulation, and oil resistance, as well as flame retardancy. Since a vinyl chloride resin composition containing a vinyl chloride polymer and processing auxiliary materials such as plasticizers and heat stabilizers is easy to process, it can be widely used in wires, fabrics, flooring materials, tarpaulins, hoses, etc.

[0006] However, since vinyl chloride-based resin compositions lack permanent compression set and cold resistance, when applied to window gaskets and automobile door belts, problems such as reduced durability and increased wind noise may occur as the winter season passes.

[0007] Therefore, there is a need for research to solve the problems of permanent compression set and cold resistance of vinyl chloride-based resin compositions.

[0008] [Prior Art Literature]

[0009] [Patent Literature]

[0010] (Patent Document 1) JP2912950B

[0011] The problem that the present invention aims to solve is to provide a vinyl chloride-based polymer resin composition with improved cold resistance and permanent compression set while maintaining basic physical properties.

[0012] To solve the above-mentioned problem, 1) the present invention provides a vinyl chloride resin composition comprising 100 parts by weight of a vinyl chloride-based polymer having a degree of polymerization of 3,700 or more and 5,000 or less and a polydispersity index of 3.5 or more; and 40 parts by weight or more and 100 parts by weight or less of a partially cross-linked diene rubbery polymer comprising vinyl cyanide-based monomer units and diene-based monomer units.

[0013] 2) The present invention may provide a vinyl chloride-based resin composition in which the vinyl chloride polymer has a plasticizer absorption rate of 40 phr or more and 90 phr or less, in accordance with 1).

[0014] 3) The present invention may provide a vinyl chloride-based resin composition in which, in 1) or 2), the degree of polymerization is 3,800 or more and 4,500 or less.

[0015] 4) The present invention may provide a vinyl chloride-based resin composition in which, in any one of 1) to 3), the polydispersity index is 3.5 or higher and 4.1 or lower.

[0016] 5) The present invention may provide a vinyl chloride resin composition in any one of 1) to 4), wherein the vinyl chloride polymer comprises a mixture of 28% or more and 32% or less of a low molecular weight vinyl chloride polymer having a molecular weight of 100,000 g / mol or less.

[0017] 6) The present invention can provide a vinyl chloride resin composition in which, in any one of 1) to 5), the vinyl chloride polymer has an area of ​​the left region based on the molecular weight value at which a peak appears in the molecular weight graph obtained through gel penetration chromatography analysis that is 50% or more of the total area of ​​the graph.

[0018] 7) The present invention may provide a vinyl chloride resin composition in any one of 1) to 6), wherein the diene-based rubbery polymer is a partially cross-linked acrylonitrile-butidiene rubbery polymer.

[0019] 8) The present invention may provide a vinyl chloride resin composition in which, in any one of 1) to 7), the diene-based rubbery polymer has a gel content of 60 weight% or more and 90 weight% or less.

[0020] 9) The present invention may provide a vinyl chloride resin composition comprising, in any one of 1) to 8), 70 parts by weight or more and 100 parts by weight or less of the diene rubbery polymer with respect to 100 parts by weight of the vinyl chloride-based polymer.

[0021] 10) The present invention may provide a vinyl chloride resin composition comprising, in any one of 1) to 9), an olefinic rubbery polymer comprising two or more olefinic monomer units having 2 or more carbon atoms and 12 or fewer carbon atoms; a plasticizer; an acrylic processing aid; and an acrylic impact modifier, comprising one or more additives selected from the group consisting of an acrylic impact modifier.

[0022] 11) The present invention may provide a vinyl chloride resin composition according to 10), wherein the olefinic rubbery polymer comprises one or more olefinic monomer units having 2 or more carbon atoms and 4 or fewer carbon atoms; and one or more olefinic monomer units having 5 or more carbon atoms and 12 or fewer carbon atoms.

[0023] 12) The present invention may provide a vinyl chloride resin composition comprising an ethylene monomer unit and a 1-octene monomer unit, wherein the olefinic rubbery polymer in 10) or 11) comprises the ethylene monomer unit and the 1-octene monomer unit.

[0024] 13) The present invention may provide a vinyl chloride resin composition comprising, in any one of 10) to 12), 5 parts by weight or more and 20 parts by weight or less of the olefinic rubbery polymer with respect to 100 parts by weight of the vinyl chloride polymer.

[0025] 14) The present invention may provide a vinyl chloride resin composition according to 10), wherein the plasticizer is one or more selected from the group consisting of phthalate-based plasticizers, isophthalate-based plasticizers, terephthalate-based plasticizers, hydrogenated phthalate-based plasticizers, hydrogenated isophthalate-based plasticizers, hydrogenated terephthalate-based plasticizers, citrate-based plasticizers, trimellitate-based plasticizers, and adipate-based plasticizers.

[0026] 15) The present invention may provide a vinyl chloride resin composition comprising 50 parts by weight or more and 130 parts by weight or less of the plasticizer with respect to 100 parts by weight of the vinyl chloride polymer in accordance with 10) or 14).

[0027] 16) The present invention may provide a vinyl chloride resin composition in which the acrylic processing aid has a weight average molecular weight of 5,000,000 g / mol or more and 15,000,000 g / mol or less.

[0028] 17) The present invention may provide a vinyl chloride resin composition according to 10) or 16), wherein the acrylic processing aid comprises a core comprising 80% to 85% by weight of a unit derived from a methyl methacrylate monomer and 10% to 15% by weight of a unit derived from an alkyl acrylate monomer; and a shell comprising 5% to 10% by weight of a unit derived from an alkyl methacrylate monomer crosslinked to the core; wherein the shell comprises a unit derived from a crosslinking agent comprising a metal salt compound of a saturated fatty acid and a metal salt compound of a dicarboxylic acid.

[0029] 18) The present invention may provide a vinyl chloride resin composition comprising, in any one of 10), 16), and 17), 0.7 parts by weight or more and 4.5 parts by weight or less of the acrylic processing aid per 100 parts by weight of the vinyl chloride polymer.

[0030] 19) The present invention may provide a vinyl chloride resin composition comprising an acrylic impact reinforcing agent comprising an acrylic rubber core and a shell comprising an acrylate monomer unit, in accordance with 10).

[0031] 20) The present invention may provide a vinyl chloride resin composition comprising 3 parts by weight or more and 10 parts by weight or less of the acrylic impact reinforcing agent with respect to 100 parts by weight of the vinyl chloride polymer in accordance with 10) or 19).

[0032] The vinyl chloride-based resin composition according to the present invention not only has excellent basic physical properties, but can also improve cold resistance and permanent compression set.

[0033] The vinyl chloride-based resin composition according to the present invention can also be applied to window and door gaskets and automobile door belts.

[0034] The present invention will be described in more detail below.

[0035] Terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0036]

[0037] Meanwhile, in this specification, “vinyl chloride-based polymer” refers to a polymer prepared from a vinyl chloride-based monomer. Specifically, the vinyl chloride-based polymer may be a vinyl chloride homopolymer prepared by polymerizing a vinyl chloride monomer. The vinyl chloride-based polymer may be a vinyl chloride copolymer prepared by polymerizing a mixture comprising a vinyl chloride monomer and a vinyl monomer copolymerizable with the vinyl chloride monomer. The mixture may contain 50 weight% or more of the vinyl chloride monomer.

[0038]

[0039] In this specification, “vinyl cyanide monomer” may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, among which acrylonitrile is preferred.

[0040]

[0041] In this specification, “diene monomer” may be one or more selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene, among which 1,3-butadiene is preferred.

[0042]

[0043] In this specification, “degree of polymerization” can be measured by the method described below.

[0044] First, 0.5 g of the obtained vinyl chloride-based polymer is mixed with 100 ml of cyclohexanone and heated at 110 °C for 2 hours to completely dissolve it, thereby preparing a solution. Afterward, the flask containing the solution is cooled by placing it in a water bath at 30 °C, and then 10 ml of the cooled solution is poured into a viscometer. The viscosity is measured by measuring the time based on passing the reference scale line (ASTM-D1243), and the degree of polymerization is calculated from the measured viscosity using a conversion table for viscosity, K-Value, and degree of polymerization (refer to PVC Technology literature).

[0045]

[0046] In this specification, “molecular weight” can be measured by gel permeation chromatography.

[0047] Specifically, 0.02 g of the obtained vinyl chloride-based polymer is dissolved in 20 ml of tetrahydrofuran, foreign substances are removed using a 0.45 µm filter, and the sample is fed into a gel permeation chromatography (GPC) facility (Waters 2414 RID, column: PLgel mini-mixed B × 2) to measure and analyze under conditions of a flow rate of 0.3 ml / min and a column temperature of 40 ℃.

