KR102266841B1 - Method for preparing thermoplastic resin composition - Google Patents

Abstract

The present invention comprises the steps of putting the first copolymer and the second copolymer into an extruder and first melt-mixing; and adding (2-hydroxyalkyl)-β-cyclodextrin and water to the extruder and secondary melt mixing, wherein the first copolymer is a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl It includes a cyan-based monomer-derived unit, and the second copolymer relates to a method for producing a thermoplastic resin composition comprising an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit.

Description

Method for producing a thermoplastic resin composition {METHOD FOR PREPARING THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a method for producing a thermoplastic resin composition, and more particularly, to a method for producing a thermoplastic resin composition having a remarkable odor reduction effect by adding (2-hydroxyalkyl)-β-cyclodextrin during melt mixing. .

Acrylonitrile-butadiene-styrene graft copolymer (hereinafter referred to as 'ABS graft copolymer') is being applied for various interior and exterior materials of automobiles due to its excellent processability.

Recently, interest in the environment has grown in general in society, and as a result, standards for air quality or smell inside automobiles have been strengthened. Accordingly, automobile manufacturers are strengthening the management of raw materials and parts used in automobiles.

Conventionally, an inorganic porous material such as zeolite has been used to remove the odor of the thermoplastic resin composition containing the ABS graft copolymer, but the impact strength is significantly lowered, so there is a limitation in the amount used, and thus the odor removal effect is not large. couldn't In addition, in the case of a stripping process in which water is added during melt mixing to remove odor-causing residues, etc., there is a limitation in removing odors because the time during which the residues are removed through discharge is short.

KR2016-0048011A

An object of the present invention is to provide a method for producing a thermoplastic resin composition having a remarkably reduced odor.

In order to solve the above problems, the present invention comprises the steps of putting a first copolymer and a second copolymer in an extruder and first melt-mixing; and adding (2-hydroxyalkyl)-β-cyclodextrin and water to the extruder and secondary melt mixing, wherein the first copolymer is a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl It includes a cyan-based monomer-derived unit, and the second copolymer provides a method for producing a thermoplastic resin composition comprising an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit.

The present invention provides a thermoplastic resin molded article made of the thermoplastic resin composition prepared by the above-described manufacturing method, and having an odor rating of 3 or less according to MS300-34.

In the method for producing a thermoplastic resin composition according to the present invention, by adding (2-hydroxyalkyl)-β-cyclodextrin and water during melt mixing, odor-causing substances are not only removed while the water is vaporized, but also (2-hydroxyl) Since it is captured by hydroxyalkyl)-β-cyclodextrin, the odor reduction effect is remarkably excellent.

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

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

A method for producing a thermoplastic resin composition according to an embodiment of the present invention comprises: 1. Putting the first copolymer and the second copolymer into an extruder and first melt-mixing; and 2. (2-hydroxyalkyl)-β-cyclodextrin and water are added to the extruder and secondary melt-mixing, wherein the first copolymer is a unit derived from a conjugated diene-based polymer and an aromatic vinyl-based monomer. and a vinyl cyan-based monomer-derived unit, wherein the second copolymer provides a method for preparing a thermoplastic resin composition comprising an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit.

Hereinafter, each step of the method for producing a thermoplastic resin composition according to an embodiment of the present invention will be described in detail.

1. First melt mixing step

First, the first copolymer and the second copolymer are put into the extruder and first melt-mixed.

It is preferable to introduce the first copolymer and the second copolymer to the main feeder of the extruder. When the first copolymer and the second copolymer are introduced into the main feeder, the first copolymer and the second copolymer are formed between the kneading block between the main feeder and the side feeder and the side feeder and the extrusion port to be described later. Since it can pass through the kneading block, it can be melt-mixed more uniformly.

The kneading block between the main feeder and the side feeder may be a kneading block installed on the outer peripheral surface of the shaft between the main feeder and the side feeder in the inner space of the barrel of the extruder.

The kneading block between the side feeder and the extrusion hole may be a kneading block installed on the outer peripheral surface of the shaft between the side feeder and the extrusion hole in the inner space of the barrel of the extruder.

The first melt mixing step may be performed at 210 to 280 °C, 220 to 270 °C or 230 to 260 °C, of which 230 to 260 °C is preferable. When the above-described range is satisfied, the first and second copolymers or the first to third copolymers may be uniformly melt-mixed.

