KR101982573B1 - Thermoplastic resin composition, preparation method thereof and thermoplastic resin molded article produced by the same - Google Patents

Abstract

The present invention provides a thermoplastic resin composition capable of producing a molded article having low plasticizer migration property and excellent processability, particularly low-temperature processability, a method for producing the thermoplastic resin composition, and a thermoplastic resin molded article produced therefrom. Since the thermoplastic resin composition exhibits a low melt viscosity characteristic without containing a separate plasticizer, the thermoplastic resin molded article produced therefrom exhibits excellent plasticizer migration properties and low-temperature flexible temperature characteristics as well as processability, particularly low-temperature processability .

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition, a method for producing the same, and a thermoplastic resin composition produced from the thermoplastic resin composition.

The present invention relates to a thermoplastic resin composition capable of producing a molded article having a low plasticizer migration property and excellent processability, particularly low-temperature processability, a method for producing the same, and a thermoplastic resin molded article produced therefrom.

The vinyl chloride polymer is a homopolymer of vinyl chloride or an interpolymer containing 50% or more of vinyl chloride, and is widely used in piping materials, construction materials, and the like due to its excellent mechanical strength, weather resistance, and chemical resistance. However, since the vinyl chloride polymer itself has low moldability, various additives such as plasticizers are suitably added to impart processing properties.

In general, the molding processability of a vinyl chloride polymer greatly depends on the particle characteristics of the vinyl chloride polymer. In order to improve the productivity in the production of a molded article using a vinyl chloride polymer, the bulk density, internal porosity, particle size or particle distribution of the vinyl chloride polymer particles are controlled to improve the gelation property, plasticizer absorbability or powder fluidity .

As a method for improving the molding processability of a conventional vinyl chloride polymer, there has been proposed a process for improving the processability of the vinyl chloride polymer itself by using a dispersion stabilizer such as polyvinyl alcohol or the like when polymerizing a vinyl chloride polymer. However, according to this method, although the volume specific gravity of the vinyl chloride-based polymer is increased, there is a problem that the melting property of the polymer is lowered.

On the other hand, as a method for improving the processability and melting properties of the vinyl chloride polymer, a method of controlling the degree of polymerization distribution by changing the temperature during the polymerization reaction of the vinyl chloride polymer has been proposed. However, although the vinyl chloride-based polymer having a high bulk density and improved workability can be prepared, the polymerization reaction time is prolonged and the productivity is lowered. Further, the vinyl chloride- There has been a problem that the physical properties of the polymer itself, such as an increase in colorability and a decrease in mechanical properties, are deteriorated due to side reactions between the reactant and the additive.

As another method for improving the moldability of a vinyl chloride polymer, a method of using a plasticizer together with a vinyl chloride polymer in the production of a molded product is mainly used. However, when such a plasticizer is used, there is a problem that the plasticizer moves to the surface of the product to cause stickiness on the surface, and the plasticity gradually decreases with time. Especially, in the case of the phthalate plasticizer mainly used, A large amount of smoke is generated, flexibility is exhibited at a high temperature, and high energy is required for processing.

Therefore, there is a need to develop a technique for producing a vinyl chloride polymer having high processability while having excellent mechanical properties and chemical properties

Korea Patent No. 160332 (registered on August 18, 1998)

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art, and an object of the present invention is to provide a thermoplastic resin composition capable of obtaining a thermoplastic resin molded article having low plasticizer migration property and excellent processability, particularly low-temperature processability.

Another object of the present invention is to provide a method for producing the thermoplastic resin composition.

It is still another object of the present invention to provide a thermoplastic resin molded article produced from the thermoplastic resin composition.

In order to solve the above problems, according to one embodiment of the present invention, a vinyl chloride copolymer is contained in an amount of 90 wt% or more, and the vinyl chloride copolymer is copolymerized in an amount of 3 wt% to 35 wt% Unit, and the repeating unit derived from the unsaturated fatty acid ester includes repeating units derived from a cis isomer of an unsaturated fatty acid ester and a trans isomer of an unsaturated fatty acid ester in a weight ratio of 60:40 to 99: 1 And a thermoplastic resin composition.

According to another embodiment of the present invention, there is provided a process for producing a vinyl chloride copolymer, which comprises polymerizing 3 to 53 parts by weight of an unsaturated fatty acid ester with 100 parts by weight of a vinyl chloride monomer in the presence of a polymerization initiator to prepare a vinyl chloride- , And the unsaturated fatty acid ester comprises a cis isomer of an unsaturated fatty acid ester and a trans isomer in a weight ratio of 60:40 to 99: 1.

Still further, according to another embodiment of the present invention, there is provided a thermoplastic resin molded article produced from the thermoplastic resin composition.

The thermoplastic resin composition according to the present invention contains a vinyl chloride-based copolymer containing a repeating unit derived from an unsaturated fatty acid ester, and can exhibit low melt viscosity characteristics without containing a separate plasticizer as an additive.

Further, the thermoplastic resin molded article according to the present invention is excellent in plasticizer migration property and low-temperature softening temperature characteristic as well as in processability, especially low-temperature processability, by being produced from the thermoplastic resin composition.

