KR20190073995A - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition which includes: a first copolymer which includes an alkyl (meth)acrylate-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyanide monomer-derived unit; a second copolymer which includes a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyanide monomer-derived unit; a third copolymer which includes an aromatic vinyl-based monomer and a vinyl cyanide monomer; a fourth copolymer which includes a maleimide-based monomer-derived unit, an aromatic vinyl-based monomer-derived unit, and a maleic acid-based monomer-derived unit; a fifth copolymer which includes a 1,4-benzene dicarboxylic acid-derived unit and a 1,4-butadiol-derived unit; and a sixth copolymer which includes a 1,4-benzene dicarboxylic acid-derived unit, a dianhydrohexitol-derived unit, a 1,4-cyclohexanedimethanol-derived unit, and an ethylene glycol-derived unit. The thermoplastic resin composition of the present invention is excellent in chemical resistance, impact resistance, heat resistance, and flexural modulus.

Description

[0001] THERMOPLASTIC RESIN COMPOSITION [0002]

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

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

Acrylate-styrene-acrylonitrile copolymer (hereinafter, referred to as 'ASA copolymer') has excellent impact resistance, appearance and workability and has a high heat distortion temperature, The use of such is increasingly expanding.

The thermoplastic resin composition including the ASA copolymer and the ABS copolymer is widely used as a material for automobile exterior materials exposed to sunlight, and the use thereof is also increasing for interior materials requiring some weatherability.

The automobile interior material has a high possibility of contact with various chemicals such as fragrance, deodorant and the like, so that high chemical resistance is required.

However, the conventional thermoplastic resin composition has poor chemical resistance. Especially, when a chemical such as a fragrance, a deodorant, or a fungicide is applied to an automobile air conditioner, cracks are generated in the air vent portion of the automobile. In order to solve this problem, a polyester elastomer was added to a conventional thermoplastic resin composition, but mechanical properties were deteriorated when the polyester elastomer was added in an excessive amount.

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 relates to a first copolymer comprising an alkyl (meth) acrylate-based polymer, an aromatic vinyl-based monomer-derived unit and a vinylcyanide monomer-derived unit; A second copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer-derived unit, and a vinyl cyan monomer-derived unit; A third copolymer comprising an aromatic vinyl monomer and a vinyl cyan monomer; 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; A fifth copolymer comprising a 1,4-benzene dicarboxylic acid-derived unit and a 1,4-butadiol-derived unit; And a sixth copolymer including a unit derived from 1,4-benzene dicarboxylic acid, a unit derived from dianhydrohexitol, a unit derived from 1,4-cyclohexanedimethanol, and an ethylene glycol derived unit To provide a resin composition.

The present invention also relates to a thermoplastic resin molded article made of the above-mentioned thermoplastic resin composition and having a flexural modulus in accordance with ASTM D790 of 18,000 to 21,000 kgf / cm2 and a crack width of less than 10 占 퐉 during ESCR evaluation according to ASTM D1693 to provide.

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

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

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

In the present invention, the average particle diameter can be defined as the particle diameter corresponding to 50% or more of the volume accumulation amount in the particle diameter distribution curve of the particles.

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

In the present invention, the weight average molecular weight can be measured relative to a standard polystyrene (PS) sample through gel permeation chromatography (waters breeze) using THF (tetrahydrofuran) as an eluent.

The thermoplastic resin composition according to one 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 vinylcyanide monomer-derived unit; 2. A second copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer-derived unit and a vinyl cyan monomer-derived unit; 3. A third copolymer comprising an aromatic vinyl monomer and a vinyl cyan 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 a sixth copolymer comprising a unit derived from 1,4-benzene dicarboxylic acid, a unit derived from dianhydrohexitol, a unit derived from 1,4-cyclohexanedimethanol and an ethylene glycol derived unit do.

Hereinafter, the constituent elements of the thermoplastic resin composition according to one 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 can impart excellent impact resistance, appearance, workability, and weatherability to the thermoplastic resin composition.

The alkyl (meth) acrylate-based polymer may include an alkyl acrylate-based polymer in which an alkyl acrylate polymer is modified by graft-polymerizing an aromatic vinyl monomer and a vinyl cyan monomer.

The alkyl (meth) acrylate-based polymer may be prepared by polymerization of an alkyl acrylate-based monomer, in particular, a cross-linking reaction to produce a seed, and the seed and the alkyl acrylate-based monomer are polymerized, .

The alkyl (meth) acrylate monomer may be an alkyl (meth) acrylate of C ₁ to C ₁₀ , and the C ₁ to C ₁₀ alkyl (meth) acrylate may be methyl acrylate, ethyl acrylate, And ethylhexyl acrylate, and among these, butyl acrylate is preferable.

