阅读说明：本技术 热塑性树脂组合物 (Thermoplastic resin composition ) 是由 裴宰涓 南基荣 柳济善 沈在用 裵宣炯 金仁晳 于 2019-01-10 设计创作，主要内容包括：本发明提供一种热塑性树脂组合物,该热塑性树脂组合物包含：第一共聚物,该第一共聚物包含共轭二烯类聚合物、来自芳香族乙烯基类单体的单元和来自乙烯基氰基类单体的单元；第二共聚物,该第二共聚物包含来自芳香族乙烯基类单体的单元和来自乙烯基氰基类单体的单元；以及,相对于100重量份的所述第一共聚物和所述第二共聚物的总和,2.0重量份至10重量份的第三共聚物,该第三共聚物具有包含来自聚亚烷基二醇的单元的软链段和包含来自芳香族二羧酸或芳香族二羧酸酯的单元和来自直链脂肪族二元醇的单元的硬链段；和2.5重量份至10重量份的第四共聚物,该第四共聚物包含来自芳香族二羧酸的单元、来自直链脂肪族二元醇的单元和来自环状脂肪族二元醇的单元。(The present invention provides a thermoplastic resin composition comprising: a first copolymer comprising a conjugated diene-based polymer, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a vinyl cyano-based monomer; a second copolymer comprising a unit derived from an aromatic vinyl monomer and a unit derived from a vinyl cyano monomer; and, with respect to 100 parts by weight of the sum of the first copolymer and the second copolymer, 2.0 parts by weight to 10 parts by weight of a third copolymer having a soft segment comprising units derived from a polyalkylene glycol and a hard segment comprising units derived from an aromatic dicarboxylic acid or an aromatic dicarboxylate and units derived from a linear aliphatic diol; and 2.5 to 10 parts by weight of a fourth copolymer comprising units derived from an aromatic dicarboxylic acid, units derived from a linear aliphatic diol, and units derived from a cyclic aliphatic diol.)

1. A thermoplastic resin composition comprising: a first copolymer comprising a conjugated diene-based polymer, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a vinyl cyano-based monomer; a second copolymer comprising a unit derived from an aromatic vinyl monomer and a unit derived from a vinyl cyano monomer; and, with respect to 100 parts by weight of the sum of the first copolymer and the second copolymer, 2.0 parts by weight to 10 parts by weight of a third copolymer having a soft segment comprising units derived from a polyalkylene glycol and a hard segment comprising units derived from an aromatic dicarboxylic acid or an aromatic dicarboxylate and units derived from a linear aliphatic diol; and 2.5 to 10 parts by weight of a fourth copolymer comprising units derived from an aromatic dicarboxylic acid, units derived from a linear aliphatic diol, and units derived from a cyclic aliphatic diol.

2. The thermoplastic resin composition according to claim 1, wherein the average particle diameter of the conjugated diene-based polymer is 0.2 μm to 0.5 μm.

3. The thermoplastic resin composition of claim 1, wherein said first copolymer is an acrylonitrile/butadiene/styrene graft copolymer.

4. The thermoplastic resin composition of claim 1, wherein said second copolymer is one or more selected from the group consisting of styrene/acrylonitrile copolymer and α -methylstyrene/acrylonitrile copolymer.

5. The thermoplastic resin composition of claim 1, wherein the third copolymer is contained in an amount of 2.5 to 7 parts by weight, relative to 100 parts by weight of the sum of the first and second copolymers.

6. The thermoplastic resin composition of claim 1, wherein said unit derived from a polyalkylene glycol in said third copolymer is a unit derived from one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, poly (1, 2-butanediol), polypentanediol, polyhexamethylene glycol, polyheptaethylene glycol, polynonanediol, polydecamediol, and α -hydro- ω -hydroxypoly (oxy-1, 4-butanediyl),

the unit derived from an aromatic dicarboxylic acid or an aromatic dicarboxylate is a unit derived from one or more selected from the group consisting of 1, 4-phthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate and dimethyl 2, 6-naphthalenedicarboxylate,

the unit derived from the linear aliphatic diol is a unit derived from one or more selected from the group consisting of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol.