[0048]

[0049] In this specification, the “polydispersity index” can be calculated by measuring the number average molecular weight and weight average molecular weight using the molecular weight measurement method described above, and substituting the values ​​into the following formula.

[0050] Polydispersity index = (Weight average molecular weight of vinyl chloride polymer) / (Number average molecular weight of vinyl chloride polymer)

[0051]

[0052] In this specification, the “plasticizer absorption rate” can be measured by the method described below.

[0053] Specifically, the plasticizer absorption rate is measured by introducing vinyl chloride-based polymer resin, cotton, and plasticizer into a specified glass tube, centrifuging, and measuring the content of the plasticizer absorbed in the resin. It can be measured under conditions of 1.0 g of vinyl chloride polymer, 2.0 g of plasticizer, a centrifuge speed of 3,900 rpm, and operation at 20 ℃ for 30 minutes (partially utilizing the measurement method based on ASTM-D3367). More specifically, the plasticizer absorption rate value can be calculated using the following formula.

[0054] Plasticizer absorption rate = {(m3-m2) / (m2-m1)} × 100

[0055] m1 = combined weight of glass tube and cotton

[0056] m2 = combined weight of glass tubes, resin, and cotton

[0057] m3 = Combined weight of glass tube, resin, and cotton after plasticizer absorption

[0058]

[0059] In this specification, “gel content” can be measured by the following method.

[0060] 1 g of diene-based rubbery polymer powder and 100 g of toluene are sequentially added to a beaker (capacity: 250 ml), stored in a dark room for 12 hours, and then filtered through a mesh to obtain the insoluble matter. After drying the insoluble matter at 85 ℃ for 4 hours, the weight of the dried matter can be calculated by substituting it into the following formula.

[0061] Gel content (weight%) = (Weight of dry matter) / (Weight of diene-based rubbery polymer powder added to the beaker) × 100

[0062]

[0063] In this invention, “gas chromatography analysis” can be performed under the following conditions.

[0064] Injector temperature: 300 ℃ (isothermal)

[0065] Carrier gas: Helium gas (Flow rate: 1.4 ml / min)

[0066] Column: HP-5MS capillary (30 m × 250 µm × 0.25 µm)

[0067] Oven: 40 ℃ / 3 min, 10 ℃ / min, hold at 320 ℃ for 15 minutes

[0068] Detector: MSD(scan mode)

[0069]

[0070] In the present invention, the “permanent compression set” can be measured according to KS M 6518:2021 and ASTM D396.

[0071] Specifically, after manufacturing a specimen (shape: cylindrical, thickness: 12.70 ± 0.13 mm, diameter: 29.0 mm), the permanent compression set can be measured according to KS M 6518:2021 and ASTM D396 for 22 hours at 70 ± 1 ℃.

[0072]

[0073] 1. Vinyl chloride-based resin composition

[0074]

[0075] A vinyl chloride-based resin composition according to one embodiment of the present invention comprises 100 parts by weight of a vinyl chloride-based polymer having a degree of polymerization of 3,700 or more and 5,000 or less and a polydispersity index of 3.5 or more; and 40 parts by weight or more and 100 parts by weight or less of a partially cross-linked diene rubbery polymer comprising vinyl cyanide-based monomer units and diene-based monomer units.

[0076]

[0077] In addition, a vinyl chloride-based resin composition according to one embodiment of the present invention may further include one or more additives selected from plasticizers, stabilizers, fillers, lubricants, and processing aids.

[0078]

[0079] Hereinafter, the components of a vinyl chloride-based resin composition according to one embodiment of the present invention will be described in detail.

[0080]

[0081] 1) Vinyl chloride-based polymer

[0082]

[0083] (1) Vinyl chloride-based polymer

[0084]

[0085] The present invention provides a vinyl chloride-based polymer having a degree of polymerization of 3,700 or more and 5,000 or less, and a polydispersity index of 3.5 or more.

[0086]

[0087] Existing vinyl chloride-based polymer products known to possess a high degree of polymerization have limitations in that, even with a high degree of polymerization, their polydispersity index is low, resulting in insufficient mechanical properties and insufficiently fast melting speeds. The present invention provides a vinyl chloride-based polymer that possesses both a high degree of polymerization and a high polydispersity index, thereby enabling the simultaneous realization of the advantages of a high degree of polymerization, namely heat resistance, and the advantages of a high polydispersity index, namely excellent melting characteristics.

[0088]

[0089] More specifically, the degree of polymerization of the vinyl chloride-based polymer provided by the present invention may be 3,700 or more, 3,800 or more, 3,900 or more, 4,000 or more, or 4,050 or more, and 5,000 or less, 4,900 or less, 4,800 or less, 4,700 or less, 4,600 or less, 4,500 or less, 4,400 or less, 4,300 or less, or 4,200 or less. It is not easy to significantly increase the degree of polymerization of the vinyl chloride-based polymer itself beyond the range described above, and the vinyl chloride-based polymer of the present invention can have excellent heat resistance properties by having a degree of polymerization within the range described above.

[0090]

[0091] The number average molecular weight of the vinyl chloride-based polymer provided by the present invention may be 100,000 g / mol or more and 150,000 g / mol or less, preferably 100,000 g / mol or more, 105,000 g / mol or more, 110,000 g / mol or more, 115,000 g / mol or more, or 120,000 g / mol or more, and may be 150,000 g / mol or less, 145,000 g / mol or less, 140,000 g / mol or less, 135,000 g / mol or less, or 130,000 g / mol or less. In addition, the weight average molecular weight of the vinyl chloride-based polymer provided by the present invention may be 430,000 g / mol or more and 5,150,000 g / mol or less, and preferably 430,000 g / mol or more, 440,000 g / mol or more, 445,000 g / mol or more, 450,000 g / mol or more, 455,000 g / mol or more, or 460,000 g / mol or more, and may be 515,000 g / mol or less, 510,000 g / mol or less, 505,000 g / mol or less, 500,000 g / mol or less, 495,000 g / mol or less, or 490,000 g / mol or less. The number average molecular weight and weight average molecular weight mentioned above can be measured by conventional methods, and for example, can be measured using a GPC (gel penetration chromatograph) facility.

[0092]

[0093] The polydispersity index (PDI) of the vinyl chloride-based polymer provided by the present invention may be 3.5 or higher, preferably 3.5 or higher, 3.6 or higher, 3.7 or higher, 3.8 or higher, or 3.85 or higher, and may be 4.1 or lower, 4.0 or lower, or 3.95 or lower. The polydispersity index is a value calculated by dividing the weight-average molecular weight (Mw) of the polymer by the number-average molecular weight (Mn), and the melting characteristics of the vinyl chloride-based polymer may be superior when the polydispersity index is within the range described above. More specifically, the vinyl chloride-based polymer provided by the present invention may maintain excellent processability by maintaining a high relative proportion of low-molecular-weight vinyl chloride-based polymers compared to other vinyl chloride-based polymers having a similar degree of polymerization, and accordingly may have a polydispersity index within the range described above.

[0094]

[0095] In the vinyl chloride-based polymer provided by the present invention, the vinyl chloride-based polymer may be a mixture comprising a low molecular weight vinyl chloride-based polymer having a molecular weight of 100,000 g / mol or less. The content of the low molecular weight vinyl chloride-based polymer included in the vinyl chloride-based polymer may be 28.0 wt% or more and 32.0 wt% or less, and preferably 28.0 wt% or more, 28.5 wt% or more, 29.0 wt% or more, 29.5 wt% or more, or 30.0 wt% or more, and may be 32.0 wt% or less, 31.5 wt% or less, or 31.0 wt% or less. As previously explained, the content of the low molecular weight vinyl chloride polymer is higher than the content of the low molecular weight vinyl chloride polymer included in existing similar high-polymerization-degree vinyl chloride polymers, and the vinyl chloride polymer of the present invention can have superior processability by including the low molecular weight vinyl chloride polymer within the aforementioned range. Meanwhile, the content of the low molecular weight vinyl chloride polymer can be calculated as the ratio of the area occupied by the region with a molecular weight of 100,000 g / mol or less to the total area of ​​the molecular weight graph obtained through GPC (gel penetration chromatography) analysis of the vinyl chloride polymer.

[0096]

[0097] In addition, the vinyl chloride-based polymer provided by the present invention may have an area of ​​the left region based on the molecular weight value where a peak appears in the molecular weight graph obtained through the GPC analysis that is 50% or more of the total area of ​​the graph. The left region refers to a region where the molecular weight is relatively low, and the vinyl chloride-based polymer of the present invention may exhibit such characteristics because the content of low molecular weight is maintained at a relatively high level. Meanwhile, the GPC analysis may be performed by dissolving 0.02 g of the vinyl chloride-based polymer in 20 ml of tetrahydrofuran, filtering out impurities with a 0.45 μm filter, and then performing the analysis under conditions of a flow rate of 0.3 ml / min and a column temperature of 40 ℃. The molecular weight graph obtained through the GPC analysis may have the horizontal axis as the logarithm of the molecular weight (log(M)) and the vertical axis as the value obtained by differentiating the fraction w with the log(M) value (dw / dlog(M)).