Therefore, the thermoplastic resin composition according to the present invention and the thermoplastic resin molded article produced therefrom can be easily applied to an industry that requires it, particularly, a vinyl chloride thermoplastic resin molded article industry.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and form a part of the specification, illustrate preferred embodiments of the invention and, together with the description of the invention given above, serve to further the understanding of the technical idea of the invention, It should not be construed as limited.
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a graph showing changes in melt viscosity according to shear rates of the thermoplastic resin compositions in Examples 1 to 3 and Comparative Examples 1 to 4; FIG.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The present invention provides a thermoplastic resin composition capable of producing a thermoplastic resin molded article having low plasticizer migration property and excellent processability, particularly low-temperature processability.

Specifically, the thermoplastic resin composition according to an embodiment of the present invention comprises 90% by weight or more of a vinyl chloride-based copolymer, and the vinyl chloride-based copolymer contains 3 to 35% by weight of an unsaturated fatty acid ester- Wherein the repeating unit derived from an unsaturated fatty acid ester comprises a repeating unit derived from a cis isomer of an unsaturated fatty acid ester and a repeating unit derived from a trans isomer of an unsaturated fatty acid ester in a weight ratio of 60:40 to 99: .

In the thermoplastic resin composition according to one embodiment of the present invention, the vinyl chloride-based copolymer may specifically include a repeating unit derived from a vinyl chloride-based monomer and an unsaturated fatty acid ester-derived repeating unit.

The repeating unit derived from the vinyl chloride monomer may be a repeating unit derived from a vinyl chloride monomer or a repeating unit derived from a vinyl chloride monomer and a polymer or oligomer of a vinyl monomer capable of polymerization with the vinyl chloride monomer. When the repeating unit derived from the vinyl chloride monomer is a repeating unit derived from a vinyl chloride monomer and a polymer or oligomer of the vinyl monomer, the polymer or oligomer may contain 50% by weight or more of vinyl chloride derived structural units.

Examples of the vinyl monomer copolymerizable with the vinyl chloride monomer include olefin compounds such as ethylene, propylene and butene; vinyl esters such as vinyl acetate, vinyl propionate and vinyl stearate; and acrylonitrile and the like Unsaturated nitriles, vinyl alkyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl octyl ether and vinyl launy ether, halogenated vinylidene halides such as vinylidene chloride, acrylic acid, methacrylic acid, itaconic acid, Unsaturated fatty acids such as maleic acid, fumaric acid, maleic anhydride and itaconic anhydride and anhydrides of these fatty acids, unsaturated fatty acid esters such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate and butyl benzyl maleate, And the like.

In the vinyl chloride-based copolymer in the thermoplastic resin composition according to the embodiment of the present invention, the repeating unit derived from the unsaturated fatty acid ester is derived from an unsaturated fatty acid ester, and the unsaturated fatty acid ester may be a vinyl chloride- Is a comonomer that forms a copolymer. Accordingly, when the vinyl chloride-based copolymer is copolymerized with the vinyl chloride-based monomer, the plasticizer serves as an internal plasticizer to improve the plasticity of the produced vinyl chloride-based copolymer. As a result, the vinyl chloride- The processability of the thermoplastic resin composition can be improved.

As described above, the repeating unit derived from the unsaturated fatty acid ester may contain a repeating unit derived from a cis isomer of an unsaturated fatty acid ester and a repeating unit derived from a trans isomer. Specifically, the repeating unit derived from the unsaturated fatty acid ester may be an unsaturated And a cis isomer and a trans isomer of a fatty acid ester in a weight ratio of 60:40 to 99: 1. The cis isomer of the unsaturated fatty acid ester exhibits excellent reactivity, while the trans isomer of the unsaturated fatty acid ester exhibits lower reactivity than the cis isomer due to steric hindrance, and is advantageous in copolymerization rather than homopolymerization. Therefore, it may be important to control the ratio of the cis isomer of the unsaturated fatty acid ester to the trans isomer in order to improve the plasticity of the vinyl chloride-based copolymer containing it. In the thermoplastic resin composition according to one embodiment of the present invention, the vinyl chloride-based copolymer is obtained by copolymerizing a repeating unit derived from a cis isomer of an unsaturated fatty acid ester and a repeating unit derived from a trans isomer in a repeating unit derived from an unsaturated fatty acid ester It is possible to exhibit excellent plasticity and to reduce the plasticizer migration property of the thermoplastic resin molded article produced from the thermoplastic resin composition and to improve the processability.

The unsaturated fatty acid ester may specifically be an unsaturated dicarboxylic acid ester. More specifically, the unsaturated fatty acid ester cis isomer may be a compound represented by the following formula (1), wherein the trans isomer of the unsaturated fatty acid ester is represented by the following formula 2: < RTI ID = 0.0 >

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

R ₁ to R ₄ each independently may be selected from the group consisting of a linear or branched alkyl group having 5 to 14 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and combinations thereof. More specifically, each of R ₁ to R ₄ may independently be a straight or branched alkyl group having 6 to 14 carbon atoms, more particularly 6 to 12 carbon atoms.

In the present invention, the term " a combination thereof "'means an alkylene group having 2 to 20 carbon atoms (for example, a methylene group, , A methylene group (-CH ₂ -) or an ethylene group (-CH ₂ CH ₂ -), etc.), or two or more functional groups are condensed and connected.