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

The alkyl (meth) acrylate polymer may be contained in an amount of 35 to 65% by weight, 40 to 60% by weight or 45 to 55% by weight based on the total weight of the first copolymer, and 45 to 55% . When the above-mentioned range is satisfied, a molded article made of the thermoplastic resin composition can have better impact resistance.

The aromatic vinyl-based monomer-derived unit may be at least one derived unit selected from the group consisting of styrene,? -Methylstyrene,? -Ethylstyrene, and p-methylstyrene, and styrene-derived units are preferred.

The aromatic vinyl-based monomer-derived unit may be contained in an amount of 25 to 45% by weight, 30 to 40% by weight or 35 to 40% by weight based on the total weight of the first copolymer, and 35 to 40% . When the above-mentioned range is satisfied, the processability of the thermoplastic resin composition is further improved and the appearance characteristics of the molded article made of the thermoplastic resin composition can be further improved.

The unit derived from the vinyl cyan monomer may be at least one derived unit selected from the group consisting of acrylonitrile, methacrylonitrile, phenyl acrylonitrile and? -Chloroacrylonitrile, and the unit derived from acrylonitrile Unit is preferable.

The unit derived from the vinyl cyan monomer may be contained in an amount of 5 to 20% by weight, 10 to 20% by weight or 10 to 15% by weight based on the total weight of the first copolymer, and 10 to 15% . When the above-mentioned range is satisfied, the chemical resistance and weather resistance of the thermoplastic resin composition can 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, and more preferably 140,000 to 200,000 g / mol. When the above-mentioned range is satisfied, the impact resistance of the thermoplastic resin composition can be further improved.

The weight average molecular weight of the first copolymer is determined by the weight average molecular weight of the alkyl acrylate polymer and the weight average molecular weight of the aromatic vinyl monomer-derived unit graft-polymerized to the alkyl acrylate polymer and the vinyl-based monomer- May be the sum of.

The first copolymer is prepared by graft polymerization using at least one polymerization method selected from the group consisting of bulk polymerization, emulsion polymerization and suspension polymerization of an alkyl acrylate type polymer, an aromatic vinyl type monomer and a vinyl cyan type monomer And it is preferable that the polymer is produced by graft polymerization using emulsion polymerization.

The first copolymer may be prepared in an amount of 5 to 35% by weight, 10 to 30% by weight, or 15 to 25% by weight based on the total weight of the thermoplastic resin composition, and preferably 15 to 25% by weight of the first copolymer . When the above-mentioned range is satisfied, excellent impact resistance, appearance, workability, and heat resistance can be imparted to a molded article made of the thermoplastic resin composition.

2. Second copolymer

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

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

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

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

The conjugated diene-based polymer may have an average particle diameter of 1 to 8 占 퐉, 2 to 6 占 퐉, or 3 to 4 占 퐉, preferably 3 to 4 占 퐉. When the above-mentioned range is satisfied, the mechanical properties of the second copolymer can be further improved.

The conjugated diene polymer may be contained 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, preferably 10 to 20% by weight Do. When the above-mentioned range is satisfied, the impact resistance and processability of the second 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,? -Methylstyrene,? -Ethylstyrene, and p-methylstyrene, and styrene-derived units are preferred.

The aromatic vinyl monomer-derived unit may be contained in an amount of 50 to 85% by weight, 55 to 80% by weight or 60 to 75% by weight based on the total weight of the second copolymer, and 60 to 75% by weight thereof . When the above-mentioned range is satisfied, the appearance characteristics of the thermoplastic resin composition can be further improved.

The unit derived from the vinyl cyan monomer may be at least one derived unit selected from the group consisting of acrylonitrile, methacrylonitrile, phenyl acrylonitrile and? -Chloroacrylonitrile, and the unit derived from acrylonitrile Unit is preferable.

The unit derived from the vinyl cyan monomer may be contained 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 10 to 20% by weight thereof desirable. When the above-mentioned range is satisfied, the chemical resistance of the heat-resistant resin composition can be further improved.

The second copolymer may be produced by polymerizing an aromatic vinyl monomer and a vinyl cyan monomer in the presence of a conjugated diene polymer by at least one method selected from the group consisting of emulsion polymerization, suspension polymerization and bulk polymerization, Lt; / RTI > by mass bulk polymerization.

The second copolymer may be prepared in an amount of from 1 to 25% by weight, from 5 to 20% by weight, or from 10 to 15% by weight based on the total weight of the thermoplastic resin composition, and preferably from 10 to 15% by weight . When the above-mentioned range is satisfied, excellent impact resistance, processability and chemical resistance can be imparted 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 vinylcyanide monomer-derived unit.