[0098]

[0099] The vinyl chloride-based polymer provided by the present invention may be characterized in that the time between the point where the torque reaches a maximum value and the point where the torque reaches a maximum value in the graph obtained from the melting rate analysis of a specimen obtained by compounding the vinyl chloride-based polymer is 60 seconds or less. The time between the two points may preferably be 55 seconds or less, 50 seconds or less, or 45 seconds or less.

[0100] In addition, the vinyl chloride-based polymer provided by the present invention may be characterized in that the time between the point in time when the torque reaches a maximum point and the point in time when the torque recovers to a torque value corresponding to the torque value of the maximum point after said point, as shown in the graph obtained from the melting rate analysis result of a specimen obtained by compounding the vinyl chloride-based polymer, is 30 seconds or less. In addition, the time between said two points in time may preferably be 28 seconds or less, 26 seconds or less, or 24 seconds or less.

[0101] The above compound formulation may be formulated by mixing 80 parts by weight or less of a plasticizer, 10 parts by weight or less of a stabilizer, and 10 to 150 parts by weight of a filler, based on 100 parts by weight of a vinyl chloride-based polymer. More specifically, the above compound formulation may be formulated by mixing 70 parts by weight of triisononyl trimellitate (plasticizer), 6 parts by weight of RUP-166S (stabilizer), and 20 parts by weight of calcium carbonate (filler) with respect to 100 parts by weight of a vinyl chloride-based polymer.

[0102]

[0103] The melting rate analysis of the specimen obtained after the above compound formulation may be performed using a Brabender plastograph with the resin composition, and may be performed while operating the device at a temperature of 135°C and a speed of 70 rpm. The graph obtained from the melting rate analysis may be a graph with time on the horizontal axis and torque value on the vertical axis.

[0104]

[0105] The vinyl chloride-based polymer provided by the present invention may have a bulk density of 0.5 g / cm³ or less, preferably 0.45 g / cm³ or less, and may be 0.1 g / cm³ or more, 0.2 g / cm³ or more, 0.3 g / cm³ or more, or 0.4 g / cm³ or more. The bulk density can be measured according to a conventional method, and can be calculated by filling a container with a certain volume of vinyl chloride-based polymer, measuring the weight, and dividing the measured weight by the volume of the container.

[0106]

[0107] In addition, the vinyl chloride-based polymer provided by the present invention may have a cold plasticizer absorption (CPA) of 40 phr or more, 43 phr or more, 45 phr or more, 47 phr or more, 49 phr or more, or 50 phr or more, and may have a cold plasticizer absorption of 90 phr or less, 80 phr or less, 70 phr or less, or 60 phr or less. The above plasticizer absorption is measured by introducing a vinyl chloride-based polymer resin and a plasticizer into a specified glass tube, centrifuging, and measuring the content of the plasticizer absorbed in the resin. It may be measured under conditions of 1.0 g of vinyl chloride-based polymer, 2.0 g of plasticizer, a centrifuge speed of 3,900 rpm, and operation at 20 ℃ for 30 minutes.

[0108]

[0109] In addition, the vinyl chloride-based polymer provided by the present invention is characterized by having a peak in the region between 19.40 and 19.60 minutes of retention time in the graph obtained from the pyrolysis-gas chromatography analysis results. The said peak may indicate that the isophthalate-based chain extender used in the polymerization process of the vinyl chloride-based polymer is appropriately distributed within the polymer chain, and in particular, the vinyl chloride-based polymer provided by the present invention may exhibit a peak in the region between 19.4 and 19.6 minutes of retention time, preferably in the region between 19.45 and 19.5 minutes. The said peak may be derived from an isophthalate-based compound, and more specifically, may be derived from diallyl isophthalate.

[0110] Meanwhile, the above-mentioned pyrolysis-gas chromatography analysis (Py-GC / MSD) involves heat-treating a vinyl chloride-based polymer at a constant temperature to remove impurities, then pyrolyzing the polymer at a higher temperature to form a mixture of compounds with relatively small molecular weights, and subsequently performing gas chromatographic analysis on such a mixture.

[0111] The heat treatment may be performed at 250 to 350 ℃, and more specifically, it may be performed by starting at a temperature of 250 to 300 ℃, heating at a constant heating rate until the temperature reaches 300 to 350 ℃, and then maintaining the temperature for a certain period of time from the point at which the temperature is reached. Even more specifically, the heat treatment may be performed by starting at a temperature of 280 ℃, heating at a rate of 20 ℃ / min, reaching 320 ℃, and then maintaining the temperature at 320 ℃ for 2 minutes. In this case, the total heat treatment time may be 4 minutes.

[0112] After the above heat treatment, the thermal decomposition may be performed at a temperature sufficient for the polymer chains within the polymer to decompose, more specifically at a temperature of 500°C or higher and 700°C or lower, more specifically at a temperature of 550°C to 650°C, and particularly preferably at 590°C.

[0113]

[0114] In addition, the vinyl chloride-based polymer provided by the present invention may have a crosslinked gel content of 3% by weight or less, and preferably 2.5% by weight or less, 2.0% by weight or less, 1.5% by weight or less, 1.0% by weight or less, 0.8% by weight or less, 0.5% by weight or less, 0.3% by weight or less, 0.2% by weight or less, or 0.1% by weight or less. The crosslinked gel content may be measured using a Soxhlet extractor, and due to the low crosslinked gel content, the vinyl chloride-based polymer included in the resin composition of the present invention may not produce any or almost no unmelted particles during processing. If unmelted particles are produced during processing, this may act as a defect in the product.

[0115]

[0116] The vinyl chloride-based polymer provided by the present invention may be in powder form.

[0117]

[0118] (2) Method for manufacturing vinyl chloride-based polymer

[0119]

[0120] The present invention provides a method for manufacturing a vinyl chloride-based polymer as described above.

[0121]

[0122] More specifically, the present invention provides a method for manufacturing a vinyl chloride polymer comprising the steps of: preparing a chain extension aid by uniformly dispersing an isophthalate-based chain extender, a nonionic emulsifier, and polyvinyl alcohol (S1); introducing polymerization water, an initiator, the chain extension aid, and a vinyl chloride monomer into a polymerization reactor and initiating a polymerization reaction (S2); and performing a polymerization reaction at a temperature of 50°C or lower to synthesize a vinyl chloride polymer (S3).

[0123]

[0124] The vinyl chloride-based polymer of the present invention can be prepared by using the chain extension aid and performing the polymerization reaction at a low temperature of 50°C or lower. Below, the method for preparing the vinyl chloride-based polymer of the present invention will be described in more detail.

[0125]

[0126] S1 stage

[0127] Prior to carrying out the polymerization reaction, a step of preparing a chain extension aid by uniformly dispersing a chain extender, a nonionic emulsifier, and polyvinyl alcohol may be performed. The chain extender is used in the polymerization reaction to increase the degree of polymerization by extending the polymer chain. However, if the chain extender is directly introduced into the polymerization reactor, the chain extender may not be uniformly dispersed, resulting in the production of a non-uniform vinyl chloride-based polymer. Therefore, in the method for producing a vinyl chloride-based polymer according to the present invention, a chain extension aid prepared by mixing the chain extender with a nonionic emulsifier and polyvinyl alcohol and then uniformly dispersing it is used.

[0128] Meanwhile, the chain extender used in the present invention may be an isophthalate-based chain extender, and more specifically, the isophthalate-based chain extender may be diallyl isophthalate. Unlike phthalate-based chain extenders that have been used frequently in the past, the isophthalate-based chain extender is harmless to the human body and can provide an excellent chain extension effect even at a low concentration.

[0129] The above isophthalate-based chain extender may be used in an amount of 0.5 parts by weight or less per 100 parts by weight of vinyl chloride-based monomer, preferably 0.40 parts by weight or less, 0.30 parts by weight or less, 0.20 parts by weight or less, or 0.15 parts by weight or less, and may be used in an amount of 0.01 parts by weight or more, 0.03 parts by weight or more, 0.05 parts by weight or more, 0.06 parts by weight or more, or 0.07 parts by weight or more. Within the above-described range, the degree of polymerization of the polymer can be sufficiently increased while minimizing the cross-linked gel content.

[0130] The above nonionic emulsifier has lipophilicity and is intended to disperse the above isophthalate-based chain extender more uniformly. It may be one or more selected from the group consisting of polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, glyceryl monooleate, and glyceryl monostearate, and preferably may be sorbitan monolaurate.