Specifically, the cis isomer and trans isomer of the unsaturated fatty acid ester are dihexyl maleate and fumarate; Didecyl malate and fumarate; Diundecyl malates and fumarates; Didodecyl malate and fumarate; Or hexyloctyl malate and fumarate.

Further, in the thermoplastic resin composition according to one embodiment of the present invention, the vinyl chloride-based copolymer contains 65% by weight to 97% by weight of repeating units derived from a vinyl chloride monomer as described above; And 3 to 35% by weight of repeating units derived from unsaturated fatty acid esters.

If the repeating unit derived from the vinyl chloride monomer in the vinyl chloride copolymer exceeds 97 wt% and the repeating unit derived from the unsaturated fatty acid ester is less than 3 wt%, a reversed digitization phenomenon may occur, And the mechanical properties of the thermoplastic resin composition produced from the thermoplastic resin composition containing the thermoplastic resin composition may deteriorate. On the other hand, when the repeating unit derived from vinyl chloride monomer in the vinyl chloride copolymer is less than 65% by weight and the repeating unit derived from unsaturated fatty acid ester is more than 35% by weight, the repeating unit derived from an excess of unsaturated fatty acid ester, And the mechanical properties may be deteriorated. More specifically, the vinyl chloride-based copolymer may contain 65 wt% to 80 wt% of repeating units derived from a vinyl chloride monomer and 20 wt% to 35 wt% of repeating units derived from an unsaturated fatty acid ester .

In the thermoplastic resin composition according to an embodiment of the present invention, the vinyl chloride-based copolymer may be in the form of a secondary particle formed by incorporating primary particles, and the vinyl chloride- An average pore diameter of 100 nm or less and a porosity of 40 vol% or less. Specifically, the pores may have an average pore diameter of 60 nm or less, more specifically 1 nm to 20 nm, and more particularly 10 nm to 20 nm. In addition, the vinyl chloride-based copolymer has pores having an average pore diameter as described above in the total volume of secondary particles of not more than 30% by volume, more specifically not more than 20% by volume, more specifically not more than 18% .

In the thermoplastic resin composition according to one embodiment of the present invention, the unsaturated fatty acid ester used in the polymerization of the vinyl chloride-based copolymer acts as an internal plasticizer, so that the microvoided pores are reduced in pore size . As a result, the processability of the thermoplastic resin composition containing the same can be improved.

In the present invention, the average pore diameter (4 V / A) and the porosity of the vinyl chloride copolymer are measured by a mercury porosity analyzer, specifically, Auto Pore IV 9520 (manufactured by Micromeritics) (P _inter ), accessible intravoid (P _acc ), and inaccessible intravoid (P _inacc ) from the amount of mercury, respectively, and calculated from the results.

In the thermoplastic resin composition according to an embodiment of the present invention, the vinyl chloride-based copolymer has a polydispersity (PDI) ratio of a weight-average molecular weight (Mw) to a number-average molecular weight (Mn) Is in the range of 1.5 to 2.5. If the PDI of the vinyl chloride-based copolymer exceeds 2.5, mechanical properties such as abrasion resistance and impact resistance may be deteriorated. Further, considering the remarkable effect of improving the mechanical properties of the copolymer due to the polydispersity control, the polydispersity of the vinyl chloride-based copolymer may be specifically from 1.8 to 2.1.

In the thermoplastic resin composition according to an embodiment of the present invention, the vinyl chloride-based copolymer may have a weight average molecular weight (Mw) of 70,000 g / mol to 300,000 g / mol, specifically 90,000 g / mol To 280,000 g / mol.

In the thermoplastic resin composition according to an embodiment of the present invention, the vinyl chloride-based copolymer may have a number average molecular weight (Mn) of 50,000 g / mol to 150,000 g / mol, specifically, 50,000 g / mol To 70,000 g / mol.

If the weight average molecular weight or the number average molecular weight of the vinyl chloride-based copolymer is out of the above-mentioned range or out of the above range of the polydispersity, the workability and mechanical properties may not be improved in a balanced manner. Here, the weight average molecular weight and the number average molecular weight may be polystyrene reduced molecular weights analyzed by gel permeation chromatography (GPC), respectively.

In addition, the thermoplastic resin composition according to an embodiment of the present invention includes the vinyl chloride-based copolymer as a main component, and the thermoplastic resin composition may contain a heat stabilizer, a lubricant, and a lubricant depending on the purpose of use of the thermoplastic resin composition, , A processing aid, a filler, a compatibilizer, an antistatic agent, and the like, which are excellent in compatibility with the vinyl chloride-based copolymer.

The additive may be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the vinyl chloride-based copolymer.

Specifically, the heat stabilizer is an organotin series heat stabilizer; A carboxylic acid metal salt-based heat stabilizer; Metal-based heat stabilizers including lead-based compounds; And non-metallic thermal stabilizers including epoxy compounds or organic phosphorous acid salts, but are not limited thereto.

The lubricant may be at least one selected from the group consisting of a hydrocarbon lubricant, a fatty acid lubricant, an amide lubricant, an alcohol lubricant and a metal salt lubricant, but is not limited thereto. More specifically, the lubricant may be an alcohol-based lubricant, more specifically, a stearyl lubricant.

The processing aid may be at least one selected from the group consisting of a hydrocarbon-based processing aid, a fatty acid derivative processing aid, a synthetic resin-based processing aid, a low molecular weight polymeric processing aid, and an organic thio compound.