7. The thermoplastic resin composition of claim 1, wherein the fourth copolymer is contained in an amount of 2.5 to 7 parts by weight, relative to 100 parts by weight of the sum of the first and second copolymers.

8. The thermoplastic resin composition according to claim 1, wherein said unit derived from an aromatic dicarboxylic acid in said fourth copolymer is a unit derived from one or more selected from the group consisting of 1, 4-phthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid and 1, 5-naphthalenedicarboxylic acid,

the unit derived from the linear aliphatic diol is a unit derived from one or more selected from the group consisting of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol,

the unit derived from the cyclic aliphatic diol is a unit derived from one or more selected from the group consisting of 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, and 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol.

9. The thermoplastic resin composition of claim 1, further comprising a flame retardant and a flame retardant aid.

10. The thermoplastic resin composition of claim 9, wherein the content of the flame retardant is 10 to 30 parts by weight with respect to 100 parts by weight of the sum of the first and second copolymers.

11. The thermoplastic resin composition of claim 9, wherein said flame retardant is one or more selected from the group consisting of tetrabromobisphenol a, decabromodiphenyl ether, decabromodiphenyl ethane, 1, 2-bis (2,4, 6-tribromophenyl) ethane, octabromo-1, 3, 3-trimethyl-1-phenylindane, tetrabromobisphenol a-bis (2, 3-dibromopropyl ether), and 2,4, 6-tris (2,4, 6-tribromophenoxy) -1,3, 5-triazine.

12. The thermoplastic resin composition of claim 9, wherein the flame retardant aid is contained in an amount of 1 to 15 parts by weight, relative to 100 parts by weight of the sum of the first and second copolymers.

13. The thermoplastic resin composition of claim 9, wherein said flame retardant aid is antimony trioxide.

Technical Field

Cross Reference to Related Applications

The present application claims the priority and benefit of korean patent application No.10-2018-0003197 filed on 10.01.2018 and korean patent application No.10-2019-0002852 filed on 09.01.2019, the disclosures of which are incorporated herein by reference in their entirety.

Background

Acrylonitrile/butadiene/styrene graft copolymers are widely used in various applications including electric and electronic products and office automation equipment due to their excellent mechanical properties and processability. However, since the resin itself does not have flame retardancy, a flame retardant and a flame retardant aid are added to impart flame retardancy to the resin.

However, the addition of flame retardants and flame retardant aids results in a significant reduction in mechanical properties and chemical resistance.

In order to solve this problem, it has been proposed to add a thermoplastic polyester elastomer as an additive. However, since the thermoplastic polyester elastomer is very expensive, the production cost of the thermoplastic resin composition increases, and there is a problem that the total volume is excessively reduced in a commercialization process and thus the dimensional stability is reduced.

Disclosure of Invention

Technical problem

The present invention aims to provide a thermoplastic resin composition which is excellent in both chemical resistance and impact resistance and exhibits excellent dimensional stability in a commercial process.

Technical scheme

According to an embodiment of the present invention, there is provided a thermoplastic resin composition comprising: a first copolymer comprising a conjugated diene-based polymer, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a vinyl cyano-based monomer; a second copolymer comprising a unit derived from an aromatic vinyl monomer and a unit derived from a vinyl cyano monomer; and, with respect to 100 parts by weight of the sum of the first copolymer and the second copolymer, 2.0 parts by weight to 10 parts by weight of a third copolymer having a soft segment comprising units derived from a polyalkylene glycol and a hard segment comprising units derived from an aromatic dicarboxylic acid or an aromatic dicarboxylate and units derived from a linear aliphatic diol; and 2.5 to 10 parts by weight of a fourth copolymer comprising units derived from an aromatic dicarboxylic acid, units derived from a linear aliphatic diol, and units derived from a cyclic aliphatic diol.

Advantageous effects

The thermoplastic resin composition according to the present invention can be excellent in chemical resistance and impact resistance and exhibit excellent dimensional stability during commercialization. Also, the thermoplastic resin composition may exhibit excellent flame retardancy.

Detailed Description

Hereinafter, the present invention will be described in more detail to help understanding the present invention.