[0131] The above nonionic emulsifier may be included in an amount of 0.005 parts by weight or more, 0.010 parts by weight or more, 0.020 parts by weight or more, 0.030 parts by weight or more, 0.040 parts by weight or more, 0.050 parts by weight or more, 0.060 parts by weight or more, or 0.070 parts by weight or more, based on 100 parts by weight of the vinyl chloride monomer, while being included in an amount of 0.30 parts by weight or less, 0.250 parts by weight or less, 0.200 parts by weight or less, or 0.105 parts by weight or less. If the above conditions are satisfied, the average particle size of the vinyl chloride polymer can be maintained at an appropriate level.

[0132] The weight ratio between the above isophthalate-based chain extender and the nonionic emulsifier may be 1:0.01 to 15.00, preferably 1:0.03 to 13.50, more preferably 1:0.50 to 10.00, even more preferably 1:0.60 to 9.00, and most preferably 1:0.07 to 8.00.

[0133] The above polyvinyl alcohol has hydrophilicity and serves to disperse isophthalate-based chain extenders more uniformly. As the above polyvinyl alcohol, various types of polyvinyl alcohols with different degrees of hydration may be mixed and used, and the polyvinyl alcohol may include low-hydration polyvinyl alcohol with a degree of hydration of 30 to 65 mol% and high-hydration polyvinyl alcohol with a degree of hydration of 70 to 95 mol%. When the low-hydration polyvinyl alcohol and high-hydration polyvinyl alcohol are mixed and used, the stability of the final particles can be increased, the basic physical properties of the polymer obtained finally can be easily controlled, and a polymer with excellent meltability can be manufactured. Meanwhile, the above polyvinyl alcohol is in the form of polyvinyl acetate hydrated to substitute a portion of the acetate with alcohol, and the degree of hydration is defined as the degree to which the acetate is substituted with alcohol. The weight ratio between the low-hydration polyvinyl alcohol and the high-hydration polyvinyl alcohol may be 3:7 to 7:3, and preferably 5:5 to 7:3.

[0134] Meanwhile, the above polyvinyl alcohol can be used in an amount of 0.5 parts by weight or less per 100 parts by weight of vinyl chloride monomer, and preferably 0.5 parts by weight or less, 0.4 parts by weight or less, 0.3 parts by weight or less, or 0.2 parts by weight or less, and can be used in an amount of 0.05 parts by weight or more or 0.1 parts by weight or more.

[0135]

[0136] The sum HLB value of the chain extension agent may be 8 or higher and 11.5 or lower, and more preferably 9 to 11.5. The HLB value refers to the hydrophilic-lipophile balance, and a higher HLB value indicates higher hydrophilicity. The sum HLB value refers to the average value based on the weight of the HLB values ​​of each component, and the sum HLB value of the chain extension agent of the present invention can be calculated from the HLB values ​​of the nonionic emulsifier and polyvinyl alcohol. For example, the sum HLB value of 60 weight% of component A with an HLB of 10 and 40 weight% of component B with an HLB of 5 is 10 × 0.6 + 5 × 0.4 = 8.

[0137]

[0138] S2 stage

[0139] A polymerization reaction can be initiated in the presence of a chain extension aid prepared through the preceding steps.

[0140] The polymerization reaction of the present invention may be a suspension polymerization, and the suspension polymerization may be carried out in the presence of a polymerization water. The polymerization water may be used as a polymerization solvent, and various types of polymerization water, such as distilled water or deionized water, may be used, and preferably, deionized water may be used. The temperature of the polymerization water may be appropriately selected considering the temperature at which the suspension polymerization is performed, and the amount of the polymerization water may also be appropriately used according to the polymerization conditions, for example, at least 70 parts by weight, specifically 70 to 300 parts by weight, per 100 parts by weight of the vinyl chloride monomer.

[0141]

[0142] The above initiator is not particularly limited as long as it is applied to the suspension polymerization of vinyl chloride monomers, and specifically, the above initiator may be one or more selected from the group consisting of polyacyl peroxide-based initiators, peroxydicarbonate-based initiators, peroxyester-based initiators, sulfate-based initiators and azo-based initiators.

[0143] More specifically, the diacyl peroxide-based initiator may be one or more selected from the group consisting of dicumyl peroxide, dipentyl peroxide, 3,3,5-trimethylhexanoyl peroxide, and dilauryl peroxide. The peroxydicarbonate-based initiator may be one or more selected from the group consisting of diisopropyl peroxydicarbonate, di-sec-butylperoxydicarbonate, and di-2-ethylhexyl peroxide. The peroxyester-based initiator may be t-butylperoxypivalate or t-butylperoxyneodecanoate, or a mixture thereof. The sulfate-based initiator may be potassium persulfate or ammonium persulfate, or a mixture thereof. The azo-based initiator may be azobis-2,4-dimethylvaleronitrile.

[0144] The above initiator may be added in an amount of 0.02 to 0.2 parts by weight per 100 parts by weight of vinyl chloride monomer, and preferably in an amount of 0.04 to 0.12 parts by weight. If the amount of initiator added is too small, the reaction time is delayed and productivity is reduced, and if the amount of initiator added is too large, the initiator may not be completely consumed during the polymerization process and may remain in the vinyl chloride polymer produced at the end, which may reduce the thermal stability of the resin.

[0145]

[0146] S3 stage

[0147] A polymerization reaction can be initiated through the preceding steps, and after the polymerization reaction has proceeded to a certain extent, the reaction can be terminated to obtain a vinyl chloride-based polymer.

[0148] In this step, the temperature condition under which the polymerization reaction is performed may be 50°C or lower, preferably 30°C to 50°C, and particularly preferably 40°C to 50°C. As the temperature at which the polymerization reaction proceeds decreases, the degree of polymerization of the obtained vinyl chloride polymer increases; however, if the reaction temperature is excessively low, the reaction rate decreases significantly, and the productivity of the vinyl chloride polymer manufacturing process decreases significantly. Therefore, under the above-described temperature conditions, it is possible to efficiently produce a high-quality vinyl chloride polymer with a high degree of polymerization while minimizing the decrease in productivity.

[0149]

[0150] After performing a polymerization reaction to some extent in this step, the reaction can be terminated by adding a reaction terminator. The reaction terminator can terminate the polymerization reaction by reacting with the remaining unreacted initiator to cause the initiator to lose its function, and may be one or more selected from the group consisting of phenol compounds, amine compounds, nitrile compounds, and sulfur compounds. The above phenol compounds are triethylene glycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate, hydroquinone, p-methoxy phenol, t-butyl-4-hydroxyanisole, n-octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, 2,5-di-t-butyl hydroquinone, and 4,4'-butylidene bis(3-methyl-6-t-butyl It may be one or more selected from the group consisting of phenol (4,4'-butylidene bis(3-methyl-t-butyl phenol), t-butyl catechol, 4,4-thiobis(6-t-butyl-m-cresol)), and tocopherol. The amine compound may be one or more selected from the group consisting of N,N-diphenyl-p-phenylenediamine and 4,4-bis(dimethylbenzyl)diphenyl.The above nitrile compound may be one or more selected from the group consisting of 2-phenyl nitronyl nitroxide, 3-imidazoline nitroxide, and 4-hydroxy-2,2,6,6-tetramethyl piperidine-1-oxyl. The above sulfur compound may be one or more selected from the group consisting of dodecyl mercaptan and 1,2-biphenyl-2-thiol.

[0151]

[0152] In the method for manufacturing a vinyl chloride-based polymer according to the present invention, additives such as antioxidants, bases, crosslinking agents, polymerization regulators, chain transfer agents, antistatic agents, anti-scaling agents, and surfactants may be additionally added. The types and amounts of said additives are not particularly limited and may be used in the usual types and amounts known in the art. The said additives may be added at any point during the polymerization process, and may be added all at once or continuously.

[0153]

[0154] 2) Diene-based gum polymer

[0155]

[0156] The above-mentioned diene-based rubbery polymer plays a role in improving the permanent compression set rate in vinyl chloride-based resin compositions.

[0157]

[0158] The above-mentioned diene-based rubbery polymer may include vinyl cyanide-based monomer units and diene-based monomer units, and may be partially cross-linked.

[0159] The vinyl cyanide monomer unit above plays a role in enabling the diene rubbery polymer to have excellent oil resistance and wear resistance, and the diene monomer unit above plays a role in enabling the diene rubbery polymer to have excellent buffering and resilience.

[0160]

[0161] The above-described diene-based rubbery polymer may contain vinyl cyanide monomer units in an amount of 20% by weight or more, preferably 25% by weight or more, more preferably 30% by weight or more, and 50% by weight or less, preferably 45% by weight or less, more preferably 40% by weight or less. When the above-described conditions are satisfied, the diene-based rubbery polymer maintains excellent oil resistance and wear resistance, while possessing appropriate cushioning action and resilience, thereby enabling the maintenance of the elasticity of the rubber.

