KR102288289B1 - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a first copolymer comprising an alkyl (meth)acrylate-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit; a second copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit; a third copolymer comprising an aromatic vinyl-based monomer and a vinyl cyan-based monomer; a fourth copolymer comprising a unit derived from a maleimide-based monomer, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a maleic acid-based monomer; a fifth copolymer comprising a unit derived from 1,4-benzenedicarboxylic acid and a unit derived from 1,4-butadiol; and 1,4-benzenedicarboxylic acid-derived units, dianhydrohexitol-derived units, 1,4-cyclohexanedimethanol-derived units, and ethylene glycol-derived units. It relates to a resin composition.

Description

Thermoplastic resin composition {THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a thermoplastic resin composition, and more particularly, to provide a thermoplastic resin composition excellent in both chemical resistance and impact resistance.

Acrylonitrile-butadiene-styrene copolymer (hereinafter referred to as 'ABS copolymer') is widely applied to electrical and electronic products and office automation equipment based on its excellent mechanical properties and processability.

Acrylate-styrene-acrylonitrile copolymer (hereinafter referred to as 'ASA copolymer') realizes excellent impact resistance, appearance characteristics and processability, and has a high thermal deformation temperature, so automobile parts, electrical/electronic products, and building materials Its use is gradually expanding.

A thermoplastic resin composition comprising an ASA copolymer and an ABS copolymer is widely used as a material for automotive exterior materials that are frequently exposed to sunlight, and its use is increasing for interior materials requiring some weather resistance.

Since automobile interior materials have many opportunities to come into contact with various chemical substances such as air fresheners and deodorants, high chemical resistance is required.

However, the conventional thermoplastic resin composition has weak chemical resistance. In particular, when chemicals such as air fresheners, deodorants, and mold removers are applied to automobile air conditioners, it has been found that cracks occur in automobile air vents. In order to solve this problem, a polyester elastomer was additionally added to the conventional thermoplastic resin composition, but there was a problem in that mechanical properties were lowered when an excessive amount was added.

KR2009-0025134A

An object of the present invention is to provide a thermoplastic resin composition excellent in chemical resistance, impact resistance, heat resistance and flexural modulus.

In order to solve the above problems, the present invention provides a first copolymer comprising an alkyl (meth)acrylate-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit; a second copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit; a third copolymer comprising an aromatic vinyl-based monomer and a vinyl cyan-based monomer; a fourth copolymer comprising a unit derived from a maleimide-based monomer, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a maleic acid-based monomer; a fifth copolymer comprising a unit derived from 1,4-benzenedicarboxylic acid and a unit derived from 1,4-butadiol; and 1,4-benzenedicarboxylic acid-derived units, dianhydrohexitol-derived units, 1,4-cyclohexanedimethanol-derived units, and ethylene glycol-derived units. A resin composition is provided.

In addition, the present invention is made of the above-described thermoplastic resin composition, the flexural modulus according to ASTM D790 is 18,000 to 21,000 kgf / ㎠, and the crack width in ESCR evaluation based on ASTM D1693 is less than 10㎛ a thermoplastic resin molded article to provide.

The thermoplastic resin composition according to an embodiment of the present invention is excellent in chemical resistance, impact resistance, heat resistance and flexural modulus.

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.

In the present invention, the average particle size may be defined as a particle size corresponding to 50% or more of the cumulative volume in the particle size distribution curve of the particles.

In the present invention, the average particle diameter can be measured using a laser particle size analyzer (trade name: S3500, manufacturer: Micratac).

In the present invention, the weight average molecular weight can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent.

A thermoplastic resin composition according to an embodiment of the present invention comprises: 1. a first copolymer comprising an alkyl (meth)acrylate-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit; 2. A second copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit; 3. A third copolymer comprising an aromatic vinyl-based monomer and a vinyl cyan-based monomer; 4. A fourth copolymer comprising a maleimide-based monomer-derived unit, an aromatic vinyl-based monomer-derived unit and a maleic acid-based monomer-derived unit; 5. A fifth copolymer comprising a unit derived from 1,4-benzenedicarboxylic acid and a unit derived from 1,4-butadiol; and 6. A sixth copolymer comprising a unit derived from 1,4-benzenedicarboxylic acid, a unit derived from dianhydrohexitol, a unit derived from 1,4-cyclohexanedimethanol, and a unit derived from ethylene glycol. do.

