KR102260892B1 - Thermoplastic resin composition - Google Patents

Abstract

The present invention provides a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a first copolymer comprising a vinyl cyan-based monomer-derived unit; a second copolymer comprising a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyanide-based monomer; And it provides a thermoplastic resin composition comprising an additive comprising at least one selected from the group consisting of polyether amines and aromatic polyamides.

Description

Thermoplastic resin composition {THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition having excellent odor improvement effect.

Due to the issue of indoor air quality management in automobiles, the need for odor quality of vehicle materials is emerging. According to the VDA270 standard, odor evaluation grades are judged from room temperature to high temperature depending on automotive application parts.

In general, in the case of an ABS-based graft copolymer prepared by bulk polymerization, it has superior odor properties compared to ABS-based graft copolymers prepared by emulsion polymerization or suspension polymerization, but since a continuous polymerization process is applied, it is difficult to produce various products. has limitations.

Therefore, it is inevitable to apply the ABS-based graft copolymer prepared by emulsion polymerization or suspension polymerization, and various methods have been proposed to improve the smell of the product.

In CN103772884A, a method of applying water or various recycled resins has been proposed. In US2010-0029824A, a method of applying a porous inorganic material such as zeolite to reduce residual monomer has been proposed. WO 2014-208965A proposes a method for reducing impurities through wet extrusion.

However, since it is often difficult to obtain the level of odor required by the VDA270 standard only by reducing impurities, a new method for reducing odor is required.

In order to minimize the odor, there is an effort to apply a fragrance or a deodorant, but in this case, it is difficult to achieve a desired odor effect due to high extrusion and injection temperatures.

CN103772884A

In the case of the graft copolymer prepared by bulk polymerization, the odor reduction effect is excellent, but there is a limit to its application to various products. However, the graft copolymer prepared by emulsion polymerization or suspension polymerization can be applied to various products, but has a disadvantage in that it has a strong odor.

It is an object of the present invention to provide a thermoplastic resin composition in which basic physical properties are not reduced while odor is reduced even when a graft copolymer prepared by emulsion polymerization or suspension polymerization is used.

In order to solve the above problems, the present invention provides a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a first copolymer comprising a vinyl cyan-based monomer-derived unit; a second copolymer comprising a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyanide-based monomer; Provided is a thermoplastic resin composition comprising an additive comprising at least one selected from the group consisting of polyether amines and aromatic polyamides.

When the thermoplastic resin composition according to the present invention is used, it is possible to manufacture an injection-molded article with reduced odor while not lowering basic properties.

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 volume accumulation in the particle size distribution curve of the particles.

In the present invention, the average particle diameter can be measured by TEM.

In the present invention, the weight average molecular weight can be measured as a relative value with respect 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 including a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit; 2. A second copolymer comprising a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyan-based monomer; and 3. an additive comprising at least one selected from the group consisting of polyether amines and aromatic polyamides.

The thermoplastic resin composition according to an embodiment of the present invention includes 4. a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit, and the average particle diameter of the first copolymer and the conjugated diene-based polymer is each other It may further include another third copolymer.

The thermoplastic resin composition according to an embodiment of the present invention may further include 5. a fourth copolymer including a maleimide-based monomer-derived unit and an aromatic vinyl-based monomer-derived unit.

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

1. First copolymer

The first 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.

The first copolymer may impart excellent chemical resistance and impact 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.

Here, 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 0.20 to 0.5 μm, 0.25 to 0.4 μm, or 0.30 to 0.35 μm, of which 0.30 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 conjugated diene-based polymer may be included in an amount of 45 to 70 wt%, 50 to 65 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 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, a styrene-derived unit is preferable.

The aromatic vinyl-based monomer-derived unit may be included in an amount of 25 to 40 wt%, 20 to 35 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 25 wt%, 5 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, chemical resistance, rigidity, impact resistance, processability and surface gloss of the thermoplastic resin composition may be further improved.

The first copolymer may be prepared by polymerizing an aromatic vinyl-based monomer and a vinyl cyanide-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.

2. Second copolymer

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. Among them, styrene-derived units are preferable in view of mechanical properties, and α-methyl styrene-derived units are preferred in view of heat resistance.

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 80:20 to 60:40 or 78:22 to 66:34, of which 78:22 to It is preferable to include it in a weight ratio of 66:34. When the above-mentioned range is satisfied, the thermoplastic resin composition can better balance heat resistance, rigidity, and workability.

The second copolymer preferably has a weight average molecular weight of 110,000 to 180,000 g/mol. When the above-described range is satisfied, there is an advantage in that fluidity and rigidity are excellent.

The weight ratio of the first copolymer to the second copolymer is preferably in the range of 25:75 to 60:40. If the above-mentioned range is satisfied, chemical resistance, impact resistance, thermal stability, colorability, fatigue resistance, rigidity and workability may be further improved.

3. Additives

The additive includes at least one selected from the group consisting of polyether amines and aromatic polyamides.

Since the polyether amine has an excellent effect of removing aldehydes generated during extrusion and injection of the thermoplastic resin composition, it is possible to reduce the odor of the molded article additionally generated when the thermoplastic resin composition is manufactured.