[0162] The above-mentioned diene-based rubbery polymer may include the above-mentioned diene-based monomer units so that the total content of the above-mentioned diene-based rubbery polymer is 100 weight%.

[0163]

[0164] When the above-mentioned diene-based rubber polymer is partially cross-linked, its resilience can be superior compared to an uncross-linked diene-based rubber polymer.

[0165] Meanwhile, fully cross-linked diene-based rubbery polymers require a vulcanization process and are difficult to recycle. However, if the diene-based rubbery polymer is partially cross-linked, it can be processed easily and recyclable because a vulcanization process is not required.

[0166]

[0167] The above-mentioned diene-based rubbery polymer may have a gel content of 60% by weight or more, preferably 65% ​​by weight or more, more preferably 80% by weight or more, and 90% by weight or less. If the above conditions are satisfied, it exhibits excellent compatibility with vinyl chloride-based polymers, and the vinyl chloride resin composition containing it may be recyclable. Furthermore, since a separate vulcanization process is not required, the processing process can be simple while maintaining excellent resilience. Additionally, it can complement the cold resistance and permanent compression set of vinyl chloride-based polymers.

[0168]

[0169] The above rubbery polymer may be a partially cross-linked acrylonitrile-butadiene rubbery polymer.

[0170]

[0171] The vinyl chloride-based resin composition may contain the diene-based rubbery polymer in an amount of 40 parts by weight or more and 100 parts by weight or less, relative to 100 parts by weight of the vinyl chloride-based polymer. The vinyl chloride-based resin composition may contain the diene-based rubbery polymer in an amount of preferably 40 parts by weight, more preferably 70 parts by weight or more, and preferably 100 parts by weight or less, relative to 100 parts by weight of the vinyl chloride-based polymer. If the above conditions are satisfied, the physical properties of the vinyl chloride-based resin composition can be improved by supplementing the cold resistance and permanent compression set of the vinyl chloride-based polymer. However, if the diene-based rubbery polymer is included in a small amount less than the above-described range, the effect of improving the permanent compression set is negligible. If the diene-based rubbery polymer is included in an excessive amount greater than the above-described range, weather resistance is reduced.

[0172]

[0173] 3) Additives

[0174]

[0175] The above additive may include one or more selected from the group consisting of an olefinic rubbery polymer containing two or more olefinic monomer units having 2 or more and 12 or fewer carbon atoms; a plasticizer; an acrylic processing aid; and an acrylic impact modifier.

[0176] In addition, the above additive may further include other additives comprising one or more selected from the group consisting of stabilizers, fillers, and lubricants.

[0177]

[0178] (1) Olefinic rubbery polymer

[0179]

[0180] The above-mentioned olefinic rubbery polymer serves to improve the productivity, elasticity, and impact resistance of the thermoplastic resin composition. Specifically, since the olefinic rubbery polymer has a relatively low density and high elasticity, it can be lightweight and have high productivity per meter when manufactured as an extruder. Furthermore, because the olefinic rubbery polymer does not require a vulcanization process, it is easy to recycle into an elastomer that can be processed using general thermoplastic processing equipment.

[0181]

[0182] The above-described olefinic rubbery polymer may include two or more types of olefinic monomer units having 2 or more carbon atoms and 12 or fewer carbon atoms. Specifically, it may include one or more types of olefinic monomer units having 2 or more carbon atoms and 4 or fewer carbon atoms, and one or more types of olefinic monomer units having 5 or more carbon atoms and 12 or fewer carbon atoms. When the above-described conditions are satisfied, bonding points may be formed in the molecular structure due to the difference in the number of carbon atoms of the olefinic monomer units. These bonding points perform cross-linking and buffering functions between molecules, providing an impact energy reduction effect where force is dispersed upon external impact, thereby increasing impact resistance. Additionally, when tension is applied to the structure, a structure such as a formed network deforms, which can also improve the elongation at break of the structure.

[0183]

[0184] The above olefinic rubbery polymer may include ethylene monomer units and 1-octene monomer units. The above olefinic rubbery polymer may be an ethylene-1-octene rubbery polymer.

[0185]

[0186] The above vinyl chloride-based resin composition may contain 5 parts by weight or more and 35 parts by weight or less of the olefinic rubbery polymer with respect to 100 parts by weight of the vinyl chloride-based polymer. The above vinyl chloride-based resin composition may contain 10 parts by weight, more preferably 15 parts by weight or more of the olefinic rubbery polymer, preferably 30 parts by weight or less, and more preferably 25 parts by weight or less, with respect to 100 parts by weight of the vinyl chloride-based polymer. If the above conditions are satisfied, the melt index of the vinyl chloride-based resin composition increases, which facilitates the mixing of the vinyl chloride-based resin composition. In addition, the impact resistance and elongation at break of the vinyl chloride-based resin composition may be improved, and compatibility with inorganic materials may be excellent. Furthermore, the occurrence of whitening may be suppressed.

[0187]

[0188] (2) Plasticizer

[0189]

[0190] The above plasticizer may be one or more selected from the group consisting of phthalate-based plasticizers, isophthalate-based plasticizers, terephthalate-based plasticizers, hydrogenated phthalate-based plasticizers, hydrogenated isophthalate-based plasticizers, hydrogenated terephthalate-based plasticizers, citrate-based plasticizers, trimellitate-based plasticizers, and adipate-based plasticizers.

[0191] The vinyl chloride-based resin composition may contain 50 parts by weight or more and 130 parts by weight or less of the plasticizer with respect to 100 parts by weight of the vinyl chloride-based polymer. The vinyl chloride-based resin composition may contain the plasticizer with respect to 100 parts by weight of the vinyl chloride-based polymer, preferably in an amount of 50 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, or 80 parts by weight or more, while containing 130 parts by weight or less, 120 parts by weight or less, or 110 parts by weight or less.

[0192]

[0193] (3) Acrylic processing aid

[0194]

[0195] The above acrylic processing aid can be included in the resin composition to further improve the permanent compression set rate.

[0196] The above vinyl chloride-based resin composition may contain the acrylic processing aid in an amount of 0.7 parts by weight or more and 4.5 parts by weight or less, based on 100 parts by weight of the vinyl chloride-based polymer. The above vinyl chloride-based resin composition may preferably contain the acrylic processing aid in an amount of 0.7 parts by weight or more, 0.8 parts by weight or more, or 1 part by weight or more, based on 100 parts by weight of the vinyl chloride-based polymer, while containing 4.5 parts by weight or less, 4.3 parts by weight or less, or 4 parts by weight or less. If the above conditions are satisfied, the permanent extrusion set of the vinyl chloride-based resin composition can be improved while also securing mechanical properties.

[0197]

[0198] Meanwhile, the above acrylic processing aid may have a weight average molecular weight of 5,000,000 g / mol or more and 15,000,000 g / mol or less. Preferably, it may be 7,000,000 g / mol or more, 8,000,000 g / mol or more, or 9,000,000 g / mol or more, and 13,000,000 g / mol or less, 12,000,000 g / mol or less, or 11,000,000 g / mol or less. If the above conditions are satisfied, the permanent compression set of the vinyl chloride resin composition can be improved.

[0199]

[0200] The above acrylic processing aid comprises a core comprising 80% to 85% by weight of a unit derived from a methyl methacrylate monomer and 10% to 15% by weight of a unit derived from an alkyl acrylate monomer; and a shell comprising 5% to 10% by weight of a unit derived from an alkyl methacrylate monomer crosslinked to the core; wherein the shell may comprise a unit derived from a crosslinking agent comprising a metal salt compound of a saturated fatty acid and a metal salt compound of a dicarboxylic acid.

[0201] The above alkyl acrylate monomer may be an alkyl acrylate having 1 to 18 carbon atoms, and specifically, may be one or more selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and stearyl acrylate. The above alkyl methacrylate monomer may be an alkyl methacrylate having 1 to 18 carbon atoms, and specifically, may be one or more selected from the group consisting of methyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate, tridecyl methacrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate. The above crosslinking agent is a reactive crosslinking agent comprising a metal salt compound of a saturated fatty acid and a metal salt compound of a dicarboxylic acid, for example, may be a mixture of a metal salt compound of a saturated fatty acid and a metal salt compound of a dicarboxylic acid, for example, the crosslinking agent may comprise 50% to 80% by weight of a metal salt compound of a saturated fatty acid; and 20% to 50% by weight of a metal salt compound of a dicarboxylic acid, or 60% by weight of a metal salt compound of a saturated fatty acid and 40% by weight of a metal salt compound of a dicarboxylic acid.