The terms and words used in the present specification and claims should not be construed as limited to common meanings or dictionary meanings, and should be construed as meanings and concepts consistent with the technical scope of the invention based on the principle that the inventor can appropriately define the concept of the term to describe their invention in the best way.

In the present invention, the average particle diameter of the conjugated diene-based polymer may be defined to correspond to fifty percent or more of the particle diameter in the cumulative volume-based particle diameter distribution curve.

In the present invention, the average particle diameter of the conjugated diene-based polymer may be measured using a Nicomp Nano apparatus (trade name: N3000, manufactured by PSS Nicomp) after diluting a 5% polymer suspension with 60ml of distilled water and then collecting 5ml of the diluted suspension.

In the present invention, the degree of grafting can be calculated by adding a predetermined amount of the graft copolymer as the first copolymer to a solvent, then dissolving with a vibrator, centrifuging with a centrifuge and drying to obtain an insoluble component, then using the weight of the insoluble component and the following equation, specifically, the degree of grafting can be calculated by adding a predetermined amount of the graft copolymer to acetone, dissolving the graft copolymer that has been released by vibrating with a vibrator (trade name: SI-600R, manufactured by L ab. company) for 24 hours, centrifuging the resultant at 14,000rpm for 1 hour using a centrifuge, then drying at 140 ℃ for 2 hours using a vacuum drier (trade name: DRV320DB, manufactured by Advantec) to obtain an insoluble component, and then calculating the degree of grafting using the weight of the insoluble component and the following equation.

Degree of grafting (%) - (Y- (X × R))/(X × R) ] × 100

Y: weight of insoluble component

X: the weight of the graft copolymer added to obtain insoluble components

R: fraction of conjugated diene-based polymer in graft copolymer added with obtaining insoluble component

In the present invention, the weight average molecular weight of the shell of the first copolymer may refer to the weight average molecular weight of a copolymer comprising a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyano-based monomer graft-polymerized onto a conjugated diene-based polymer.

In the present invention, after the insoluble component obtained during the measurement of the degree of grafting was dissolved in Tetrahydrofuran (THF) at a concentration of 1% by weight and then filtered through a filter of 1 μm, the weight average molecular weight of the shell of the first copolymer can be measured by Gel Permeation Chromatography (GPC) in a relative value with respect to a standard Polystyrene (PS) sample.

In the present invention, the weight average molecular weight may be measured by gpc (waters breeze) using one or more selected from THF, chloroform, and chlorophenol as an elution solvent, in relative values with respect to a standard PS sample.

The thermoplastic resin composition according to one embodiment of the present invention comprises: 1) a first copolymer comprising a conjugated diene-based polymer, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a vinyl cyano-based monomer; 2) a second copolymer comprising a unit derived from an aromatic vinyl monomer and a unit derived from a vinyl cyano monomer; and, with respect to 100 parts by weight of the total of the first copolymer and the second copolymer, 3)2.0 parts by weight to 10 parts by weight of a third copolymer having a soft segment comprising a unit from a polyalkylene glycol and a hard segment comprising a unit from an aromatic dicarboxylic acid or an aromatic dicarboxylate and a unit from a linear aliphatic diol; and 4)2.5 to 10 parts by weight of a fourth copolymer comprising units derived from an aromatic dicarboxylic acid, units derived from a linear aliphatic diol, and units derived from a cyclic aliphatic diol.

The thermoplastic resin composition according to one embodiment of the present invention may further comprise: 5) a flame retardant and 6) a flame retardant aid.

Hereinafter, a thermoplastic resin composition according to one embodiment of the present invention will be described in detail.

1. First copolymer

The first copolymer is a graft copolymer and includes a conjugated diene-based polymer, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a vinyl cyano-based monomer.

The first copolymer can impart excellent chemical resistance, impact resistance, thermal stability, colorability, fatigue resistance, rigidity and processability to the thermoplastic resin composition.

The conjugated diene-based polymer may include a modified conjugated diene-based polymer prepared by graft polymerization of a conjugated diene-based polymer prepared by polymerizing a conjugated diene-based monomer with an aromatic vinyl-based monomer and a vinyl cyano-based monomer.

The conjugated diene monomer may be one or more selected from 1, 3-butadiene, isoprene, chloroprene and piperylene, and, in particular, 1, 3-butadiene is preferable.