The first copolymer includes a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit.

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

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

The conjugated diene-based monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, of which 1,3-butadiene may be preferable.

The conjugated diene-based polymer may be included in an amount of 45 to 75 wt%, 50 to 70 wt%, or 55 to 65 wt%, based on the total weight of the first copolymer, of which 55 to 65 wt% is preferable. Do. When the above-described range is satisfied, the impact resistance and processability of the first copolymer may be further improved.

The conjugated diene-based polymer may have an average particle diameter of 0.1 to 0.5 μm, 0.2 to 0.4 μm, and 0.25 to 0.35 μm, of which 0.25 to 0.35 μm is preferable. When the above-described range is satisfied, the impact resistance of the first copolymer can be further improved.

The aromatic vinyl-based monomer-derived unit may be at least one derived unit selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, and among these, styrene-derived units are preferable.

The aromatic vinyl-based monomer-derived unit may be included in an amount of 15 to 45 wt%, 20 to 40 wt%, or 25 to 35 wt%, based on the total weight of the first copolymer, of which 25 to 35 wt% it is preferable When the above-described range is satisfied, chemical resistance, rigidity, impact resistance, processability and surface gloss of the thermoplastic resin composition may be further improved.

The vinyl cyan-based monomer-derived unit may be at least one derived unit selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, of which acrylonitrile is derived from units are preferred.

The vinyl cyan-based monomer-derived unit may be included in an amount of 1 to 20 wt%, 3 to 17 wt%, or 5 to 12 wt%, based on the total weight of the first copolymer, of which 5 to 12 wt% it is preferable When the above-described range is satisfied, chemical resistance, rigidity, impact resistance, processability and surface gloss of the thermoplastic resin composition may be further improved.

The first copolymer may have a graft rate of 25 to 55%, 30 to 50%, or 35 to 45%, of which 35 to 45% is preferable. When the above-described range is satisfied, a balance between thermal stability and mechanical properties of the first copolymer may be achieved.

The first copolymer may have a weight average molecular weight of 60,000 to 80,000 g/mol, 65,000 to 75,000 g/mol, or 70,000 to 75,000 g/mol of the shell, of which 70,000 to 75,000 g/mol is preferable. When the above-described range is satisfied, both rigidity and fluidity may be excellent.

The shell may include a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyanide-based monomer graft polymerized to the conjugated diene-based polymer.

The first copolymer may be prepared by polymerizing an aromatic vinyl-based monomer and a vinyl cyan-based monomer by at least one method selected from the group consisting of emulsion polymerization, suspension polymerization and bulk polymerization in the presence of a conjugated diene-based polymer, It is preferably prepared by heavy emulsion polymerization.

The second copolymer includes an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit.

The second copolymer may impart heat resistance, rigidity, and processability to the thermoplastic resin composition.

The aromatic vinyl-based monomer-derived unit may be at least one derived unit selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene and p-methyl styrene, and among these, styrene-derived units are preferable.

The vinyl cyan-based monomer-derived unit may be at least one derived unit selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, of which acrylonitrile is derived from units are preferred.

The second copolymer may include the aromatic vinyl-based monomer-derived unit and the vinyl cyan-based monomer-derived unit in a weight ratio of 85:15 to 60:40, 80:20 to 65:35, or 75:25 to 70:30. and it is preferably included in a weight ratio of 75:25 to 70:30. When the above-described range is satisfied, the thermoplastic resin composition may better realize a balance of heat resistance, impact resistance, and processability.

The second copolymer may have a weight average molecular weight of 80,000 to 120,000 g/mol, 85,000 to 115,000 g/mol, or 90,000 to 110,000 g/mol, of which 90,000 to 110,000 g/mol is preferable. When the above-mentioned range is satisfied, it is possible to provide a copolymer having excellent fluidity and rigidity.

The first copolymer and the second copolymer may be added in a weight ratio of 15:85 to 35:65 or 20:80 to 30:70, of which the weight ratio of 20:80 to 30:70 is added. desirable. If the above-mentioned range is satisfied, chemical resistance, impact resistance, thermal stability, colorability, fatigue resistance, rigidity and workability may be further improved.

The mixture may further include a third copolymer including units derived from maleimide-based monomers and units derived from aromatic vinyl-based polymers.