[0202] As the above acrylic processing aid, one or more products selected from the group consisting of LG Chem’s PA950 and PA932 may be used, and preferably, PA950 may be used.

[0203]

[0204] (4) Acrylic impact modifier

[0205]

[0206] The above acrylic impact modifier can be included in the vinyl chloride resin composition to further improve the permanent compression set.

[0207] The above vinyl chloride-based resin composition may contain at least 3 parts by weight and no more than 10 parts by weight of the acrylic impact modifier with respect to 100 parts by weight of the above vinyl chloride-based polymer. The above vinyl chloride-based resin composition may contain, preferably with respect to 100 parts by weight of the above vinyl chloride-based polymer, at least 3.5 parts by weight or at least 4 parts by weight of the acrylic impact modifier, while containing no more than 10 parts by weight, no more than 9 parts by weight or no more than 8 parts by weight. If the above conditions are satisfied, the permanent extrusion set of the vinyl chloride-based resin composition can be improved while also securing mechanical properties.

[0208] The above acrylic impact modifier may comprise an acrylic rubber core and a shell comprising units derived from acrylate monomers. The acrylic rubber core constituting the core may be copolymerized with an alkyl acrylate monomer having 2 to 18 carbon atoms and a crosslinkable monomer, and the shell may be copolymerized with an acrylate monomer, a water-soluble comonomer, and a polyfunctional monomer.

[0209] More specifically, the alkyl acrylate monomer included in the core may be one or more selected from the group consisting of ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, and allyl acrylate.

[0210] The above crosslinkable monomer may be one or more selected from the group consisting of 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, alkyl acrylate having 1 to 8 carbon atoms, allyl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, divinylbenzene, polyethylene glycol acrylate, polyethylene glycol methacrylate, and butylene glycol dimethacrylate.

[0211] The content of the alkyl acrylate monomer in the core may be 90 to 99 weight% based on the total weight of the core, and the content of the crosslinkable monomer may be 0.1 to 10 weight% based on the total weight of the core.

[0212] The acrylate monomer constituting the shell may be an alkyl methacrylate monomer having 2 to 18 carbon atoms, and more specifically, may be one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate. The acrylate monomer may be included in an amount of 70 to 99 weight% based on the total weight of the shell.

[0213] The above-mentioned water-soluble comonomer may be one or more selected from the group consisting of anionic comonomers and cationic comonomers. The above-mentioned anionic comonomer may be one or more selected from the group consisting of acrylic acid, methacrylic acid, sodium p-styrene sulfonate, sodium methallyl sulfonate, sodium salt of 2-sulfoethyl methacrylate, and sodium undecylenic isothionate. The cationic comonomer may be one or more selected from the group consisting of acrylamide, 1,2-dimethyl 5-vinyl-pyridinium methylsulfate, and 1-methyl 2-ethyl 5-vinyl pyridinium bromide. The water-soluble comonomer may be included in an amount of 0.05 to 30 weight% based on the total weight of the shell.

[0214] The above-mentioned polyfunctional monomer is poly(ethylene glycol) monoacrylate, poly(ethylene glycol) monomethacrylate, poly(ethylene glycol) diacrylate, poly(ethylene glycol) dimethacrylate, methoxy poly(ethylene glycol) monoacrylate, methoxy (ethylene glycol) monomethacrylate, phenoxy poly(ethylene glycol) monoacrylate, phenoxy poly(ethylene glycol), poly(propylene glycol) monoacrylate, poly(propylene glycol) monomethacrylate, poly(propylene glycol) diacrylate, poly(propylene glycol) dimethacrylate, methoxy poly(propylene glycol) monoacrylate, methoxy poly(propylene glycol) monomethacrylate, phenoxy poly(propylene glycol) monoacrylate, phenoxy poly(propylene glycol) monomethacrylate, poly(ethylene propylene glycol) monoacrylate, It may be one or more selected from the group consisting of poly(ethylene propylene glycol) monomethacrylate, poly(ethylene propylene glycol) diacrylate, poly(ethylene propylene glycol) dimethacrylate, methoxy poly(ethylene propylene glycol) monoacrylate, methoxy (ethylene propylene glycol) monomethacrylate, methoxy poly(ethylene propylene glycol) monomethacrylate, phenoxy poly(ethylene propylene) monoacrylate, and phenoxy poly(ethylene propylene) monomethacrylate. The polyfunctional monomer may be included in an amount of 0.05 to 30 weight% based on the total weight of the shell.

[0215] The above acrylic impact modifier may comprise 70 to 99 weight percent of the core and 1 to 30 weight percent of the shell based on 100 weight percent of the total.

[0216] As the above acrylic impact modifier, one or more products selected from the group consisting of LG Chem’s IM812N and IM810 may be used.

[0217]

[0218] (5) Other additives

[0219]

[0220] The above other additives may further include one or more selected from the group consisting of stabilizers, fillers, and lubricants.

[0221] The above stabilizer may be a conventional stabilizer used with vinyl chloride-based polymers, specifically Ca-Zn compounds; Ba-Zn compounds; mercaptide compounds; organic tin compounds such as maleic acid compounds or carboxylic acid compounds; metallic soap compounds such as Mg-stearate, Ca-stearate, Pb-stearate, Cd-stearate, or Ba-stearate; phenol compounds; phosphate ester compounds; or phosphite ester compounds; and one or more of the fillers listed above may be selected and used according to the application. Preferably, in the present invention, a Ca-Zn compound may be used.

[0222] The above vinyl chloride-based resin composition may contain the stabilizer in an amount of 1 part by weight or more and 15 parts by weight or less per 100 parts by weight of the above vinyl chloride-based polymer, and preferably may contain 1 part by weight or more, 3 parts by weight or more, or 5 parts by weight or more, while containing 15 parts by weight or less, 13 parts by weight or less, or 10 parts by weight or less.

[0223]

[0224] The above filler may be a conventional filler used with vinyl chloride-based polymers, and specifically, calcium carbonate, clay, talc, or diatomaceous earth may be used.

[0225] The above vinyl chloride-based resin composition may contain the filler in an amount of 10 parts by weight or more and 50 parts by weight or less per 100 parts by weight of the above vinyl chloride-based polymer, preferably in an amount of 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight or more, and may contain 50 parts by weight or less, 45 parts by weight or less, or 40 parts by weight or less.

[0226]

[0227] The above vinyl chloride-based resin composition may contain the above lubricant in an amount of 0.05 parts by weight or more and 1 part by weight or less per 100 parts by weight of the above vinyl chloride-based polymer, preferably in an amount of 0.1 parts by weight or more, 0.15 parts by weight or more, or 0.2 parts by weight or more, and may contain 1 part by weight or less, 0.8 parts by weight or less, 0.6 parts by weight or less, or 0.5 parts by weight or less.

[0228]

[0229] As previously discussed, the vinyl chloride-based polymer of the present invention exhibits excellent melting characteristics, and accordingly, the time between the point where the torque reaches a maximum value and the point where the maximum value is reached in the graph obtained from the melting rate analysis of the vinyl chloride-based resin composition may be 60 seconds or less, preferably 55 seconds or less, 50 seconds or less, or 45 seconds or less. In addition, the time between the point where the torque reaches a maximum value and the point where the torque recovers to a torque value corresponding to the maximum value after the point obtained from the melting rate analysis of the vinyl chloride-based resin composition may be 30 seconds or less, preferably 28 seconds or less, 26 seconds or less, or 24 seconds or less.

[0230] The melting rate analysis of the vinyl chloride-based resin composition may be performed using a Brabender plastograph, and the analysis may be performed while operating the device at a temperature of 135°C and a speed of 70 rpm. The graph obtained from the melting rate analysis may be a graph with time on the horizontal axis and torque value on the vertical axis.

[0231]

[0232] Preferred embodiments are presented below to aid in understanding the present invention. However, the following embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

[0233]

[0234] Examples and Comparative Examples

[0235]

[0236] The information on the components used in the following examples and comparative examples is as follows.