The filler may be at least one selected from the group consisting of glass fiber, talc, carbon black, carbon fiber, and metal filler, but is not limited thereto.

The compatibilizer may be at least one selected from the group consisting of a polyolefin-based polymer including polyethylene and polypropylene, and a compatibilizing agent having a vinyl polymer as a side chain, but is not limited thereto.

The antistatic agent may be selected from cationic surfactants including quaternary ammonium compounds, anionic surfactants including alkyl sulfonates, alkyl sulfates, alkyl phosphites, sodium alkyl sulfonates, escylated alkyl amines, But are not limited to, at least one selected from the group consisting of a nonionic surfactant including a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether,

The thermoplastic resin composition according to an embodiment of the present invention has a low melt viscosity and thus can exhibit excellent processability. Specifically, the thermoplastic resin composition may have a melt viscosity of 350 Pas to 400 Pas at a shear rate of 500 s ^-1 and a temperature of 120 ° C. The melt viscosity was measured by using a thermoplastic resin composition prepared by mixing 3 parts by weight of an organotin-based heat stabilizer and 1 part by weight of a stearyl type lubricant in 100 parts by weight of a vinyl chloride-based copolymer using Rheo-tester 2000 (Gottfert) It is the value obtained by measuring the viscoelastic behavior.

The thermoplastic resin composition according to one embodiment of the present invention contains 90 wt% or more of a vinyl chloride-based copolymer containing an unsaturated fatty acid ester-derived repeating unit acting as an internal plasticizer, and the above- It is possible to produce a thermoplastic resin molded article having low plasticizer migration property and excellent processability, particularly low-temperature processability.

The present invention also provides a process for producing a thermoplastic resin composition comprising the vinyl chloride-based copolymer.

Specifically, 3 to 53 parts by weight of an unsaturated fatty acid ester, which contains a cis isomer of an unsaturated fatty acid ester and a trans isomer in a weight ratio of 60:40 to 99: 1, relative to 100 parts by weight of a vinyl chloride monomer, And then polymerizing in the presence of an initiator to prepare a vinyl chloride-based copolymer. The production method may further include a step of adding and mixing at least one additive selected from a heat stabilizer, a lubricant, a processing aid, a filler, a compatibilizer, and an antistatic agent after the production of the vinyl chloride copolymer.

The vinyl chloride-based copolymer may be one prepared by adding an unsaturated fatty acid ester to a vinyl chloride-based monomer in the presence of a polymerization initiator and a protective colloid assistant and then suspending the copolymer.

The addition may be carried out batchwise before the initiation of polymerization, or may be carried out batchwise or continuously in the polymerization conversion ratio within 35%, but is not limited thereto.

Specifically, the vinyl chloride-based copolymer may be obtained by introducing an unsaturated fatty acid ester mixture into a polymerization reactor equipped with a vinyl chloride monomer, followed by suspension polymerization. The polymerization reactor may be a reactor filled with a solvent, a polymerization initiator, and a protective colloid preparation before the vinyl chloride monomer is provided. Here, the above-mentioned " packed reactor " may mean a state in which a solvent, a polymerization initiator and a protective colloid assistant are introduced into the polymerization reactor before the vinyl chloride monomer is provided.

The vinyl chloride monomer may be a pure vinyl chloride monomer alone. The vinyl chloride monomer may be a combination of a vinyl chloride monomer and a vinyl monomer capable of copolymerizing with the vinyl chloride monomer as desired, and when the vinyl chloride monomer is a combination of a vinyl chloride monomer and a vinyl monomer, The content of vinyl chloride in the vinyl chloride polymer to be produced is 50% by weight or more. The vinyl-based monomer copolymerizable with the vinyl chloride monomer may be as described above.

The unsaturated fatty acid ester is added as a comonomer forming a copolymerization with a vinyl chloride monomer and is contained in a vinyl chloride-based copolymer finally produced to improve the plasticity of the copolymer. As well as cis isomers of unsaturated fatty acid esters and trans isomers of unsaturated fatty acid esters, and the cis isomers and trans isomers of the unsaturated fatty acid esters may have a weight ratio of 60:40 to 99: 1.

The unsaturated fatty acid ester may be used in an amount of 3 to 53 parts by weight based on 100 parts by weight of the vinyl chloride monomer.

The above-mentioned unsaturated fatty acid ester may be added in a batch or continuously to a polymerization reactor equipped with a vinyl chloride monomer within the range of polymerization conversion within 35% as described above. Here, the polymerization conversion may be a conversion rate of a vinyl chloride monomer to a polymer, and the polymerization conversion may be measured using a butane tracer equipped with a gas chromatography. Specifically, a polymerization conversion curve according to the ratio of the vinyl chloride monomer to butane over time under predetermined polymerization conditions may be prepared for each polymerization condition, and the polymerization conversion ratio according to polymerization conditions may be measured based on the curve. In addition, the polymerization conversion rate may be up to an error range depending on the measurement, for example, up to 35 +/- 3%.

The continuous introduction may be to continuously feed an unsaturated fatty acid ester into a polymerization reactor equipped with a vinyl chloride monomer within a range of polymerization conversion within 35%. Specifically, the unsaturated fatty acid ester may be added at a polymerization conversion rate of 20% And the addition may be terminated at a point of time when the polymerization conversion rate is within 35%, or the entire unsaturated fatty acid ester may be added at a constant rate from the start to the end of the addition.