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

1. First copolymer

The first copolymer includes an alkyl (meth)acrylate-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit.

The first copolymer may impart excellent impact resistance, appearance characteristics, processability and weather resistance to the thermoplastic resin composition.

The alkyl (meth) acrylate-based polymer may include an alkyl acrylate-based polymer modified by graft polymerization of the alkyl acrylate-based polymer with an aromatic vinyl-based monomer and a vinyl cyan-based monomer.

The alkyl (meth) acrylate-based polymer may be prepared by polymerization of an alkyl acrylate-based monomer, specifically, a cross-linking reaction to prepare a seed, and polymerization of the seed and an alkyl acrylate-based monomer, specifically, a cross-linking reaction. .

The alkyl (meth) acrylate-based monomer may be C ₁ to C ₁₀ alkyl (meth) acrylate, and the C ₁ to C ₁₀ alkyl (meth) acrylate is methyl acrylate, ethyl acrylate, butyl acryl It may be at least one selected from the group consisting of acrylate and ethylhexyl acrylate, of which butyl acrylate is preferable.

The alkyl acrylate-based polymer may have an average particle diameter of 0.30 to 0.60 μm, 0.35 to 0.55 μm, or 0.40 to 0.50 μm, of which 0.40 to 0.50 μm is preferable. When the above-mentioned range is satisfied, more excellent impact resistance can be imparted to the thermoplastic resin composition.

The alkyl (meth)acrylate-based polymer may be included in 35 to 65% by weight, 40 to 60% by weight, or 45 to 55% by weight, of which 45 to 55% by weight, based on the total weight of the first copolymer. It is preferable to include When the above-described range is satisfied, it is possible to impart better impact resistance to a molded article made of 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 aromatic vinyl-based monomer-derived unit may be included in an amount of 25 to 45 wt%, 30 to 40 wt%, or 35 to 40 wt%, based on the total weight of the first copolymer, of which 35 to 40 wt% it is preferable When the above-described range is satisfied, the processability of the thermoplastic resin composition may be further improved, and the appearance characteristics of a molded article made 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 5 to 20 wt%, 10 to 20 wt%, or 10 to 15 wt%, based on the total weight of the first copolymer, of which 10 to 15 wt% it is preferable When the above-described range is satisfied, the chemical resistance and weather resistance of the thermoplastic resin composition may be further improved.

The first copolymer may have a weight average molecular weight of 100,000 to 240,000 g/mol, 120,000 to 220,000 g/mol, or 140,000 to 200,000 g/mol, more preferably 140,000 to 200,000 g/mol. When the above-described range is satisfied, the impact resistance of the thermoplastic resin composition may be further improved.

The weight average molecular weight of the first copolymer is the weight average molecular weight of the alkyl acrylate-based polymer and the weight average molecular weight of the unit derived from the aromatic vinyl monomer and the unit derived from the vinyl cyanide monomer graft polymerized to the alkyl acrylate polymer. can mean the sum of

The first copolymer may be prepared by graft polymerization of an alkyl acrylate-based polymer, an aromatic vinyl-based monomer and a vinyl cyan-based monomer using one or more polymerization methods selected from the group consisting of bulk polymerization, emulsion polymerization, and suspension polymerization. It is preferable to be prepared by graft polymerization using emulsion polymerization among them.

The first copolymer may be prepared in an amount of 5 to 35 wt%, 10 to 30 wt%, or 15 to 25 wt%, based on the total weight of the thermoplastic resin composition, of which 15 to 25 wt% is preferably included. . When the above-mentioned range is satisfied, it is possible to impart superior impact resistance, appearance characteristics, processability and heat resistance to a molded article made of the thermoplastic resin composition.