[0237]

[0238] 1) Vinyl chloride-based polymer

[0239] (1) Vinyl chloride-based polymer 1: HRTP4000 of LG Chem (degree of polymerization: 4,100, weight average molecular weight: 485,170 g / mol, number average molecular weight: 125,949 g / mol, polydispersity index: approx. 3.85, content of low molecular weight vinyl chloride-based polymer: 28.9 wt%, plasticizer absorption rate: 52.0 phr)

[0240] (2) Vinyl chloride-based polymer 2: LG Chem's LS100 (Degree of polymerization: 990, Weight average molecular weight: 141,997 mol / g, Number average molecular weight: 64,764 mol / g, Polydispersity index: approx. 2.19, Plasticizer absorption rate: 24.0 phr)

[0241] (3) Vinyl chloride-based polymer 3: LG Chem's LS130S (degree of polymerization: 1,280, weight average molecular weight: 191,876 mol / g, number average molecular weight: 71,409 mol / g, polydispersity index: approx. 2.687, plasticizer absorption rate: 28.5 phr)

[0242]

[0243] 2) Diene-based gum polymer

[0244] (1) Diene-based rubbery polymer 1: A partially cross-linked acrylonitrile-butadiene rubbery polymer comprising 35 wt% acrylonitrile monomer units and 65 wt% butadiene monomer units, with a gel content of 65 wt% (Manufacturer: SYNTHOMER, Trade name: CHEMIGUM TM P35)

[0245]

[0246] (2) Diene-based gummous polymer 3: A partially cross-linked acrylonitrile-butadiene gummous polymer comprising 33 wt% acrylonitrile monomer units and 67 wt% butadiene monomer units, with a gel content of 65 wt% (Manufacturer: SYNTHOMER, Trade name: CHEMIGUM TM P83)

[0247]

[0248] (3) Diene-based gum polymer 3: Uncrosslinked acrylonitrile-butadiene gum polymer comprising 33 wt% acrylonitrile monomer units and 67 wt% butadiene monomer units (Manufacturer: Hualan Technology, Trade name: HNL35-2)

[0249]

[0250] 3) Olefinic rubber polymer: Olefinic rubber polymer: Ethylene-1-octene rubber polymer (Manufacturer: LG Chem Corp., Trade name: LUCENETM LC170)

[0251]

[0252] 4) Plasticizer

[0253] (1) Plasticizer 1: Tri(2-ethylhexyl) trimellitate

[0254] (2) Plasticizer 2: Triisononyl trimellitate

[0255] (3) Plasticizer 3: Diisononyl phthalate

[0256] (4) Plasticizer 4: Di(2-ethylhexyl) terephthalate (Manufacturer: LG Chem, Trade name: GL300)

[0257] (4) Plasticizer 5: Polydi(2-ethylhexyl)glycol adipate (Manufacturer: Songwon Industrial, Product name: P-3000)

[0258]

[0259] 5) Processing aids

[0260] (1) Processing aid 1: Methyl methacrylate-butyl acrylate copolymer (Manufacturer: LG Chem Co., Ltd., Product name: PA932)

[0261] (2) Processing aid 2: Acrylic processing aid with a weight-average molecular weight of about 1,000,000 g / mol (Manufacturer: LG Chem Co., Ltd., Product name: PA912)

[0262] (3) Processing aid 3: Acrylic processing aid with a weight-average molecular weight of about 10,000,000 g / mol (Manufacturer: LG Chem Co., Ltd., Product name: PA950)

[0263]

[0264] 6) Acrylic Impact Modifier: IM812N (Product Name, Manufacturer: LG Chem Corp.)

[0265]

[0266] 7) Stabilizer: Zinc complex type stabilizer (Manufacturer: ADEKA, Trade name: RUP-144S)

[0267]

[0268] 8) Filler: Calcium carbonate

[0269]

[0270] 9) Lubricant: Low-density oxidized polyethylene homopolymer (Manufacturer: Honeywell, Trade name: AC ® 629A)

[0271]

[0272] <Preparation of Vinyl Chloride Resin Composition>

[0273] A vinyl chloride-based resin composition was prepared by mixing and stirring the above-mentioned components in the amounts listed in Tables 1 to 6 below.

[0274]

[0275] Experimental Example 1

[0276] The physical properties of the vinyl chloride-based resin compositions of the examples and comparative examples were measured by the method described below, and the results are shown in Tables 1 to 6 below.

[0277]

[0278] 1) Permanent compression set (%): After preparing specimens (shape: cylindrical, thickness: 12.70 ± 0.13 mm, diameter: 29.0 mm) according to KS M 6518:2021 and ASTM D396, the permanent compression set was measured at 70 ± 1 ℃ for 22 hours.

[0279]

[0280] 2) Cold resistance (unit: ℃): The 50% impact embrittlement temperature was determined by the graphical method in accordance with KS M 6676:2008, and the cold resistance (low-temperature impact embrittlement test) was evaluated.

[0281]

[0282] 3) Weather resistance: Weather resistance was evaluated in accordance with JIS D205-1987.

[0283]

[0284] 4) Hardness: The hardness of specimens (thickness: 12 mm) was measured using a ZwickRoell hardness tester of the Shore A type in accordance with KS M 6518 and ASTM D2240. Specifically, the prepared specimen was placed on the specimen measuring plate, and the hardness value was measured after 10 seconds by tipping down at 5 points on the specimen. The average values ​​of the measured hardness values ​​are listed in Tables 1 to 6 below.

[0285]

[0286] 5) Specific gravity: The weight and volume of the permanent compression set specimen prepared according to the KS M 6518 test method were measured, and the value obtained by dividing the measured weight by the measured volume (weight / volume) was defined as the specific gravity.

[0287]

[0288] 6) Tensile strength (MPa) and elongation (%): Dumbbell-shaped specimens No. 3 were prepared in accordance with KS M 6518:2021 and ISO 37, and the tensile strength and elongation of 5 specimens were measured using a tensile testing machine (Manufacturer: Instron, Product Name: 3345 Machine Serial Number Locator). The average values ​​of the measured tensile strength and elongation are listed in Tables 1 to 6 below.

[0289] Classification Example 1 Example 2 Example 3 Example 4 Example 5 Vinyl chloride resin composition (parts by weight) Vinyl chloride polymer 1100.0100.0100.0100.0100.0 Dienene rubbery polymer 140.070.0100.00.00.0 Dienene rubbery polymer 20.00.00.040.070.0 Plasticizer 1100.0100.0100.0100.0100.0 Processing aid 12.02.02.02.02.0 Stabilizer 7.07.07.07.07.0 Fillant 30.030.030.030.030.0 Lubricant 0.30.30.30.30.30.3 Physical properties: Permanent Compression Set (%) 45 40 35 48 42 Cold Resistance -50.0 ≤ -52.0 ≤ -52.0 -50.0 ≤ -52.0 Weather Resistance ○○○○○ Hardness 60 60 60 60 Specific Gravity 1.1 3 1.1 2 1.1 0 1.1 3 1.1 Tensile Strength (MPa) 10.4 1 1.1 1 1.2 10.4 1 1.1 Elongation (%) 34 9 35 0 35 1 34 9 35 1

[0290] Classification Example 6 Example 7 Example 8 Vinyl chloride resin composition (parts by weight) Vinyl chloride polymer 1100.0 100.0 100.0 Vinyl chloride polymer 30.0 0.0 0.0 Dienine rubbery polymer 1100.0 100.0 100.0 Olefinic rubbery polymer 5.0 10.0 20.0 Plasticizer 1100.0 100.0 100.0 Processing aid 12.0 2.0 2.0 Stabilizer 7.0 7.0 7.0 Fillant 30.0 30.0 30.0 Lubricant 0.3 0.3 0.3 Physical properties Permanent Compression set (%) 35 35 35 Cold resistance -50 ≤ -52 ≤ -52 Weather resistance --- Hardness 60 60 60 Specific gravity 1.18 1.09 1.07 Tensile strength (MPa) 11.0 11.0 11.0 Elongation (%) 35 35 0 350

[0291] Classification Example 9 Example 10 Example 11 Example 12 Example 13 Vinyl chloride-based resin composition (parts by weight) Vinyl chloride-based polymer 1100.0100.0100.0100.0100.0 Dienene-based rubbery polymer 140.070.0100.0100.0100.0 Dienene-based rubbery polymer 20.00.00.00.00.0 Plasticizer 1100.0100.030.00.015.0 Plasticizer 20.00.00.00.00.0 Plasticizer 30.00.00.00.00.0 Plasticizer 40.00.070.0100.035.0 Plasticizer 50.00.00.00.050.0 Processing aid 12.02.02.02.02.0 Stabilizer 7.07.07.07.07.0 Filler 30.030.030.030.030.0 Lubricant 0.30.30.30.30.3 Physical Properties Permanent Compression Set (%) 4540354040 Cold Resistance-----Weather Resistance-----6 Hardness 6060606363 Specific Gravity 1.141.121.091.081.10 Tensile Strength (MPa) 10.011.011.010.010.0 Elongation (%) 350350350350350

[0292] Classification Example 14 Example 15 Example 16 Vinyl chloride resin composition (parts by weight) Vinyl chloride polymer 1100.0100.0100.0 Dienene rubbery polymer 1100.0100.0100.0 Dienene rubbery polymer 20.00.00.0 Plasticizer 1100.0100.0100.0 Processing aid 10.00.00.0 Processing aid 20.00.00.0 Processing aid 31.02.04.0 Stabilizer 7.07.07.0 Fillant 30.030.030.0 Lubricant 0.30.30.3 Physical properties Permanent Compression set (%) 333434 Cold resistance ≤ -55 ≤ -55 ≤ -55 Weather resistance --- Hardness 6 36060 Specific gravity 1.07 1.07 1.07 Tensile strength (MPa) 11.5 11.0 11.0 Elongation (%) 360 350 350