The third copolymer may impart excellent heat resistance and rigidity to the thermoplastic resin composition.

The maleimide-based monomer-derived unit is maleimide, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-isobutyl maleimide, Nt -Butyl maleimide, N-lauryl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-(4-chlorophenyl) maleimide, 2-methyl-N-phenyl maleimide, N-(4 -Bromophenyl) maleimide, N-(4-nitrophenyl) maleimide, N-(4-hydroxyphenyl) maleimide, N-(4-methoxyphenyl) maleimide, N-(4-carboxyphenyl) ) may be at least one derived unit selected from the group consisting of maleimide and N-benzyl maleimide, of which N-phenyl maleimide-derived units are preferred.

The aromatic vinyl-based polymer-derived unit may be a polymer-derived unit prepared from at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, among which the styrene polymer is derived from units are preferred.

The third copolymer may include the maleimide-based monomer-derived unit and the aromatic vinyl-based polymer-derived unit in a weight ratio of 60:40 to 50:50 or 55:45 to 50:50, of which 55:45 to It is preferable to include it in a weight ratio of 50:50.

When the above-described range is satisfied, the heat resistance and processability of the third copolymer may be further improved.

The third copolymer may have a glass transition temperature of 180 to 210 °C, 185 to 205 °C, or 190 to 200 °C, of which 190 to 200 °C is preferable. When the above-described range is satisfied, the heat resistance of the thermoplastic resin composition may be further improved.

The third copolymer may have a weight average molecular weight of 125,000 to 150,000 g/mol, 130,000 to 145,000 g/mol, or 135,000 to 140,000 g/mol, of which 135,000 to 140,000 g/mol is preferable. If the above-described range is satisfied, fluidity and mechanical properties may be further improved.

If the third copolymer is further added, with respect to the total weight of the first to third copolymers, 15 to 40% by weight of the first copolymer, 40 to 65% by weight of the second copolymer, and the third air It may be added in an amount of 5 to 30% by weight of the coal.

Preferably, based on the total weight of the first to third copolymer, 20 to 35% by weight of the first copolymer, 45 to 60% by weight of the second copolymer, and 10 to 25% by weight of the third copolymer can be put in

More preferably, with respect to the total weight of the first copolymer to the third copolymer, 25 to 30% by weight of the first copolymer, 50 to 55% by weight of the second copolymer, and 15 to 20% by weight of the third copolymer It may be added in weight %.

When the above-described range is satisfied, the chemical resistance, impact resistance, thermal stability, colorability, fatigue resistance, rigidity and processability of the thermoplastic resin composition may be further improved.

The first to third polymers may be a base resin.

2. Second melt mixing step

Then, (2-hydroxyalkyl)-β-cyclodextrin and water are introduced into the extruder, and secondary melt mixing is performed.

The second melt-mixing may be a step of removing odor-causing substances remaining in the thermoplastic resin composition.

Preferably, the (2-hydroxyalkyl)-β-cyclodextrin and water are fed into the side feeder of the extruder. When the (2-hydroxyalkyl)-β-cyclodextrin and water are added between the first melt mixing and the second melt mixing, the odor-causing substance discharged from the first melt mixing is (2-hydroxyalkyl)- The odor can be remarkably reduced by being captured by β-cyclodextrin. In addition, since the odor-causing substances emitted while the water is vaporized can be removed together, the odor can be remarkably reduced.

If the (2-hydroxyalkyl)-β-cyclodextrin and water are put into the main feeder together with the first copolymer and the second copolymer before the first melt mixing, (2-hydroxyalkyl)- Since an excessive amount of odor-causing substances is collected in β-cyclodextrin, yellowing occurs in the thermoplastic resin composition and water volatilizes before the odor-causing substances are discharged, so the effect of reducing odors due to water cannot be realized.

The secondary melt mixing may be performed in a kneading block between the side feeder and the extrusion hole.

The (2-hydroxyalkyl)-β-cyclodextrin may be at least one selected from the group consisting of (2-hydroxyethyl)-β-cyclodextrin and (2-hydroxypropyl)-β-cyclodextrin; , of which (2-hydroxypropyl)-β-cyclodextrin is preferable.