2. Second copolymer

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

The second copolymer may impart excellent impact resistance, processability and chemical 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 have an average particle diameter of 1 to 8 μm, 2 to 6 μm, or 3 to 4 μm, of which 3 to 4 μm is preferable. When the above-described range is satisfied, the mechanical properties of the second copolymer may be further improved.

The conjugated diene-based polymer may be included in an amount of 5 to 25% by weight, 10 to 25% by weight, or 10 to 20% by weight, based on the total weight of the second copolymer, and it is preferable to include it in an amount of 10 to 20% by weight. do. When the above-described range is satisfied, the impact resistance and processability of the second copolymer may 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 50 to 85% by weight, 55 to 80% by weight, or 60 to 75% by weight, of which 60 to 75% by weight, based on the total weight of the second copolymer. it is preferable When the above-described range is satisfied, the appearance characteristics 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 5 to 25 wt%, 10 to 25 wt%, or 10 to 20 wt%, based on the total weight of the second copolymer, of which 10 to 20 wt% is included desirable. When the above-described range is satisfied, the chemical resistance of the heat-resistant resin composition may be further improved.

The second copolymer may be prepared by polymerization of 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 bulk polymerization.

The second copolymer may be prepared in an amount of 1 to 25 wt%, 5 to 20 wt%, or 10 to 15 wt%, based on the total weight of the thermoplastic resin composition, of which 10 to 15 wt% is preferably included. . When the above-described range is satisfied, it is possible to impart superior impact resistance, processability and chemical resistance to a molded article made of the thermoplastic resin composition.

3. Third copolymer

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

The third copolymer may impart excellent heat resistance to the thermoplastic resin composition. In addition, the second copolymer and excellent compatibility can improve the impact resistance of 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, of which the α-methyl styrene-derived unit is preferable. do.

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 third 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-mentioned range is satisfied, the balance of mechanical properties, fluidity and heat resistance of the thermoplastic resin composition can be better achieved.

The third copolymer may have a weight average molecular weight of 70,000 to 130,000 g/mol, 80,000 to 120,000 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, the balance of mechanical properties, fluidity and heat resistance of the thermoplastic resin composition can be better achieved.

The third copolymer may have a glass transition temperature of 110 to 135°C, 115 to 130°C, or 120 to 125°C, of which 120 to 125°C is preferable. When the above-described conditions are satisfied, it is possible to impart better heat resistance to the thermoplastic resin composition.

The third copolymer may be prepared by polymerization of 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, of which one is prepared by bulk polymerization desirable.

The third copolymer may be prepared in an amount of 30 to 55 wt%, 35 to 50 wt%, or 40 to 45 wt%, based on the total weight of the thermoplastic resin composition, of which 40 to 45 wt% is preferably included. . When the above-mentioned range is satisfied, better heat resistance and mechanical properties can be imparted to a molded article made of the thermoplastic resin composition.

4. Fourth copolymer

The fourth copolymer includes a unit derived from a maleimide-based monomer, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a maleic acid-based monomer.

The fourth copolymer may impart excellent heat resistance and chemical resistance to the thermoplastic resin composition.

The fourth copolymer may have a glass transition temperature of 185 to 210 °C, 190 to 205 °C, or 190 to 200 °C, of which 190 to 200 °C is preferable. When the above-described range is satisfied, it is possible to impart better heat resistance 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 maleimide-based monomer-derived unit may be included in 35 to 65 wt%, 40 to 60 wt%, or 45 to 55 wt%, based on the total weight of the fourth copolymer, of which 45 to 55 wt% it is preferable When the above-described range is satisfied, the heat resistance and chemical resistance of the fourth copolymer may 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 30 to 60 wt%, 35 to 55 wt%, or 40 to 50 wt%, based on the total weight of the fourth copolymer, of which 40 to 50 wt% desirable. When the above-described range is satisfied, the processability and appearance characteristics of the fourth copolymer may be improved.

The maleic acid-based monomer-derived unit may be one or more derived units selected from the group consisting of maleic anhydride, maleic acid, maleic monoester and maleic diester, Among these, the unit derived from maleic anhydride is preferable.