The conjugated diene-based polymer may be a conjugated diene-based rubber polymer.

The content of the conjugated diene-based polymer may be 45 to 75% by weight, 50 to 70% by weight, or 55 to 65% by weight, relative to the total weight of the first copolymer, and the content is preferably 55 to 65% by weight. When the content of the conjugated diene-based polymer falls within the above range, the impact resistance and processability of the first copolymer can be further improved.

The average particle diameter of the conjugated diene-based polymer may be 0.20 to 0.5 μm, 0.25 to 0.4 μm, or 0.30 to 0.35 μm, and the average particle diameter is preferably 0.30 to 0.35 μm. When the average particle diameter of the conjugated diene-based polymer falls within the above range, the mechanical properties of the first copolymer can be further improved.

The unit derived from the aromatic vinyl monomer may be a unit derived from one or more selected from styrene, α -methylstyrene, α -ethylstyrene and p-methylstyrene, and, in particular, a unit derived from styrene is preferable.

The content of the unit derived from the aromatic vinyl monomer may be 15 to 45% by weight, 20 to 40% by weight, or 25 to 35% by weight, relative to the total weight of the first copolymer, and the content is preferably 25 to 35% by weight. When the content of the unit derived from the aromatic vinyl-based monomer falls within the above range, chemical resistance, rigidity, impact resistance, processability and surface gloss of the thermoplastic resin composition can be further improved.

The unit derived from a vinyl cyano-based monomer may be a unit derived from one or more selected from acrylonitrile, methacrylonitrile, phenylacetonitrile and α -chloroacrylonitrile, and, in particular, is preferably a unit derived from acrylonitrile.

The content of the unit from the vinyl cyanide-based monomer may be 1 to 20 wt%, 3 to 17 wt%, or 5 to 12 wt%, and preferably 5 to 12 wt%, relative to the total weight of the first copolymer. When the content of the unit derived from the vinyl cyanide-based monomer falls within the above range, chemical resistance, rigidity, impact resistance, processability and surface gloss of the thermoplastic resin composition can be further improved.

The degree of grafting of the first copolymer may be from 10% to 60%, from 20% to 50%, or from 30% to 40%, and preferably from 30% to 40%. When the degree of grafting of the first copolymer falls within the above range, thermal stability and mechanical properties of the first copolymer can be achieved in harmony.

The shell of the first copolymer may have a weight average molecular weight of 10,000 to 150,000g/mol, 30,000 to 120,000g/mol, or 50,000 to 100,000g/mol, and preferably has a weight average molecular weight of 50,000 to 100,000 g/mol. When the weight average molecular weight of the shell of the first copolymer falls within the above range, it is easy to control the polymerization reaction, and mechanical properties and processability are achieved in harmony.

The shell of the first copolymer may include a unit derived from an aromatic vinyl-based monomer graft-polymerized with a conjugated diene-based polymer and a unit derived from a vinyl cyano-based monomer.

The first copolymer is preferably an acrylonitrile/butadiene/styrene graft copolymer.

The first copolymer may be prepared by one or more methods selected from emulsion polymerization, suspension polymerization, and bulk polymerization, and, in particular, preferably by polymerizing an aromatic vinyl-based monomer and a vinyl cyano-based monomer in the presence of a conjugated diene-based polymer using emulsion polymerization.

2. Second copolymer

The second copolymer contains a unit derived from an aromatic vinyl monomer and a unit derived from a vinyl cyano monomer.

The second copolymer can impart properties, i.e., mechanical properties, flowability and heat resistance, to the thermoplastic resin composition in a coordinated manner.

The unit derived from the aromatic vinyl monomer may be a unit derived from one or more selected from styrene, α -methylstyrene, α -ethylstyrene and p-methylstyrene, and, in particular, a unit derived from styrene is preferable.

The unit derived from a vinyl cyano-based monomer may be a unit derived from one or more selected from acrylonitrile, methacrylonitrile, phenylacetonitrile and α -chloroacrylonitrile, and, in particular, is preferably a unit derived from acrylonitrile.