The protective colloid assistant serves to stabilize the reactants during polymerization and to produce uniform and stable particles. It is used in an amount of 0.03 parts by weight to 5 parts by weight based on 100 parts by weight of the vinyl chloride monomer used in the polymerization. .

Specifically, the protective colloid aid may be used in an amount of 0.001 part by weight to 2.5 parts by weight based on 100 parts by weight of the vinyl chloride monomer. If the protective colloid preparation is used in an amount of less than 0.001 part by weight, the particle size of the finally produced vinyl chloride-based copolymer becomes excessively large, so that the molded article produced using the thermoplastic resin composition containing the vinyl chloride- There is a possibility that Miglyring particles will be formed in the vinyl chloride copolymer. When the amount of the crosslinking agent is more than 5 parts by weight, the amount of the fine particles in the vinyl chloride- The initial coloring property of the resulting molded article may deteriorate.

The protective colloid aid may be one or a mixture of two or more selected from the group consisting of a vinyl alcohol resin, a cellulose, and an unsaturated organic acid polymer. Specifically, the protective colloid aid may be a mixture of a vinyl alcohol resin and a cellulose in a ratio of 5: To 7: 7 by weight. At this time, the vinyl alcohol resin preferably has a polyvinyl alcohol having a degree of hydration of more than 50% by weight but not more than 90% by weight and a polyvinyl alcohol having a degree of hydration of 30% by weight to 50% by weight in a ratio of 2: 1 to 1: 2 Based on the total weight of the composition.

Examples of the cellulose include methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose and the like, and any one or a mixture of two or more thereof may be used. More specifically, it may be hydroxypropyl methylcellulose. More specifically, the content of the hydroxypropyl group in the molecule is 3 wt% to 20 wt%, the viscosity of 2% aqueous solution at 23 ± 5 ° C is 10 cps to 20,000 cps Lt; / RTI >

Examples of the unsaturated organic acid polymer include acrylic acid polymer, methacrylic acid polymer, itaconic acid polymer, fumaric acid polymer, maleic acid polymer, and succinic acid polymer, and any one or a mixture of two or more thereof may be used.

The polymerization initiator may be used in an amount of 0.0001 part by weight to 0.2 part by weight based on 100 parts by weight of the vinyl chloride monomer used for polymerization. Specifically, the polymerization initiator may be used in an amount of 0.0005 parts by weight to 0.12 parts by weight based on 100 parts by weight of the vinyl chloride monomer. If the content of the polymerization initiator is less than 0.0001 parts by weight, the polymerization reaction time becomes long, the conversion to vinyl chloride type copolymer becomes low, and the productivity may be deteriorated. When the content exceeds 0.2 parts by weight, the polymerization initiator is not completely consumed There is a possibility of remaining in the vinyl chloride-based copolymer finally produced to deteriorate physical properties, particularly thermal stability, of the copolymer.

The polymerization initiator is not particularly limited. Peroxide-based compounds such as dicumylperoxide, dipentylperoxide, di-3,5,5-trimethylhexanoylperoxide or dilaurylperoxide; Peroxydicarbonate-based compounds such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate or di-2-ethylhexyl peroxydicarbonate; peroxy ester compounds such as t-butyl peroxy pivalate, 1,1,3,3-tetramethyl butyl peroxyneodecanoate or t-butyl peroxyneodecanoate; Azo-based compounds such as azobis-2,4-dimethylvaleronitrile; hydroperoxide-based compounds such as t-butyl hydroperoxide; Or sulfate compounds such as potassium persulfate or ammonium persulfate. Any one or a mixture of two or more of them may be used.

The suspension polymerization is not particularly limited, but may be carried out, for example, in a temperature range of 30 ° C to 70 ° C, and the temperature during the suspension polymerization may be appropriately controlled within the above range according to the desired polymerization degree. For example, the higher the desired degree of polymerization, the lower the temperature, and the lower the desired degree of polymerization, the higher the temperature can be.

The suspension polymerization may be terminated by introducing the reaction termination, and the termination time may be a time when the pressure in the reactor is 6 kg / cm ² to 8 kg / cm ² (or when the polymerization conversion rate exceeds 85%), Lt; / RTI >

The reaction termination is not particularly limited, but may be, for example, a phenol compound, an amine compound, a nitrile compound, a sulfur compound or the like. Specifically, the above-mentioned reaction termination is carried out in the presence of triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, hydroquinone, p-methoxyphenol, N-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 2,5-di-t-butylhydroquinone, (6-t-butyl-m-cresol), tocopherol, and the like, phenol compounds such as N, N'- Amine compounds such as N, N'-diphenyl-p-phenylenediamine and 4,4'-bis (dimethylbenzyl) diphenylamine, 2-phenylnitronylnitroxide, 3- 3-imidazoline nitroxide, 4-hydroxy-2,2 ', 6,6'-tetramethyl-piperidine-1-oxyl, -tetramethyl-piperidine-1-oxyl), and sulfur compounds such as dodecyl mercaptan and 1,2-diphenyl-2-thiol The.