The (2-hydroxyalkyl)-β-cyclodextrin is added in an amount of 0.05 to 5 parts by weight, 0.1 to 3 parts by weight, or 0.5 to 2 parts by weight based on 100 parts by weight of the total of the first copolymer and the second copolymer. and it is preferable to add 0.5 to 2 parts by weight of them. When the above-mentioned range is satisfied, the odor-causing substance of the thermoplastic resin composition discharged during melt mixing can be easily collected, and the odor can be remarkably reduced. In addition, mechanical properties of the thermoplastic resin composition are not deteriorated due to (2-hydroxyalkyl)-β-cyclodextrin, and yellowing can be minimized.

The water may be added in an amount of 0.05 to 5 parts by weight, 0.1 to 3 parts by weight, or 0.5 to 2 parts by weight, of which 0.5 to 2 parts by weight, based on 100 parts by weight of the total of the first copolymer and the second copolymer. It is preferable to put If the above-mentioned range is satisfied, the odor-causing substances of the thermoplastic resin composition discharged during the primary and secondary melt mixing while water is volatilized may be removed together.

The (2-hydroxyalkyl)-β-cyclodextrin and water may be added in a ratio of 10:90 to 50:50, 20:80 to 50:50, or 40:60 to 50:50 while satisfying the above-mentioned contents. and, among them, it is preferably added in a ratio of 40:60 to 50:50. When the above-mentioned range is satisfied, the odor-causing substances of the thermoplastic resin composition discharged during the primary and secondary melt mixing while water is volatilized can be more efficiently removed together.

The (2-hydroxyalkyl)-β-cyclodextrin and water may be added as an aqueous solution of (2-hydroxyalkyl)-β-cyclodextrin. When it is added in the above-described state, it is uniformly introduced into the first melt-mixed mixture, so that odor-causing substances can be easily collected and removed.

The secondary melt mixing may be performed at 210 to 280°C, 220 to 270°C or 230 to 260°C, of which 230 to 260°C is preferable. When the above-described range is satisfied, the first and second copolymers or the first to third copolymers are uniformly melt-mixed, and odor-causing substances can be easily collected and removed.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Example One

28 parts by weight of an ABS graft copolymer (product name: DP270, manufacturer: LG Chem) as the first copolymer, 50 parts by weight of a SAN copolymer (product name: 92HR, manufacturer: LG Chem) as the second copolymer, and a third copolymer A mixture containing 20 parts by weight of a PMI-PS copolymer (trade name: MSNB, manufacturer: DENKA) was put into the main feeder of a twin-screw extruder set at 250° C., and first melt-mixed.

Then, in the stripping process of the twin-screw extruder, that is, with a side feeder, 1 part by weight of (2-hydroxypropyl)-β-cyclodextrin aqueous solution (HPCD aqueous solution, concentration: 50% by weight) of the first melt-mixed mixture was put into the secondary melt-mixing to prepare a thermoplastic resin composition in the form of pellets.

Example 2

A thermoplastic resin composition in pellet form was prepared in the same manner as in Example 1, except that 2 parts by weight of (2-hydroxypropyl)-β-cyclodextrin aqueous solution (concentration: 50% by weight) was added.

Example 3

A thermoplastic resin composition in pellet form was prepared in the same manner as in Example 1, except that 4 parts by weight of (2-hydroxypropyl)-β-cyclodextrin aqueous solution (HPCD aqueous solution, concentration: 50% by weight) was added.

Example 4

A mixture containing 30 parts by weight of an ABS graft copolymer (trade name: DP270, manufacturer: LG Chem) as the first copolymer and 70 parts by weight of a SAN copolymer (product name: 92HR, manufacturer: LG Chem) as the second copolymer was added to 250 It was put into the main feeder of the twin-screw extruder set at ℃, and first melt-mixed.

Then, in the stripping process of the twin-screw extruder, that is, with a side feeder, 2 parts by weight of (2-hydroxypropyl)-β-cyclodextrin aqueous solution (HPCD aqueous solution, concentration: 50% by weight) of the first melt-mixed mixture was put into the secondary melt-mixing to prepare a thermoplastic resin composition in the form of pellets.

Example 5

32 parts by weight of an ABS graft copolymer (product name: DP270, manufacturer: LG Chem) as the first copolymer, 50 parts by weight of a SAN copolymer (product name: 92HR, manufacturer: LG Chem) as the second copolymer, and a third copolymer A mixture containing 18 parts by weight of a PMI-PS copolymer (trade name: MSNB, manufacturer: DENKA) was put into the main feeder of a twin-screw extruder set at 250° C., and first melt-mixed.