The second copolymer may include a unit derived from an aromatic vinyl monomer and a unit derived from a vinyl cyano monomer in a weight ratio of 85:15 to 60:40, 80:20 to 65:35, or 75:25 to 70:30, preferably in a weight ratio of 65:35 or 75:25 to 70: 30. When the weight ratio of the unit derived from the aromatic vinyl-based monomer and the unit derived from the vinyl cyano-based monomer falls within the above range, the properties, i.e., mechanical properties, flowability and heat resistance, of the thermoplastic resin composition can be imparted in harmony.

The second copolymer may have a weight average molecular weight of 100,000 to 180,000g/mol, 120,000 to 160,000g/mol, or 130,000 to 150,000g/mol, and preferably has a weight average molecular weight of 130,000 to 150,000 g/mol. When the weight average molecular weight of the second copolymer falls within the above range, it is easy to control the polymerization reaction, and mechanical properties and processability are achieved in harmony.

The second copolymer may be one or more selected from the group consisting of a styrene/acrylonitrile copolymer and α -methylstyrene/acrylonitrile copolymer, and, in particular, is preferably a styrene/acrylonitrile copolymer.

The second copolymer may be prepared by one or more methods selected from emulsion polymerization, suspension polymerization, and bulk polymerization, and, in particular, preferably by polymerizing an aromatic vinyl-based monomer and a vinyl cyano-based monomer using bulk polymerization.

The weight ratio of the first copolymer to the second copolymer can be from 15:85 to 45:55, from 20:40 to 40:60, or from 25:75 to 35:65, and preferably from 25:75 to 35: 70. When the weight ratio falls within the above range, excellent mechanical strength, chemical resistance, processability, thermal stability and impact resistance are exhibited.

3. Third copolymer

The third copolymer has a soft segment comprising a unit derived from a polyalkylene glycol and a hard segment comprising a unit derived from an aromatic dicarboxylic acid or an aromatic dicarboxylate and a unit derived from a linear aliphatic diol.

The third copolymer may be a thermoplastic polyester elastomer. The third copolymer has excellent compatibility with the first copolymer, and can improve impact resistance and chemical resistance of the thermoplastic resin composition and minimize a decrease in flame retardancy.

The unit derived from a polyalkylene glycol may be a unit derived from one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, poly (1, 2-butanediol), polypentanediol, polyhexamethylene glycol, polyheptanediol, polynonanediol, polydecamediol, and α -hydrogen- ω -hydroxypoly (oxy-1, 4-butanediyl). specifically, a unit derived from one or more selected from the group consisting of polypropylene glycol and α -hydrogen- ω -hydroxypoly (oxy-1, 4-butanediyl) is preferable, and a unit derived from α -hydrogen- ω -hydroxypoly (oxy-1, 4-butanediyl) is more preferable.

The unit derived from an aromatic dicarboxylic acid may be a unit derived from one or more selected from 1, 4-phthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid and 1, 5-naphthalenedicarboxylic acid, and, in particular, a unit derived from 1, 4-naphthalenedicarboxylic acid is preferable.

The unit derived from the aromatic dicarboxylic acid ester may be a unit derived from one or more selected from dimethyl terephthalate, dimethyl isophthalate and dimethyl 2, 6-naphthalenedicarboxylate, and, in particular, a unit derived from dimethyl terephthalate is preferable.

The unit derived from the linear aliphatic diol may be a unit derived from one or more selected from the group consisting of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol, and, in particular, a unit derived from 1, 4-butanediol is preferable.

The hard segment may comprise units derived from an aromatic dicarboxylic acid or an aromatic dicarboxylate and units derived from a linear aliphatic diol in a weight ratio of 50:50 to 75:25 or 50:50 to 65:35, preferably in a weight ratio of 50:50 to 65: 35. When the weight ratio of the unit derived from the aromatic dicarboxylic acid or the aromatic dicarboxylate ester to the unit derived from the linear aliphatic diol falls within the above range, impact resistance, mechanical strength, heat resistance, chemical resistance and processability are further improved.

The third copolymer may comprise a soft segment and a hard segment in a weight ratio of 50:50 to 30:70 or 50:50 to 35:65, preferably in a weight ratio of 50:50 to 35: 65. When the weight ratio of the soft segment to the hard segment falls within the above range, the impact resistance, processability, chemical resistance and flame retardancy of the third copolymer are further improved.