The third copolymer can impart excellent heat resistance to the thermoplastic resin composition. In addition, it is excellent in compatibility with the second copolymer and 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,? -Methylstyrene,? -Ethylstyrene and p-methylstyrene, and the unit derived from? -Methylstyrene is preferably Do.

The unit derived from the vinyl cyan monomer may be at least one derived unit selected from the group consisting of acrylonitrile, methacrylonitrile, phenyl acrylonitrile and? -Chloroacrylonitrile, and the unit derived from acrylonitrile Unit is preferable.

The third copolymer may contain the aromatic vinyl-based monomer unit and the vinylcyanide monomer-derived unit at a weight ratio of 85:15 to 60:40, 80:20 to 65:35, or 75:25 to 70:30 , And it is preferable that the weight ratio is 75:25 to 70:30. When the above-mentioned range is satisfied, the balance of the 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, and preferably 90,000 to 110,000 g / mol. When the above-mentioned range is satisfied, the balance of the 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, and preferably 120 to 125 ° C. When the above-mentioned conditions are satisfied, the thermoplastic resin composition can be provided with better heat resistance.

The third copolymer may be prepared by polymerizing an aromatic vinyl monomer and a vinyl cyan monomer with at least one method selected from the group consisting of emulsion polymerization, suspension polymerization and bulk polymerization, desirable.

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

4. The fourth copolymer

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

The fourth copolymer can 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, and preferably 190 to 200 ° C. When the above-mentioned range is satisfied, superior heat resistance can be imparted to the thermoplastic resin composition.

The unit derived from the maleimide monomer is at least one selected from the group consisting of maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, Nt N-phenylmaleimide, N-phenylmaleimide, 2-methyl-N-phenylmaleimide, N- (4-chlorophenylmaleimide, (4-hydroxyphenyl) maleimide, N- (4-methoxyphenyl) maleimide, N- (4-nitrophenyl) maleimide, N- ) Maleimide, and N-benzylmaleimide. Of these, units derived from N-phenylmaleimide are preferable.

The maleimide-based monomer-derived unit may comprise 35 to 65% by weight, 40 to 60% by weight or 45 to 55% by weight based on the total weight of the fourth copolymer, and 45 to 55% . When the above range is satisfied, the heat resistance and chemical resistance of the fourth 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,? -Methylstyrene,? -Ethylstyrene, and p-methylstyrene, and styrene-derived units are preferred.

The aromatic vinyl monomer-derived unit may be contained 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, and 40 to 50 wt% desirable. When the above-mentioned range is satisfied, the processability and appearance characteristics of the fourth copolymer can be improved.

The unit derived from the maleic acid monomer may be at least one derived unit selected from the group consisting of maleic anhydride, maleic acid, maleic monoester and maleic diester, Of these, maleic anhydride-derived units are preferred.

The vinyl monomer unit derived from maleic anhydride monomer may be contained in an amount of 0.1 to 10% by weight, 1 to 7% by weight, or 2 to 5% by weight based on the total weight of the fourth copolymer, and 2 to 5% desirable. When the above range is satisfied, the chemical resistance and compatibility with other copolymers can be improved.

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

5. Fifth copolymer

The fifth copolymer is a thermoplastic polyester elastomer including a 1,4-benzene dicarboxylic acid-derived unit and a 1,4-butadiol-derived unit.

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

The fifth copolymer is obtained by copolymerizing the 1,4-benzene dicarboxylic acid-derived unit and the 1,4-butadiol-derived unit in a ratio of 90:10 to 60:40, 80:20 to 60:40, or 70:30 to 60: 40, and preferably 70:30 to 60:40. When the above-mentioned range is satisfied, excellent workability, impact resistance and chemical resistance can be imparted to the thermoplastic resin composition.

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

The fifth copolymer may have a flexural modulus (6.4 mm, 15 mm / min) according to ASTM D790 of 650 to 950 kg / cm 2, 700 to 900 kg / cm 2, or 750 to 850 kg / 850 kg / cm < 2 > is preferable. When the above-mentioned range is satisfied, there is an advantage that the stress acting on the thermoplastic resin composition during ESCR evaluation is reduced to prevent cracking.

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

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

6. The sixth copolymer

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

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

The 1,4-benzene dicarboxylic acid-derived unit may be contained in an amount of 40 to 80% by weight, 45 to 75% by weight or 50 to 70% by weight based on the total weight of the sixth copolymer, By weight to 70% by weight. When included in the above-mentioned range, heat resistance, chemical resistance and weather resistance of the sixth copolymer can be improved.