The vinyl maleate-based monomer-derived unit may be included in 0.1 to 10 wt%, 1 to 7 wt%, or 2 to 5 wt%, based on the total weight of the fourth copolymer, of which 2 to 5 wt% is included. desirable. If the above-mentioned range is satisfied, chemical resistance and compatibility with other copolymers may be improved.

The fourth copolymer may be prepared in an amount of 1 to 25 wt%, 5 to 20 wt%, or 10 to 15 wt%, based on the total weight of the thermoplastic resin composition, of which 10 to 15 wt% is preferably included. . When the above-described range is satisfied, the heat resistance and chemical resistance of the thermoplastic resin composition may be further improved.

5. Fifth copolymer

The fifth copolymer is a thermoplastic polyester elastomer and includes units derived from 1,4-benzenedicarboxylic acid and units derived from 1,4-butadiol.

The fifth copolymer may impart excellent chemical resistance, impact resistance and processability to the thermoplastic resin composition.

The fifth copolymer comprises the 1,4-benzenedicarboxylic acid-derived unit and the 1,4-butadiol-derived unit from 90:10 to 60:40, 80:20 to 60:40, or 70:30 to 60: It may be included in a weight ratio of 40, of which it is preferably included in a ratio of 70:30 to 60:40. When the above-mentioned range is satisfied, excellent processability, impact resistance and chemical resistance can be imparted to the thermoplastic resin composition.

The fifth copolymer may have a melt index (230° C., 2.16 kg) according to ASTM D570 of 2 to 10 g/10min, 3 to 8 g/10min, or 4 to 6 g/10min, of which 4 to 6 g/10min is preferred. When the above-described range is satisfied, excellent processability can be imparted to the thermoplastic resin composition.

The fifth copolymer may have a flexural modulus (6.4mm, 15mm/min) of 650 to 950 kg/cm2, 700 to 900 kg/cm2, or 750 to 850 kg/cm2 based on ASTM D790, of which 750 to 850 kg/cm 2 is preferred. When the above-described range is satisfied, there is an advantage in preventing cracks by reducing stress acting on the thermoplastic resin composition during ESCR evaluation.

The fifth copolymer may be directly manufactured or commercially available, and KEYFLEX BT2140D (CAS No. 37282-12-5) of LG Chem may be used.

The fifth copolymer may be prepared in an amount of 1 to 25 wt%, 5 to 20 wt%, or 10 to 15 wt%, based on the total weight of the thermoplastic resin composition, of which 10 to 15 wt% is preferably included. . When the above-described range is satisfied, the chemical resistance, impact resistance and processability of the thermoplastic resin composition may be further improved.

6. 6th copolymer

The sixth copolymer is a polyester copolymer, comprising a unit derived from 1,4-benzenedicarboxylic acid, a unit derived from dianhydrohexitol, a unit derived from 1,4-cyclohexanedimethanol, and a unit derived from ethylene glycol. include

The sixth copolymer may impart excellent impact resistance and chemical resistance to the thermoplastic resin composition.

The 1,4-benzenedicarboxylic acid-derived unit may be included in an amount of 40 to 80% by weight, 45 to 75% by weight, or 50 to 70% by weight, of which 50 to 80% by weight, based on the total weight of the sixth copolymer. It is preferably included in 70% by weight. When included in the above range, the heat resistance, chemical resistance and weather resistance of the sixth copolymer may be improved.

The dianhydrohexitol-derived unit may be included in an amount of 1 to 35 wt%, 5 to 30 wt%, or 10 to 25 wt%, based on the total weight of the sixth copolymer, of which 10 to 25 wt% preferably included. When included in the above range, the heat resistance, chemical resistance and chemical resistance of the sixth copolymer may be improved.

The 1,4-cyclohexanedimethanol-derived unit may be included in an amount of 1 to 35% by weight, 5 to 30% by weight, or 10 to 25% by weight based on the total weight of the sixth copolymer, of which 10 to 25 It is preferably included in weight %. When included in the above range, it is possible to improve the impact resistance of the sixth copolymer.