The weight average molecular weight of the third copolymer may be 50,000 to 200,000g/mol or 100,000 to 150,000g/mol, and the weight average molecular weight is preferably 100,000 to 150,000 g/mol. When the weight average molecular weight of the third copolymer falls within the above range, impact resistance and processability can be further improved.

The third copolymer has a melt flow index (230 ℃, 2.16kg) measured according to ASTM D1238 of from 0.1g/10min to 30g/10min, from 0.5g/10min to 25g/10min, or from 3g/10min to 10g/10min, and preferably has a melt flow index of from 3g/10min to 10g/10 min. When the melt flow index of the third copolymer falls within the above range, the heat resistance, elongation, tensile strength and processability of the third copolymer can be further improved.

The third copolymer may be prepared by melt polycondensation of a polyester prepared by esterification of an aromatic dicarboxylic acid with a linear aliphatic diol or transesterification of an aromatic dicarboxylic acid ester with a linear aliphatic diol and a polyalkylene glycol. In this case, the hard segment may contain units derived from a polyester, and the soft segment may contain units derived from a polyalkylene glycol.

The third copolymer may be one or more selected from the group consisting of a polymer of 1, 4-phthalic acid with 1, 4-butanediol and α -hydro-omega-hydroxypoly (oxy-1, 4-butanediyl) (CAS No.37282-12-5) and a polymer of dimethyl 1, 4-phthalate with 1, 4-butanediol and α -hydro-omega-hydroxypoly (oxy-1, 4-butanediyl) (CAS No. 9078-71-1).

For example, PBT KEYF L EX BT2140D (trade name; CAS No.9078-71-1) manufactured by L G Chem L td. or KEYF L EX BT2140D (trade name; CAS No.37282-12-5) manufactured by L G Chem L td. may be used.

The content of the third copolymer is 2.0 to 10 parts by weight, preferably 2.5 to 7 parts by weight, and more preferably 5 to 7 parts by weight, relative to 100 parts by weight of the sum of the first and second copolymers. When the content of the third copolymer is less than the above range, the overall properties of the thermoplastic resin composition are reduced, and excellent chemical resistance cannot be imparted. When the content of the third copolymer is greater than the above range, the production cost may be increased without additional improvement. In addition, the percentage of moisture content in the thermoplastic resin composition is increased due to the third copolymer, and thus it is difficult to process the thermoplastic resin composition, and heat shrinkage is also increased during commercialization, and thus dimensional stability is significantly reduced.

4. Fourth copolymer

The fourth copolymer comprises units derived from an aromatic dicarboxylic acid, units derived from a linear aliphatic diol, and units derived from a cyclic aliphatic diol.

The fourth copolymer is a modified polyester, and can impart chemical resistance and impact resistance in harmony, while imparting excellent chemical resistance to the thermoplastic resin composition. In addition, the fourth copolymer can impart excellent extrusion moldability and blow moldability to the thermoplastic resin composition. In addition, the fourth copolymer can impart excellent dimensional stability during commercialization of the thermoplastic resin composition. In addition, since the fourth copolymer can assist the third copolymer, the amount of the expensive third copolymer can be reduced, and thus the production cost of the thermoplastic resin composition can be reduced.

The unit derived from an aromatic dicarboxylic acid may be a unit derived from one or more selected from 1, 4-phthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid and 1, 5-naphthalenedicarboxylic acid, and, in particular, a unit derived from 1, 4-naphthalenedicarboxylic acid is preferable.

The content of the unit from the aromatic dicarboxylic acid may be 10 to 70% by weight or 45 to 65% by weight, relative to the total weight of the fourth copolymer, and the content is preferably 45 to 65% by weight. When the content of the unit derived from the aromatic dicarboxylic acid falls within the above range, heat resistance, mechanical properties and processability can be achieved in harmony.

The unit derived from the linear aliphatic diol may be a unit derived from one or more selected from the group consisting of 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol, and, in particular, a unit derived from 1, 2-ethanediol is preferable.