The unit derived from dianhydrohexitol may be contained 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, and 10 to 25% by weight . When included in the above-mentioned range, heat resistance, chemical resistance and chemical resistance of the sixth copolymer can be improved.

The unit derived from 1,4-cyclohexane dimethanol may be contained 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, By weight. When included in the above-mentioned range, the impact resistance of the sixth copolymer can be improved.

The ethylene glycol-derived unit may be contained in an amount of 0.1 to 25% by weight, 0.5 to 20% by weight or 1 to 15% by weight based on the total weight of the sixth copolymer, and 1 to 15% by weight thereof desirable. When included in the above-mentioned range, the processability of the sixth copolymer can 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, and preferably 50,000 to 60,000 g / mol. When the above-mentioned range is satisfied, the impact resistance and the chemical resistance of the thermoplastic resin composition can be further improved.

The sixth copolymer may have a flexural modulus (1.27 mm / min) according to ASTM D790 of 20,000 to 24,000 kgf / cm 2, 21,000 to 23,000 kgf / cm 2, or 21,700 to 22,200 kgf / To 22,200 kgf / cm < 2 >. When the above-mentioned range is satisfied, the flexural modulus of the thermoplastic resin degraded by the fifth copolymer can be improved.

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

The sixth copolymer may be produced directly or may be 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% by weight, 4 to 15% by weight, or 5 to 10% by weight based on the total weight of the thermoplastic resin composition, and preferably 5 to 10% by weight . When the above range is satisfied, the flexural modulus, rigidity, chemical resistance, and heat resistance of the thermoplastic resin composition can be further improved.

The thermoplastic resin composition according to an embodiment of the present invention may further include an additive, and the additive may be selected from the group consisting of an impact modifier, a heat stabilizer, a dropping inhibitor, an antioxidant, a light stabilizer, a UV- It can be more than a species.

The thermoplastic resin molded article produced from the thermoplastic resin composition according to an embodiment of the present invention has a flexural modulus of 18,000 to 21,000 kgf / cm2 according to ASTM D790 and a crack width of less than 10 mu m in ESCR evaluation based on ASTM D1693. Also, the impact strength according to ASTM D256 is 10 kgf · cm / cm or more. When the above-mentioned numerical values are satisfied, it can 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 skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Manufacturing example  1: Preparation of first copolymer

50 parts by weight of a butyl acrylate polymer having an average particle diameter of 0.45 mu m, 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 Second Copolymer

15 parts by weight of a butadiene 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 tertiary copolymer

70 parts by weight of? -methylstyrene 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

MS-NB (trade name: DENKA) was used as the first copolymer, the copolymer of Preparation Example 2 was used as the second copolymer, the copolymer of Production Example 3 was used as the third copolymer, and the fourth copolymer was used as the first copolymer. ECOZEN T110 (trade name, manufactured by SK Chemical) and ECOZEN T120 (trade name, manufactured by SK Chemicals) as a sixth copolymer were mixed in the same manner as in Example 1, , And the mixture was homogeneously mixed. The mixture was then fed into a twin-screw extruder set at 240 DEG C to prepare a thermoplastic resin composition in the form of a pellet.

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) The first copolymer 20 20 20 20 20 20 The second copolymer 10 10 10 10 10 10 The third copolymer 45 40 45 40 25 47 The fourth copolymer 10 10 10 10 10 10 The fifth copolymer 10 10 10 10 10 10 The sixth 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 the following Table 2, 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 the following Table 2, except that 50 parts by weight of the third copolymer was added and 20 parts by weight of ECOZEN T110 was added as the sixth copolymer without adding the fifth copolymer, The thermoplastic resin composition was prepared in the same manner.

The components and contents of Comparative Examples and Reference Examples are summarized 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) The first copolymer 20 20 20 20 The second copolymer 10 10 10 10 The third copolymer 60 50 40 50 The fourth copolymer 10 10 10 10 The fifth copolymer - 10 15 - The sixth copolymer ECOZEN T110 - - - 20 ECOZEN T120 - - - -

Experimental Example

The thermoplastic resin compositions of Examples and Comparative Examples were injected to prepare specimens, and the properties were evaluated by the methods described below. The results are shown in Table 3 below.

1) Chemical resistance (crack width, 탆): The tensile specimen prepared in accordance with ASTM D638 was mounted on an ESCR (Environmental Stress Crack Resistance) jig having a curvature of 2% according to ASTM D1693, and Aroma Naturals : Life Tech) was applied and left for 168 hours, and the surface was observed with an optical microscope.