Further, the suspension polymerization may use a solvent, and the solvent may be deionized water. At this time, the solvent may be appropriately adjusted depending on the amount of the vinyl chloride monomer used in the polymerization and the size of the polymerization reactor. For example, the solvent may be used in an amount of 70 parts by weight or more based on 100 parts by weight of the vinyl chloride monomer.

In addition to the above-described active ingredients, additives such as polymerization regulators, chain transfer agents, pH adjusters, antioxidants, crosslinking agents, antistatic agents, anti-scale agents and surfactants may be further added to the suspension polymerization. Is not particularly limited and can be used in the usual kinds and contents known in the art. The additive may be added at any time of the suspension polymerization, during polymerization or after polymerization, and may be added all at once or continuously added.

In addition, the vinyl chloride-based copolymer may be one prepared by further performing the step of drying after the suspension polymerization, and the drying is not particularly limited and may be carried out by a method commonly known in the art.

The vinyl chloride-based copolymer produced by the above method may be used alone as a thermoplastic resin or may be used as a thermoplastic resin in combination with at least one additive selected from heat stabilizers, lubricants, processing aids, fillers, compatibilizing agents and antistatic agents as described above Or may be used in the form of a mixed resin composition.

If the thermoplastic resin composition further comprises the above-mentioned additives, at least one additive selected from a heat stabilizer, a lubricant, a processing aid, a filler, a compatibilizing agent and an antistatic agent is added to the vinyl chloride copolymer produced in the above step The mixing step may optionally be further performed.

The mixing of the vinyl chloride-based copolymer and the additive is not particularly limited, but may be performed, for example, by simple kneading, using a ribbon blender, a high-temperature mixer or a high-speed mixer.

In addition, the present invention provides a thermoplastic resin molded article produced from the thermoplastic resin composition.

Hereinafter, the present invention will be described in more detail with reference to Production Examples and Experimental Examples. However, the following Preparation Examples and Experiments are for illustrative purposes only and are not intended to limit the scope of the present invention.

Production Example 1

390 kg of deionized water was introduced into a 1 m ³ internal volume reactor equipped with a reflux condenser, and 160 g of polyvinyl alcohol having a hydration degree of 80.5%, 120 g of polyvinyl alcohol having a hydration degree of 42.3%, hydroxypropyl methylcellulose 50 g were introduced into a reactor and 300 kg of a vinyl chloride monomer was added thereto. Then, 60 g of di-2-ethylhexyl peroxydicarbonate and 150 g of t-butyl peroxyneodecanonate were added to initiate the reaction. At the polymerization conversion rate of 20%, a mixture of dioctyl malate and dihexyl fumarate was started to be added, and the addition was terminated at a polymerization conversion rate of 35%. At this time, the total charge of the mixture was 75 kg, and the mixture of dhexelalate and dihexyl fumarate in the mixture had a weight ratio of 90:10. In order to achieve a target average polymerization degree of 1000, the reaction temperature was maintained at 57 ° C during the entire polymerization reaction, and when the reactor pressure reached 6.3 kg / cm ² , 4-hydroxy-2,2,6,6,6 15 g of tetramethyl-piperidine-1-oxyl and 90 g of triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate were added to terminate the reaction . Thereafter, the unreacted monomer and the resulting vinyl chloride copolymer slurry were separately recovered, and the vinyl chloride copolymer slurry was dried in a fluidized bed dryer to obtain a vinyl chloride copolymer.

Production Example 2

A vinyl chloride-based copolymer was obtained in the same manner as in Preparation Example 1, except that didesyl malate and didecyl fumarate were used instead of dhechelalate and dihexyl fumarate, respectively.

Production Example 3

A vinyl chloride-based copolymer was obtained in the same manner as in Preparation Example 1, except that didodecyl malate and didodecyl fumarate were used instead of dicyclohexyl malate and dihexyl fumarate, respectively.

Production Example 4

A vinyl chloride copolymer was obtained in the same manner as in Preparation Example 1, except that hexyloctyl malate and hexyloctyl fumarate were used instead of dicyclohexyl malate and dihexyl fumarate, respectively.

 Production Example 5

A vinyl chloride-based copolymer was obtained in the same manner as in Preparation Example 1, except that dichexylalate and dihexyl fumarate were used in a weight ratio of 60:40.

Production Example 6

A vinyl chloride-based copolymer was obtained in the same manner as in Preparation Example 1, except that dioctyl malate and dihexyl fumarate were used in a weight ratio of 99: 1.

Comparative Preparation Example 1

A vinyl chloride-based copolymer was obtained in the same manner as in Preparation Example 1, except that dioctyl malate and dihexyl fumarate were not used.

Comparative Production Example 2

A vinyl chloride-based copolymer was obtained in the same manner as in Preparation Example 1, except that dibutyl malate and dibutyl fumarate were used instead of dioctyl malate and dihexyl fumarate.

Comparative Production Example 3

A vinyl chloride-based copolymer was obtained in the same manner as in Preparation Example 1, except that dihexadecyl malate and dihexadecyl fumarate were used instead of dicyclohexyl malate and dihexyl fumarate.

Comparative Production Example 4

A vinyl chloride-based copolymer was obtained in the same manner as in Preparation Example 1, except that octyl hexadecyl malate and octyl hexadecyl fumarate were used instead of dioctyl malate and dihexyl fumarate.