The content of the unit derived from the linear aliphatic diol may be 1 to 50% by weight or 3 to 30% by weight, relative to the total weight of the fourth copolymer, and the content is preferably 3 to 30% by weight. When the content of the unit derived from the linear aliphatic diol falls within the above range, chemical resistance, impact resistance, mechanical properties and processability are achieved in harmony.

The unit derived from the cyclic aliphatic diol may be a unit derived from one or more selected from the group consisting of 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol and 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, and, particularly, a unit derived from 1, 4-cyclohexanedimethanol is preferable.

The content of the unit derived from the cyclic aliphatic diol may be 20 to 50% by weight or 25 to 45% by weight, relative to the total weight of the fourth copolymer, and the content is preferably 25 to 45% by weight. When the content of the unit derived from the cyclic aliphatic diol falls within the above range, excellent transparency, chemical resistance and processability are exhibited.

The weight average molecular weight of the fourth copolymer may be 50,000 to 400,000g/mol or 60,000 to 300,000g/mol, and the weight average molecular weight is preferably 60,000 to 300,000 g/mol. When the weight average molecular weight of the fourth copolymer falls within the above range, chemical resistance, heat resistance, processability and mechanical properties are achieved in harmony.

The fourth copolymer is preferably a polymer of 1, 4-phthalic acid with 1, 4-cyclohexanedimethanol and 1, 2-ethylene glycol (CAS No. 25038-91-9).

The fourth copolymer may be directly prepared or may be a commercially available copolymer. For example, JN100 (trade name) manufactured by SK Chemicals may be used.

The content of the fourth copolymer may be 2.5 to 10 parts by weight, preferably 2.5 to 7 parts by weight, with respect to 100 parts by weight of the sum of the first and second copolymers. When the content of the fourth copolymer is less than the above range, impact resistance and chemical resistance may be reduced, and when the content of the fourth copolymer is greater than the above range, flame retardancy may be reduced.

5. Flame retardant

The flame retardant may be included to impart flame retardancy to the thermoplastic resin composition.

The flame retardant may be a halogen-based flame retardant, and, in particular, a bromine-based flame retardant is preferably used. When the bromine-based flame retardant is used, an excellent flame-retardant effect can be achieved when the thermoplastic resin composition is formed into a film.

The bromine-based flame retardant may be one or more selected from tetrabromobisphenol a, decabromodiphenyl ether, decabromodiphenyl ethane, 1, 2-bis (2,4, 6-tribromophenyl) ethane, octabromo-1, 3, 3-trimethyl-1-phenylindane, tetrabromobisphenol a-bis (2, 3-dibromopropyl ether), and 2,4, 6-tris (2,4, 6-tribromophenoxy) -1,3, 5-triazine, and, in particular, preferably 2,4, 6-tris (2,4, 6-tribromophenoxy) -1,3, 5-triazine.

The content of the flame retardant may be 10 to 30 parts by weight or 15 to 25 parts by weight with respect to 100 parts by weight of the sum of the first and second copolymers, and the content is preferably 15 to 25 parts by weight. When the content of the flame retardant falls within the above range, excellent flame retardancy can be achieved even when the thermoplastic resin composition is processed into a film, and more excellent flowability can be imparted to the thermoplastic resin composition.

6. Flame-retardant auxiliary agent

The flame retardant aid may assist the flame retardant in the following manner: the thermoplastic resin composition can achieve excellent flame retardancy even when a small amount of a flame retardant is contained in the thermoplastic resin composition.

The flame-retardant auxiliary is preferably antimony trioxide.

The content of the flame retardant aid may be 1 to 15 parts by weight or 3 to 8 parts by weight with respect to 100 parts by weight of the sum of the first and second copolymers, and the content is preferably 3 to 8 parts by weight. When the content of the flame retardant aid falls within the above range, excellent flame retardancy can be achieved without degrading other properties of the thermoplastic resin composition.

The thermoplastic resin composition according to one embodiment of the present invention may further include an additive, and the additive may be one or more selected from the group consisting of an impact modifier, a heat stabilizer, an anti-dripping agent, an antioxidant, a light stabilizer, an ultraviolet ray blocking agent, a pigment and an inorganic filler.

Hereinafter, the present invention will be described in detail with reference to examples so that those skilled in the art can easily practice the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described in this specification.