The ethylene glycol-derived unit may be included in 0.1 to 25% by weight, 0.5 to 20% by weight, or 1 to 15% by weight, of which 1 to 15% by weight, based on the total weight of the sixth copolymer. desirable. When included in the above-described range, the processability of the sixth copolymer may be improved.

The sixth copolymer may have a weight average molecular weight of 30,000 to 80,000 g/mol, 40,000 to 70,000 g/mol, or 50,000 to 60,000 g/mol, of which 50,000 to 60,000 g/mol is preferable. When the above-described range is satisfied, the impact resistance and chemical resistance of the thermoplastic resin composition may be further improved.

The sixth copolymer may have a flexural modulus (1.27 mm/min) of 20,000 to 24,000 kgf/cm, 21,000 to 23,000 kgf/cm, or 21,700 to 22,200 kgf/cm, of which, according to ASTM D790, 21,700 to 22,200 kgf/cm 2 is preferred. If the above-described range is satisfied, the flexural modulus of the thermoplastic resin lowered due to the fifth copolymer may be improved.

The sixth copolymer may have a heat deflection temperature of 95 to 135 °C, 100 to 130 °C, or 105 to 125 °C based on ASTM D648, of which 105 to 125 °C is preferable. When the above-mentioned range is satisfied, excellent heat resistance can be imparted to the thermoplastic resin composition.

The sixth copolymer may be directly manufactured or commercially available, and ECOZEN T110 and ECOZEN T120 (CAS No. 1038843-64-9) of SK Chemicals may be used.

The sixth copolymer may be prepared in an amount of 3 to 20 wt%, 4 to 15 wt%, or 5 to 10 wt%, based on the total weight of the thermoplastic resin composition, of which 5 to 10 wt% is preferably included. . When the above-described range is satisfied, the flexural modulus, rigidity, chemical resistance, and heat resistance of the thermoplastic resin composition may be further improved.

The thermoplastic resin composition according to an embodiment of the present invention may further include an additive, wherein the additive is 1 from the group consisting of an impact modifier, a heat stabilizer, an anti-drip agent, an antioxidant, a light stabilizer, a sunscreen, a pigment, and an inorganic filler. may be more than one species.

The thermoplastic resin molded article prepared from the thermoplastic resin composition according to an embodiment of the present invention has a flexural modulus of 18,000 to 21,000 kgf/cm 2 according to ASTM D790, and a crack width in ESCR evaluation according to ASTM D1693 is less than 10 μm. In addition, the impact strength according to ASTM D256 is 10 kgf·cm/cm or more. If the above-mentioned values are satisfied, it may be suitable as an automobile interior material requiring excellent chemical resistance, impact resistance and flexural modulus.

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.

manufacturing example 1: Preparation of the first copolymer

It was prepared by emulsion polymerization of 50 parts by weight of a butyl acrylate polymer having an average particle diameter of 0.45 μm, 35 parts by weight of styrene, and 15 parts by weight of acrylonitrile. At this time, the weight average molecular weight of the first copolymer was 170,000 g/mol.

manufacturing example 2: Preparation of the second copolymer

It was prepared by bulk polymerization of 15 parts by weight of butathiene polymer having an average particle diameter of 3.5 µm, 70 parts by weight of styrene and 15 parts by weight of acrylonitrile.

manufacturing example 3: Preparation of the third copolymer

It was prepared by bulk polymerization of 70 parts by weight of α-methyl styrene and 30 parts by weight of acrylonitrile. At this time, the weight average molecular weight of the third copolymer was 95,000 g/mol.