[0293] Classification Example 17 Example 18 Example 19 Vinyl chloride resin composition (parts by weight) Vinyl chloride polymer 1100.0100.0100.0 Dienene rubbery polymer 1100.0100.0100.0 Dienene rubbery polymer 20.00.00.0 Plasticizer 1100.0100.0100.0 Processing aid 12.02.02.0 Acrylic impact modifier 4.06.08.0 Stabilizer 7.07.07.0 Fillant 26.024.022.0 Lubricant 0.30.30.3 Physical properties: Permanent Compression set (%) 333434 Cold resistance ≤ -55 ≤ -55 ≤ -55 Weather resistance --- Hardness 626060 Specific gravity 1.07 1.06 1.05 Tensile strength (MPa) 11.5 11.0 11.0 Elongation (%) 360 350 350

[0294] Classification Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Vinyl chloride-based resin composition (parts by weight) Vinyl chloride-based polymer 1 100.00.00.0 100.0 100.0 100.0 Vinyl chloride-based polymer 20.0 100.00.00.00.00.0 Vinyl chloride-based polymer 30.00.0 100.00.00.00.0 Dienene-based rubbery polymer 10.00.00.00.0 35.0 110.0 Dienene-based rubbery polymer 20.00.00.00.00.00.0 Dienene-based rubbery polymer 3 (uncrosslinked) 0.00.000.0 100.00.00.0 Plasticizer 1100.0100.0100.0100.0100.0100.0 Processing aid 12.02.02.02.02.02.0 Stabilizer 7.07.07.07.07.07.0 Filler 30.030.030.030.030.030.0 Lubricant 0.30.30.30.30.30.30.3 Physical properties permanent Compression Set (%) 50 60 58 50 48 35 Cold Resistance -5 0.0 -3 8.0 -4 0.0 ≤ -5 2 -5 0.0 ≤ -5 2 Weather Resistance ○○○○○ × Hardness 60 70 70 60 65 65 Specific Gravity 1.10 1.23 1.23 1.10 1.10 1.10 Tensile Strength (MPa) 10.0 9.0 8.0 11.0 10.0 10.0 Elongation (%) 35 0 28 0 30 0 35 0 35 0 35 0

[0295] Referring to Tables 1 to 6, the vinyl chloride resin compositions of Examples 1 to 19, which include a suitable vinyl chloride polymer and a partially cross-linked rubbery polymer, had a lower permanent compression set compared to the vinyl chloride resin composition of Comparative Example 1, which does not include a partially cross-linked diene rubbery polymer.

[0296] The thermoplastic resin compositions of Comparative Examples 2 and 3, which contain an unsuitable vinyl chloride-based polymer and do not contain a partially cross-linked diene-based rubbery polymer, had a higher permanent compression set compared to the vinyl chloride-based resin compositions of Examples 1 to 19, lower tensile strength and elongation, and higher specific gravity.

[0297] The vinyl chloride resin composition of Comparative Example 4, which contains a suitable vinyl chloride polymer and a small amount of uncrosslinked diene rubbery polymer, had a higher permanent extrusion set compared to the vinyl chloride resin compositions of Examples 1 to 19.

[0298] The vinyl chloride resin composition of Comparative Example 5, which contains a suitable vinyl chloride polymer and a small amount of partially cross-linked diene rubbery polymer, had a higher permanent compression set rate compared to the vinyl chloride resin compositions of Examples 1 to 19.

[0299] In addition, the vinyl chloride resin composition of Comparative Example 6, which contains an excess amount of a suitable vinyl chloride polymer and a partially cross-linked diene rubbery polymer, showed reduced weather resistance compared to the vinyl chloride resin compositions of Examples 1 to 5.

Claims

1. 100 parts by weight of a vinyl chloride-based polymer having a degree of polymerization of 3,700 or more and 5,000 or less, and a polydispersity index of 3.5 or more; and A vinyl chloride resin composition comprising vinyl cyanide-based monomer units and diene-based monomer units, and comprising 40 parts by weight or more and 100 parts by weight or less of a partially cross-linked diene-based rubbery polymer.

2. In Claim 1, The above vinyl chloride polymer is a vinyl chloride-based resin composition having a plasticizer absorption rate of 40 phr or more and 90 phr or less.

3. In Claim 1, A vinyl chloride-based resin composition having a degree of polymerization of 3,800 or more and 4,500 or less.

4. In Claim 1, A vinyl chloride-based resin composition having a polydispersity index of 3.5 or higher and 4.1 or lower.

5. In Claim 1, The above vinyl chloride-based polymer is a vinyl chloride resin composition comprising a mixture of 28% by weight or more and 32% by weight or less of a low molecular weight vinyl chloride-based polymer having a molecular weight of 100,000 g / mol or less.

6. In Claim 1, The above vinyl chloride-based polymer is a vinyl chloride resin composition in which the area of ​​the left region, based on the molecular weight value where a peak appears in the molecular weight graph obtained through gel penetration chromatography analysis, is 50% or more of the total area of ​​the graph.

7. In Claim 1, The above diene-based rubbery polymer is a vinyl chloride-based resin composition that is a partially cross-linked acrylonitrile-butidiene rubbery polymer.

8. In Claim 1, The above diene-based rubbery polymer is a vinyl chloride-based resin composition having a gel content of 60 weight% or more and 90 weight% or less.

9. In Claim 1, With respect to 100 parts by weight of the above vinyl chloride-based polymer, A vinyl chloride-based resin composition comprising 70 parts by weight or more and 100 parts by weight or less of the above-mentioned diene-based rubbery polymer.

10. In Claim 1, A vinyl chloride resin composition comprising an olefinic rubbery polymer comprising two or more types of olefinic monomer units having 2 or more carbon atoms and 12 or fewer carbon atoms; a plasticizer; an acrylic processing aid; and an additive comprising one or more selected from the group consisting of an acrylic impact modifier.

11. In Claim 10, The above olefinic rubbery polymer comprises one or more olefinic monomer units having 2 or more and 4 or fewer carbon atoms; and one or more olefinic monomer units having 5 or more and 12 or fewer carbon atoms, comprising a vinyl chloride resin composition.

12. In Claim 10, The above olefinic rubbery polymer is a vinyl chloride-based resin composition comprising ethylene monomer units and 1-octene monomer units.

13. In Claim 10, With respect to 100 parts by weight of the above vinyl chloride-based polymer, A vinyl chloride resin composition comprising 5 parts by weight or more and 20 parts by weight or less of the above-mentioned olefinic rubbery polymer.

14. In Claim 10, The above-mentioned plasticizer is a vinyl chloride resin composition comprising one or more selected from the group consisting of phthalate-based plasticizers, isophthalate-based plasticizers, terephthalate-based plasticizers, hydrogenated phthalate-based plasticizers, hydrogenated isophthalate-based plasticizers, hydrogenated terephthalate-based plasticizers, citrate-based plasticizers, trimellitate-based plasticizers, and adipate-based plasticizers.

15. In Claim 10, With respect to 100 parts by weight of the above vinyl chloride-based polymer, A vinyl chloride-based resin composition comprising 50 parts by weight or more and 130 parts by weight or less of the above-mentioned plasticizer.

16. In Claim 10, The above acrylic processing aid is a vinyl chloride resin composition having a weight average molecular weight of 5,000,000 g / mol or more and 15,000,000 g / mol or less.

17. In Claim 10, The above acrylic processing aid comprises: a core comprising 80% to 85% by weight of a methyl methacrylate monomer-derived unit and 10% to 15% by weight of an alkyl acrylate monomer-derived unit; and a shell comprising 5% to 10% by weight of an alkyl methacrylate monomer-derived unit crosslinked to the core. A vinyl chloride-based resin composition in which the shell comprises a crosslinking agent-derived unit including a metal salt compound of a saturated fatty acid and a metal salt compound of a dicarboxylic acid.

18. In Claim 10, With respect to 100 parts by weight of the above vinyl chloride-based polymer, A vinyl chloride resin composition comprising 0.7 parts by weight or more and 4.5 parts by weight or less of the above-mentioned acrylic processing aid.

19. In Claim 10, The above acrylic impact modifier is a vinyl chloride resin composition comprising an acrylic rubber core and a shell containing acrylate monomer units.

20. In Claim 10, With respect to 100 parts by weight of the above vinyl chloride-based polymer, A vinyl chloride resin composition comprising 3 parts by weight or more and 10 parts by weight or less of the above-mentioned acrylic impact modifier.