Comparative Preparation Example 5

A vinyl chloride-based copolymer was obtained in the same manner as in Preparation Example 1, except that dichexylalate and dihexyl fumarate were used in a weight ratio of 50:50.

Comparative Preparation Example 6

A vinyl chloride-based copolymer was obtained in the same manner as in Preparation Example 1, except that dichexylalate and dihexyl fumarate were used in a weight ratio of 99.5: 0.5.

Example 1

3 parts by weight of an organotin compound (MT-800 ™, manufactured by Songwon Industrial Co., Ltd.) as a heat stabilizer and 0.5 part by weight of a lubricant (SONGSTAB SL-29 ™, manufactured by Songwon Industrial Co., Ltd.) of 0.5 part by weight were added to 100 parts by weight of the vinyl chloride- Were added and mixed to prepare a thermoplastic resin composition.

Example 2

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the vinyl chloride-based copolymer prepared in Preparation Example 2 was used instead of the vinyl chloride-based copolymer prepared in Preparation Example 1.

Example 3

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the vinyl chloride-based copolymer prepared in Preparation Example 3 was used in place of the vinyl chloride-based copolymer prepared in Preparation Example 1.

Example 4

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the vinyl chloride-based copolymer prepared in Preparation Example 4 was used in place of the vinyl chloride-based copolymer prepared in Preparation Example 1.

Example 5

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the vinyl chloride-based copolymer prepared in Preparation Example 5 was used in place of the vinyl chloride-based copolymer prepared in Preparation Example 1.

Example 6

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the vinyl chloride-based copolymer prepared in Preparation Example 6 was used in place of the vinyl chloride-based copolymer prepared in Preparation Example 1.

Comparative Example 1

The procedure of Example 1 was repeated except that the vinyl chloride polymer prepared in Comparative Preparation Example 1 was used in place of the vinyl chloride copolymer prepared in Preparation Example 1 and 50 parts by weight of dioctyl phthalate was further added. To prepare a thermoplastic resin composition.

Comparative Example 2

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the vinyl chloride-based copolymer prepared in Comparative Preparation Example 2 was used in place of the vinyl chloride-based copolymer prepared in Preparation Example 1.

Comparative Example 3

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the vinyl chloride-based copolymer prepared in Comparative Preparation Example 3 was used in place of the vinyl chloride-based copolymer prepared in Preparation Example 1.

Comparative Example 4

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the vinyl chloride-based copolymer prepared in Comparative Preparation Example 4 was used in place of the vinyl chloride-based copolymer prepared in Preparation Example 1.

Comparative Example 5

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the vinyl chloride-based copolymer prepared in Comparative Preparation Example 5 was used in place of the vinyl chloride-based copolymer prepared in Preparation Example 1.

Comparative Example 6

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that the vinyl chloride-based copolymer prepared in Comparative Preparation Example 6 was used instead of the vinyl chloride-based copolymer prepared in Preparation Example 1.

Experimental Example

In order to comparatively analyze the physical properties of the respective thermoplastic resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 6 and the respective thermoplastic resin molded articles produced using the thermoplastic resin compositions, the plasticizer migration property, the low temperature softening temperature, , Melting time, volatility and melt viscosity were measured. The results are shown in Tables 1 to 3 and FIG.

1) Measurement of plasticizer migration property

Each of the thermoplastic resin compositions of Examples 1 to 6 and Comparative Examples 1 to 6 was kneaded at 185 ° C for 3 minutes using a roll-mill to prepare a 2-mm-thick sheet . Each manufactured sheet was measured for the weight reduction rate of the sheet according to ASTM D-5227. At this time, the lower the weight reduction rate, the better the degree of plasticizer migration.

2) Low temperature flexible temperature measurement

Each of the thermoplastic resin compositions of Examples 1 to 6 and Comparative Examples 1 to 6 was kneaded at 185 占 폚 for 3 minutes using a roll-mill to prepare a sheet having a thickness of 1.5 mm . Each sheet produced had a low temperature curing temperature according to ASTM D-1043.

3) Hardness measurement

Each of the thermoplastic resin compositions of Examples 1 to 6 and Comparative Examples 1 to 6 was kneaded at 185 ° C for 3 minutes by using a roll-mill, and then a thermoplastic resin composition having a thickness of 6 mm Each sheet was produced. Each sheet produced had a hardness (shore A) measured according to ASTM D-2240.

4) Measurement of fusion time

Melting time of each of the thermoplastic resin compositions of Examples 1 to 6 and Comparative Examples 1 to 6 was measured at a temperature of 100 캜 using a Bradender plastograph. The shorter the melting time, the better the meltability.

5) Volatility measurement

Each of the thermoplastic resin compositions of Examples 1 to 6 and Comparative Examples 1 to 6 was measured for weight change ratio at a temperature of 100 占 폚 for 24 hours in accordance with ASTM D-1203. At this time, the lower the value of the volatility (% by weight), the lower the weight reduction rate, that is, the degree of volatilization of the plasticizer is low.