The polyether amine is a material having excellent oxygen removal effect, and since it can minimize oxidation during extrusion and injection of the thermoplastic resin composition, odor caused by oxidation can be minimized.

The polyether amine may be a compound represented by the following formula (1):

<Formula 1>

In Formula 1 above

R ₁ and R ₂ are the same as or different from each other, and are each independently a C ₁ to C ₁₀ alkyl group,

x is 1 to 100.

In Formula 1, x is preferably 20 to 100, more preferably 30 to 70. When the above-mentioned range is satisfied, there is an advantage of being excellent in impact strength and workability.

The compound represented by Formula 1 preferably has a weight average molecular weight of 1,000 to 5,000 g/mol, more preferably 1,500 to 4,500 g/mol. When the above-mentioned range is satisfied, there is an advantage of being excellent in impact strength and workability.

The polyetheramine may be a compound represented by Formula 2:

<Formula 2>

In Formula 2 above

R ₃ and R ₄ are the same as or different from each other, and are each independently a C ₁ to C ₁₀ alkyl group,

y and z are the same as or different from each other and are each independently 1 to 100.

In Formula 2, y and z are the same as or different from each other, and each independently is preferably 1 to 50, and more preferably 1 to 40. When the above-mentioned range is satisfied, there is an advantage of being excellent in impact strength and workability.

The compound represented by Formula 2 may have a weight average molecular weight of 1,000 to 3,000 g/mol, more preferably 1,500 to 2,500 g/mol. When the above-mentioned range is satisfied, there is an advantage of being excellent in impact strength and workability.

Since the aromatic polyamide has an excellent effect of removing aldehydes generated during extrusion and injection of the thermoplastic resin composition, it is possible to reduce the odor of the molded article additionally generated when the thermoplastic resin composition is manufactured.

The aromatic polyamide may be a compound represented by the following Chemical Formula 3:

<Formula 3>

In Formula 3,

L ₁ to L ₄ are the same as or different from each other, and each independently a C ₁ to C ₁₀ alkylene group or C ₆ to C ₂₀ arylene group, but at least one of _{L 1} to L _{4 is C 6} to C ₂₀ aryl It's Rengi,

n is 10 to 25.

In Formula 3, L ₂ is preferably a C ₆ to C ₂₀ arylene group, and L ₁ , L ₂ and L ₄ are the same as or different from each other _{and each independently a C 1} to C ₄ linear alkylene group. , n is preferably 15 to 22.

If the above conditions are satisfied, there is an advantage in that the impact strength and workability are excellent.

The compound represented by Formula 3 may have a weight average molecular weight of 2,500 to 6,000 g/mol, preferably 4,000 to 5,000 g/mol. When the above-described range is satisfied, there is an advantage in that workability and rigidity are excellent.

The additive may be included in an amount of 0.5 to 5 parts by weight, preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the total of the first copolymer and the second copolymer.

When the above-described range is satisfied, the reduction in impact resistance can be minimized while also implementing the odor reduction effect of the thermoplastic resin composition.

The amount of the additive is limited based on 100 parts by weight of the base resin, and if at least one selected from the group consisting of the third copolymer and the fourth copolymer is further included in the base resin, the first copolymer; a second copolymer; And the content may be limited based on 100 parts by weight of the sum of at least one selected from the group consisting of the third copolymer and the fourth copolymer.

4. Third copolymer

The third copolymer may include a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit, and the average particle diameter of the first copolymer and the conjugated diene-based polymer may be different from each other.

The third copolymer may impart excellent processability properties to the thermoplastic resin composition compared to the first copolymer.

When both the first copolymer having a small average particle diameter of the conjugated diene-based polymer and the third copolymer having a large average particle diameter of the conjugated diene-based polymer are included, both impact resistance and processability of the thermoplastic resin composition may be improved.

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 average particle diameter of the conjugated diene-based polymer is larger than the average particle diameter of the conjugated diene-based polymer of the first copolymer.

The average particle diameter of the conjugated diene-based polymer may be 1 to 2 μm, preferably 1 to 1.8 μm. When the above-mentioned range is satisfied, the mechanical properties of the graft copolymer can be remarkably improved.

The conjugated diene-based polymer may be included in an amount of 5 to 25 wt%, 7 to 20 wt%, or 10 to 18 wt%, based on the total weight of the third copolymer, of which 10 to 18 wt% is preferable. Do. When the above-described range is satisfied, mechanical properties, chemical resistance, and processability 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 55 to 85 wt%, 60 to 75 wt%, or 65 to 70 wt%, based on the total weight of the third copolymer, of which 65 to 70 wt% it is preferable When the above-described range is satisfied, the processability and moldability 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, and dual acrylonitrile-derived units is preferable

The vinyl cyan-based monomer-derived unit may be included in an amount of 5 to 30 wt%, 10 to 25 wt%, or 15 to 20 wt%, based on the total weight of the third copolymer, of which 15 to 20 wt% it is preferable When the above-described range is satisfied, the chemical resistance of the thermoplastic resin composition may be improved.