2) Flexural modulus (kgf / cm2): Measured according to ASTM D790.

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

4) Heat distortion temperature (占 폚): Measured according to ASTM D648.

division Chemical resistance
(Crack width, 탆) Flexural modulus
(Kgf / cm2) Impact strength
(Kgf · cm / cm) Heat distortion temperature
(° C) 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 Fracture 21,000 11 108 Comparative Example 2 Fracture 19,000 13 104 Comparative Example 3 <10 17,000 15 100 Comparative Example 4 Fracture 20,000 12 104

Referring to Table 3, it was confirmed that Examples 1 to 4 had excellent chemical resistance and excellent flexural modulus, impact strength and heat distortion temperature.

Example 5 having a small amount of the third copolymer and an excessive amount of the sixth copolymer showed excellent chemical resistance but a low flexural modulus and a low heat distortion temperature. 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 the chemical resistance and the impact strength were lowered.

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

In the case of Comparative Example 3, the sixth copolymer was not included. However, since the fifth copolymer contained an excessive amount, the chemical resistance was excellent, but the flexural modulus was decreased.

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

From the results of Example 5, Example 6, and Comparative Examples 1 to 4, it was found that not only all of the first to sixth copolymers were included, but also proper amounts of the first to sixth copolymers were required to have chemical resistance, flexural modulus, impact strength, It is possible to produce a thermoplastic resin composition having excellent properties.

Claims (14)

A first copolymer comprising an alkyl (meth) acrylate-based polymer, an aromatic vinyl-based monomer-derived unit and a vinylcyanide monomer-derived unit;
A second copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer-derived unit, and a vinyl cyan monomer-derived unit;
A third copolymer comprising an aromatic vinyl monomer and a vinyl cyan monomer;
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;
A fifth copolymer comprising a 1,4-benzene dicarboxylic acid-derived unit and a 1,4-butadiol-derived unit; And
A sixth copolymer comprising a 1,4-benzene dicarboxylic acid-derived unit, a dianhydrohexitol-derived unit, a 1,4-cyclohexanedimethanol-derived unit and an ethylene glycol-derived unit Composition.
The method according to claim 1,
Wherein the alkyl (meth) acrylate-based polymer has an average particle diameter of 0.3 to 0.6 占 퐉.
The method according to claim 1,
Wherein the conjugated diene-based polymer has an average particle diameter of 1 to 8 占 퐉.
The method according to claim 1,
Wherein the third copolymer has a glass transition temperature of 110 to 135 占 폚.
The method according to claim 1,
Wherein the fourth copolymer has a glass transition temperature of 185 to 210 占 폚.
The method according to claim 1,
Wherein the fifth copolymer comprises the 1,4-benzene dicarboxylic acid-derived unit and the 1,4-butadiene-derived unit in a weight ratio of 90:10 to 60:40.
The method according to claim 1,
Wherein the fifth copolymer has a melt index (230 DEG C, 2.16 kg) of 2 to 10 g / 10 min according to ASTM D570.
The method according to claim 1,
The sixth copolymer
With respect to the total weight of the sixth copolymer,
40 to 80% by weight of the 1,4-benzene dicarboxylic acid-derived unit;
1 to 35% by weight of the unit derived from 1,4-cyclohexanedimethanol;
1 to 35% by weight of the unit derived from dianhydrohexitol; And
And 0.1 to 25% by weight of the ethylene glycol-derived unit.
The method according to claim 1,
Wherein the sixth copolymer has a weight average molecular weight of 30,000 to 80,000 g / mol.
The method according to claim 1,
Wherein the sixth copolymer has a flexural modulus (1.27 mm / min) according to ASTM D790 of 20,000 to 24,000 kgf / cm2.
The method according to claim 1,
Wherein the sixth copolymer has a thermal deformation temperature of 95 to 135 占 폚 according to ASTM D648.
The method according to claim 1,
The thermoplastic resin composition
With respect to the total weight,
5 to 35% by weight of the first copolymer;
1 to 25% by weight of the second copolymer;
30 to 55% by weight of the third copolymer;
1 to 25% by weight of the fourth copolymer;
1 to 25% by weight of the fifth copolymer; And
And 3 to 20% by weight of the sixth copolymer.
The method of claim 12,
Wherein the sixth copolymer comprises 4 to 15% by weight based on the total weight of the thermoplastic resin composition.
A thermoplastic resin composition which is produced from the thermoplastic resin composition according to any one of claims 1 to 13,
A flexural modulus based on ASTM D790 of 18,000 to 21,000 kgf /
A thermoplastic resin molded article having a crack width of less than 10 mu m in ESCR evaluation according to ASTM D1693.