<Production of thermoplastic resin composition>

Example 1 to Example 6

The copolymer of Preparation Example 1 as the first copolymer, the copolymer of Preparation Example 2 as the second copolymer, the copolymer of Preparation Example 3 as the third copolymer, MS-NB as the fourth copolymer (trade name, manufacturer: DENKA ), KEYFLEX BT2140D (brand name, manufacturer: LG Chem) as the fifth copolymer, ECOZEN T110 (trade name, manufacturer: SK Chemicals) and ECOZEN T120 (brand name, manufacturer: SK Chemicals) as the sixth copolymer are listed in Table 1 below The content was put into a Henschel mixer and uniformly mixed, and then put into a twin-screw extruder set at 240° C. to prepare a thermoplastic resin composition in the form of pellets.

division Example 1
(parts by weight) Example 2
(parts by weight) Example 3
(parts by weight) Example 4
(parts by weight) Example 5
(parts by weight) Example 6
(parts by weight) first copolymer 20 20 20 20 20 20 second copolymer 10 10 10 10 10 10 tertiary copolymer 45 40 45 40 25 47 fourth copolymer 10 10 10 10 10 10 fifth copolymer 10 10 10 10 10 10 6th copolymer ECOZEN T110 5 10 - - 25 2 ECOZEN T120 - - 5 10 - -

comparative example One

As shown in Table 2 below, a thermoplastic resin composition was prepared in the same manner as in Example 1, except that 60 parts by weight of the third copolymer was added, and the fifth copolymer and the sixth copolymer were not added. .

comparative example 2

As shown in Table 2 below, a thermoplastic resin composition was prepared in the same manner as in Example 1, except that 50 parts by weight of the third copolymer was added and the sixth copolymer was not added.

comparative example 3

As shown in Table 2 below, a thermoplastic resin composition was prepared in the same manner as in Example 2, except that 15 parts by weight of the fifth copolymer was added and the sixth copolymer was not added.

comparative example 4

As shown in Table 2 below, the third copolymer was added in 50 parts by weight, the fifth copolymer was not added, and 20 parts by weight of ECOZEN T110 was added as the sixth copolymer in Example 1 and A thermoplastic resin composition was prepared in the same manner.

Hereinafter, the components and contents of Comparative Examples and Reference Examples are summarized and described in Table 2 below.

division Comparative Example 1
(parts by weight) Comparative Example 2
(parts by weight) Comparative Example 3
(parts by weight) Comparative Example 4
(parts by weight) first copolymer 20 20 20 20 second copolymer 10 10 10 10 tertiary copolymer 60 50 40 50 fourth copolymer 10 10 10 10 fifth copolymer - 10 15 - 6th copolymer ECOZEN T110 - - - 20 ECOZEN T120 - - - -

Experimental example

Specimens were prepared by injecting 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 3 below.

1) Chemical resistance (crack width, μm): A tensile specimen prepared according to ASTM D638 is mounted on an ESCR (Environmental Stress Crack Resistance) jig having a curvature of 2% according to ASTM D1693, and Aroma Naturals (trade name, manufacturer) as a fragrance : Lifetech) was applied and left for 168 hours, then the surface was observed with an optical microscope.

2) Flexural modulus (kgf/cm 2 ): Measured according to ASTM D790.

3) Impact strength (kgf·cm/cm, 1/4"): Measured according to ASTM D256.

4) Heat deformation temperature (°C): Measured according to ASTM D648.

division chemical resistance
(crack width, ㎛) flexural modulus
(kgf/㎠) impact strength
(kgf·cm/cm) heat deflection temperature
(℃) Example 1 < 10 19,000 13 103 Example 2 < 10 18,500 12 102 Example 3 < 10 19,500 13 104 Example 4 < 10 19,000 12 103 Example 5 < 10 17,000 14 99 Example 6 50 19,500 13 104 Comparative Example 1 break 21,000 11 108 Comparative Example 2 break 19,000 13 104 Comparative Example 3 < 10 17,000 15 100 Comparative Example 4 break 20,000 12 104

Referring to Table 3, in the case of Examples 1 to 4, it was confirmed that the chemical resistance was excellent, the flexural modulus, the impact strength, and the thermal deformation temperature were all excellent.

In the case of Example 5 containing a small amount of the third copolymer and an excessive amount of the sixth copolymer, it was confirmed that the chemical resistance was excellent, but the flexural modulus and the thermal deformation temperature were low. In the case of Example 6 containing a small amount of the sixth copolymer, it was confirmed that the chemical resistance was lowered.