6) Melt viscosity measurement

Each of the thermoplastic resin compositions of Examples 1 to 6 and Comparative Examples 1 to 6 was subjected to melt viscosity change according to shear rate at a temperature of 180 캜 and 120 캜 using a Rheo-tester 2000 machine (Gottfert) Were measured. The lower the melt viscosity, the better the processability.

division Plasticizer migration (%) Low Temperature Flexible Temperature (℃) Hardness
(Shorea) Melting time (min) Volatility (% by weight) Example 1 5.14 -21 75.3 58 1.9 Example 2 3.67 -29 76.2 61 1.1 Example 3 3.18 -30 75.9 63 0.9 Example 4 4.64 -27 75.9 59 1.2 Example 5 6.23 -19 78.3 68 0.7 Example 6 3.15 -23 74.7 56 0.6 Comparative Example 1 15.16 -19 75.1 105 6.8 Comparative Example 2 8.27 -13 76.1 91 3.4 Comparative Example 3 2.75 -31 82.4 76 2.2 Comparative Example 4 4.17 -28 80.8 83 3.0 Comparative Example 5 9.23 -15 81.3 81 4.9 Comparative Example 6 2.16 -19 78.6 84 0.5

As a result, it was found that the thermoplastic resin compositions of Examples 1 to 6 exhibited excellent plasticizability with a low plasticizer level of 3 to 6.5% while maintaining excellent mechanical properties, excellent low temperature flexibility temperature in the range of -30 to -19 캜, And a low volatility of 2 wt% or less.

Claims (15)

A vinyl chloride-based copolymer in an amount of 90% by weight or more,
Wherein the vinyl chloride-based copolymer contains 3 wt% to 35 wt% of an unsaturated fatty acid ester-derived repeating unit,
Wherein the repeating unit derived from the unsaturated fatty acid ester comprises a repeating unit derived from a cis isomer of an unsaturated fatty acid ester and a repeating unit derived from a trans isomer of an unsaturated fatty acid ester in a weight ratio of 60:40 to 99: 1.
The method according to claim 1,
Wherein the unsaturated fatty acid ester is an unsaturated dicarboxylic acid ester.
The method according to claim 1,
Wherein the cis isomer of the unsaturated fatty acid ester is a compound represented by the following formula 1 and the trans isomer of the unsaturated fatty acid ester is a compound represented by the following formula 2:
[Chemical Formula 1]

(2)

(In the above formulas (1) and (2)
R ₁ to R ₄ are each independently selected from the group consisting of a linear or branched alkyl group having 5 to 14 carbon atoms and a cycloalkyl group having 5 to 12 carbon atoms.
The method of claim 3,
Wherein R ₁ to R ₄ are each independently a linear or branched alkyl group having 6 to 14 carbon atoms.
The method according to claim 1,
Wherein the thermoplastic resin composition further comprises at least one additive selected from the group consisting of a heat stabilizer, a lubricant, a processing aid, a filler, a compatibilizer, and an antistatic agent.
And 3 parts by weight to 53 parts by weight of an unsaturated fatty acid ester based on 100 parts by weight of the vinyl chloride monomer in the presence of a polymerization initiator to prepare a vinyl chloride-
Wherein the unsaturated fatty acid ester comprises a cis isomer of an unsaturated fatty acid ester and a trans isomer in a weight ratio of 60:40 to 99: 1.
The method of claim 6,
Wherein the cis isomer of the unsaturated fatty acid ester is a compound represented by the following formula 1 and the trans isomer of the unsaturated fatty acid ester is a compound represented by the following formula 2:
[Chemical Formula 1]

(2)

(In the above formulas (1) and (2)
R ₁ to R ₄ are each independently selected from the group consisting of a linear or branched alkyl group having 5 to 14 carbon atoms and a cycloalkyl group having 5 to 12 carbon atoms.
The method of claim 6,
Wherein the polymerization reaction is carried out by introducing an unsaturated fatty acid ester into a vinyl chloride monomer in the presence of a polymerization initiator and a protective colloid assistant and performing suspension polymerization.
The method of claim 8,
Wherein the introduction of the unsaturated fatty acid ester is carried out by collectively feeding an unsaturated fatty acid ester to the vinyl chloride monomer prior to the initiation of polymerization.
The method of claim 8,
Wherein the addition of the unsaturated fatty acid ester is carried out by batchwise or continuously introducing an unsaturated fatty acid ester into the vinyl chloride monomer within a range of polymerization conversion within 35% after the initiation of polymerization.
The method of claim 10,
The continuous introduction is carried out by introducing the unsaturated fatty acid ester at a time when the polymerization conversion rate is 20% or more and terminating the charging at a time when the polymerization conversion rate is within 35%
Wherein the unsaturated fatty acid ester is fed at a constant rate from the start to the end of the feed.
The method of claim 8,
Wherein the protective colloid assistant comprises at least one member selected from the group consisting of a vinyl alcohol resin, a cellulose, and an unsaturated organic acid polymer.
The method of claim 8,
Wherein the protective colloid assistant comprises a vinyl alcohol resin and a cellulose in a weight ratio of 5: 1 to 7: 7.
14. The method of claim 13,
The vinyl alcohol resin preferably has a first polyvinyl alcohol having a degree of hydration exceeding 50 wt% to 90 wt% and a second polyvinyl alcohol having a degree of hydration of 30 wt% to 50 wt% in a weight ratio of 2: 1 to 1: 2 By weight based on the total weight of the thermoplastic resin composition.
A thermoplastic resin molded article produced from the thermoplastic resin composition of claim 1.

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