Then, in the stripping process of the twin-screw extruder, that is, with a side feeder, 2 parts by weight of (2-hydroxypropyl)-β-cyclodextrin aqueous solution (HPCD aqueous solution, concentration: 50% by weight) of the first melt-mixed mixture was put into the secondary melt-mixing to prepare a thermoplastic resin composition in the form of pellets.

comparative example One

(2-hydroxypropyl)-β-cyclodextrin aqueous solution (HPCD aqueous solution, concentration: 50% by weight) was prepared in the same manner as in Example 1, except that it was not added.

comparative example 2

28 parts by weight of an ABS graft copolymer (product name: DP270, manufacturer: LG Chem) as the first copolymer, 50 parts by weight of a SAN copolymer (product name: 92HR, manufacturer: LG Chem) as the second copolymer, and a third copolymer A mixture containing 20 parts by weight of a PMI-PS copolymer (trade name: MSNB, manufacturer: DENKA) and 0.5 parts by weight of (2-hydroxypropyl)-β-cyclodextrin (HPCD) were introduced into the main feeder of the twin-screw extruder and extruded Thus, a thermoplastic resin composition in the form of pellets was prepared.

comparative example 3

A thermoplastic resin composition was prepared in the same manner as in Comparative Example 2, except that 0.5 parts by weight of α-cyclodextrin (α-CD) was added instead of (2-hydroxypropyl)-β-cyclodextrin.

comparative example 4

A thermoplastic resin composition was prepared in the same manner as in Comparative Example 2, except that 0.5 parts by weight of β-cyclodextrin (β-CD) was added instead of (2-hydroxypropyl)-β-cyclodextrin.

comparative example 5

A thermoplastic resin composition was prepared in the same manner as in Comparative Example 2, except that 0.5 parts by weight of zeolite was added instead of (2-hydroxypropyl)-β-cyclodextrin.

comparative example 6

A thermoplastic resin composition was prepared in the same manner as in Comparative Example 2, except that 1 part by weight of zeolite was added instead of (2-hydroxypropyl)-β-cyclodextrin.

Examples and Comparative Examples are summarized in Table 1 below.

division base resin additive first copolymer
(parts by weight) second copolymer
(parts by weight) tertiary copolymer
(parts by weight) Input method Kinds content
(parts by weight) Example 1 28 50 20 side feeder HPCD aqueous solution One Example 2 28 50 20 side feeder HPCD aqueous solution 2 Example 3 28 50 20 side feeder HPCD aqueous solution 4 Example 4 30 70 - side feeder HPCD aqueous solution 2 Example 5 32 50 18 side feeder HPCD aqueous solution 2 Comparative Example 1 28 50 20 - - - Comparative Example 2 28 50 20 main feeder HPCD 0.5 Comparative Example 3 28 50 20 main feeder α-CD 0.5 Comparative Example 4 28 50 20 main feeder β-CD 0.5 Comparative Example 5 28 50 20 main feeder zeolite 0.5 Comparative Example 6 28 50 20 main feeder zeolite 1.0

Experimental example

Specimens were prepared by injection of the thermoplastic resin compositions of Examples and Comparative Examples, and physical properties were evaluated by the method described below. And the results are shown in Table 2 below.

1) Odor evaluation: According to the MS300-34 standard, a specimen of 3 mm (thickness) × 3 cm (width) × 8 cm (length) was placed in a 4 liter glass container, heated at 80° C. for 2 hours, and then at 23° C. After standing for 1 hour, the smell was judged on a scale of 1 to 6. The lower the odor grade, the better the odor characteristic. When it is grade 3 or less, it is suitable for automobile interior materials.

Grade 1: Unperceivable, Grade 2: Slightly Perceivable, Grade 3: Moderate, Grade 4: Strongly Perceivable, Grade 5: Stinging Odor, Grade 6: Unbearable

2) Color: b ^* value was measured using a color meter.

3) Izod impact strength (kg·cm/cm): According to ASTM D256, it was measured by making a notch in a specimen having a thickness of 6.4 mm.