In the case of Comparative Example 1, since the fifth and sixth copolymers were not included, it was confirmed that chemical resistance and impact strength were lowered.

In the case of Comparative Example 2, since the sixth copolymer was not included, it was confirmed that the chemical resistance was not excellent.

In the case of Comparative Example 3, although the sixth copolymer was not included, since the fifth copolymer was included in excess, it was confirmed that the chemical resistance was excellent, but the flexural modulus was lowered.

In the case of Comparative Example 4, since the fifth copolymer was not included, it was confirmed that chemical resistance was lowered.

From the results of Examples 5, 6, and Comparative Examples 1 to 4, the first to sixth copolymers must be included in an appropriate amount as well as chemical resistance, flexural modulus, impact strength and thermal deformation temperature. It was confirmed that all of the excellent thermoplastic resin compositions can be prepared.

Claims (14)

15 to 25 wt% of a first copolymer comprising an alkyl (meth)acrylate-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit;
10 to 15 wt% of a second copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit;
40 to 45 wt% of a third copolymer comprising an aromatic vinyl-based monomer and a vinyl cyan-based monomer;
10 to 15% by weight of a fourth copolymer including a maleimide-based monomer-derived unit, an aromatic vinyl-based monomer-derived unit and a maleic acid-based monomer-derived unit;
10 to 15 wt% of a fifth copolymer comprising a thermoplastic polyester elastomer comprising 1,4-benzenedicarboxylic acid-derived units and 1,4-butadiol-derived units; and
5 to 10 wt% of a sixth copolymer comprising a unit derived from 1,4-benzenedicarboxylic acid, a unit derived from dianhydrohexitol, a unit derived from 1,4-cyclohexanedimethanol, and a unit derived from ethylene glycol A thermoplastic resin composition comprising a.
The method according to claim 1,
The alkyl (meth) acrylate-based polymer has an average particle diameter of 0.3 to 0.6㎛ thermoplastic resin composition.
The method according to claim 1,
The conjugated diene-based polymer has an average particle diameter of 1 to 8㎛ thermoplastic resin composition.
The method according to claim 1,
The third copolymer has a glass transition temperature of 110 to 135 ℃ thermoplastic resin composition.
The method according to claim 1,
The fourth copolymer is a thermoplastic resin composition having a glass transition temperature of 185 to 210 °C.
The method according to claim 1,
The fifth copolymer is a thermoplastic resin composition comprising the 1,4-benzenedicarboxylic acid-derived unit and the 1,4-butadiol-derived unit in a weight ratio of 90:10 to 60:40.
The method according to claim 1,
The fifth copolymer is a thermoplastic resin composition having a melt index (230° C., 2.16 kg) of 2 to 10 g/10 min according to ASTM D570.
The method according to claim 1,
The sixth copolymer is
With respect to the total weight of the sixth copolymer,
40 to 80% by weight of the 1,4-benzenedicarboxylic acid-derived unit;
1 to 35% by weight of the 1,4-cyclohexanedimethanol-derived unit;
1 to 35% by weight of the dianhydrohexitol-derived unit; and
The thermoplastic resin composition comprising 0.1 to 25% by weight of the ethylene glycol-derived unit.
The method according to claim 1,
The sixth copolymer has a weight average molecular weight of 30,000 to 80,000 g/mol of a thermoplastic resin composition.
The method according to claim 1,
The sixth copolymer is a thermoplastic resin composition having a flexural modulus (1.27 mm/min) of 20,000 to 24,000 kgf/cm 2 according to ASTM D790.
The method according to claim 1,
The sixth copolymer is a thermoplastic resin composition having a heat deflection temperature of 95 to 135°C according to ASTM D648.
delete delete It is prepared from the thermoplastic resin composition according to any one of claims 1 to 11,
Flexural modulus according to ASTM D790 is 18,000 to 21,000 kgf / ㎠,
A thermoplastic resin molded article having a crack width of less than 10㎛ in ESCR evaluation according to ASTM D1693.