4) HDT (°C): It was measured under a load condition of 18.6 kgf/cm 2 on a specimen having a thickness of 6.35 mm according to ASTM D648.

division Odor evaluation color (b ^* ) Izod impact strength HDT Example 1 3.0 14 19.5 101.5 Example 2 3.0 15 19.0 101.7 Example 3 2.5 17 17.5 101.4 Example 4 3.0 14 23.0 91.0 Example 5 3.0 16 21.0 100.0 Comparative Example 1 4.0 12 20.0 100.0 Comparative Example 2 3.5 23 19.0 99.5 Comparative Example 3 3.5 25 18.7 99.0 Comparative Example 4 3.5 22 18.7 99.2 Comparative Example 5 3.5 21 15.0 99.5 Comparative Example 6 3.5 21 9.0 99.3

Referring to Table 2, in the case of Examples 1 to 5, since the odor grade was 3 or less, the odor characteristic was excellent, and the b ^* value was also low, so it was confirmed that yellow did not appear. In addition, since it has excellent impact strength and thermal deformation temperature, it is suitable for automotive interior materials.

In the case of Comparative Example 1, (2-hydroxypropyl) -β-cyclodextrin was not added, so the odor reduction effect was not implemented.

In the case of Comparative Example 2, since (2-hydroxypropyl)-β-cyclodextrin was introduced into the main feeder of the extruder, the contact time of (2-hydroxypropyl)-β-cyclodextrin with the odor-causing substance was increased, and the thermoplastic Yellowing of the resin composition occurred, and the odor reduction effect was not great.

In Comparative Examples 2, 3 and 4, (2-hydroxypropyl)-β-cyclodextrin, α-cyclodextrin or β-cyclodextrin was introduced into the main feeder of the extruder, and extrusion was performed, The time the cyclodextrin-based compound was in contact with the odor-causing substance was prolonged, causing yellowing of the thermoplastic resin composition, and the odor reduction effect was not great.

In Comparative Examples 5 and 6, zeolite was introduced into the main feeder of the extruder and extrusion was performed, but yellowing of the thermoplastic resin composition occurred, and the odor reduction effect was not significant.

Claims (10)

Putting the first copolymer and the second copolymer into the extruder and first melt-mixing; and
Including (2-hydroxyalkyl)-β-cyclodextrin and water in the extruder and secondary melt mixing,
The first copolymer includes a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit,
The second copolymer is a method for producing a thermoplastic resin composition comprising an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit.
The method according to claim 1,
A method for producing a thermoplastic resin composition by inputting the first copolymer and the second copolymer to the main feeder of the extruder.
The method according to claim 1,
A method for producing a thermoplastic resin composition in which the (2-hydroxyalkyl)-β-cyclodextrin and water are added to the side feeder of the extruder.
The method according to claim 1,
The (2-hydroxyalkyl)-β-cyclodextrin is at least one selected from the group consisting of (2-hydroxyethyl)-β-cyclodextrin and (2-hydroxypropyl)-β-cyclodextrin A method for producing a thermoplastic resin composition.
The method according to claim 1,
Based on 100 parts by weight of the sum of the first copolymer and the second copolymer,
0.05 to 5 parts by weight of the (2-hydroxyalkyl)-β-cyclodextrin; and
A method for producing a thermoplastic resin composition by adding the water in an amount of 0.05 to 5 parts by weight.
The method according to claim 1,
The method for producing a thermoplastic resin composition, wherein the (2-hydroxyalkyl)-β-cyclodextrin and water are added in an aqueous solution state of (2-hydroxyalkyl)-β-cyclodextrin.
The method according to claim 1,
A method for producing a thermoplastic resin composition by adding the first copolymer and the second copolymer in a weight ratio of 15:85 to 35:65.
The method according to claim 1,
In the first melt-mixing step, a third copolymer is further added,
The third copolymer is a method for producing a thermoplastic resin composition comprising a unit derived from a maleimide-based monomer and a unit derived from an aromatic vinyl-based polymer.
9. The method of claim 8,
Based on the total weight of the first copolymer to the third copolymer,
15 to 40% by weight of the first copolymer,
40 to 65% by weight of the second copolymer; and
The method for producing a thermoplastic resin composition to be added in 5 to 30% by weight of the third copolymer.
It is prepared from the thermoplastic resin composition prepared by the manufacturing method according to any one of claims 1 to 9,
A thermoplastic resin molded article with an odor rating of 3 or less according to MS300-34.