The third copolymer may be included in an amount of 70 parts by weight or less, 50 to 70 parts by weight based on 100 parts by weight of the total of the first and second copolymers. When the above-mentioned range is satisfied, the impact resistance of the thermoplastic resin composition can be further improved.

5. Fourth copolymer

The fourth copolymer may include a unit derived from a maleimide-based monomer and a unit derived from an aromatic vinyl-based polymer.

The fourth 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, of which the styrene polymer is derived from units are preferred.

The fourth 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 fourth copolymer may be further improved.

The fourth copolymer may further include a maleic acid-based monomer-derived unit, and the maleic acid-based monomer may be a by-product generated when the maleimide-based monomer and the aromatic vinyl-based polymer are melt-polymerized.

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. When the above-described range is satisfied, there is an advantage in that the impact resistance and workability are excellent.

The fourth copolymer may be included in an amount of 60 parts by weight or less, 20 to 60 parts by weight, based on 100 parts by weight of the total of the first and second copolymers. When the above-mentioned range is satisfied, the heat resistance of the thermoplastic resin composition can be further improved.

If the third and fourth copolymers are further added, with respect to the total weight of the first to fourth copolymers, 10 to 35% by weight of the first copolymer, 10 to 35% by weight of the second copolymer, and 20 to 45% by weight of the third copolymer and 15 to 40% by weight of the fourth copolymer may be added.

Preferably, based on the total weight of the first to fourth copolymers, 15 to 30% by weight of the first copolymer, 15 to 30% by weight of the second copolymer, 25 to 40% by weight of the third copolymer, and 20 to 35% by weight of the fourth copolymer may be added.

More preferably, based on the total weight of the first to fourth copolymers, 20 to 25% by weight of the first copolymer, 20 to 25% by weight of the second copolymer, 30 to 35% by weight of the third copolymer and 25 to 30% by weight of the fourth copolymer.

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 and fourth copolymers may be a base resin of the thermoplastic resin composition.

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.

<Thermoplastic resin composition>

Example 1 to Example 5

DP270 (brand name, manufacturer: LG Chem) as the first copolymer, 92HR (product name, manufacturer: LG Chem) as the second copolymer, ER400H (brand name, manufacturer: LG Chem) as the third copolymer, and the fourth copolymer PMI-PS copolymer (trade name: MSNB, manufacturer: DENKA), polyether amine (trade name: Jeffamine D-2000, manufacturer: Huntsman) or aromatic polyamide (trade name: Polyamide MXD6 S6007, manufacturer: Mistubishi Gas Chemical) as an additive The content shown in Table 1 was put into the Henschel mixer, and after mixing them uniformly, the mixture was put into a twin-screw extruder set at the temperature shown in Table 1 below, and then a thermoplastic resin composition in the form of pellets was prepared.

division Example 1 Example 2 Example 3 Example 4 Example 5 base resin first copolymer DP270 30 30 20 30 30 second copolymer 92HR 70 70 25 70 70 tertiary copolymer ER400H 30 fourth copolymer NSNB - - 25 - - additive aromatic polyamide S6007 0.5 2.0 4 - - polyether
amine D2000 - - - 0.5 2.0 Extrusion temperature (℃) 230 230 250 230 230

comparative example One

A thermoplastic resin composition was prepared in the same manner as in Example 1, except that aromatic polyamide and polyetheramine were not added.

Experimental example

The thermoplastic resin compositions of Examples and Comparative Examples were injected, and physical properties were evaluated in the following manner, and the results are shown in Table 2 below.

1) Odor evaluation: After sealing the molded product of 90 mm × 200 mm in a 3L container, it was stored in an oven at 80° C. for 2 hours. After cooling for 1 hour, the odor was evaluated according to VDA270. There are grades 1 to 6, and the lower the grade, the better the odor characteristic.

2) Impact strength (kg·cm/cm): It was measured with a 1/4" notched specimen according to ASTM D256.

3) HDT (°C): According to ASTM D648-7, it was measured under 1/4″, 18.6 kgf, 120°C/hr conditions.

division Odor evaluation impact strength heat deflection temperature Example 1 3rd grade 32 88 Example 2 3rd grade 31 88 Example 3 3rd grade 32 88 Example 4 3rd grade 31 88 Example 5 3rd grade 18 105 Comparative Example 1 4th grade 32 88

Referring to Table 2, it was confirmed that Examples 1 to 5 had superior odor grades compared to Comparative Example 1, and the impact strength and heat deflection temperature were equivalent. That is, it was confirmed that the polyether amine and aromatic polyamide used as additives improved the odor grade without reducing basic physical properties.

Claims (12)

a first copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit;
a second copolymer comprising a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyanide-based monomer; and
an additive comprising a polyether amine;
The polyester amine is a thermoplastic resin composition which is a compound represented by the following Chemical Formula 1 or Chemical Formula 2:
<Formula 1>

<Formula 2>

In Formula 1 and Formula 2,
R ₁ to R ₄ are the same as or different from each other, and each independently a C ₁ to C ₁₀ alkyl group,
x, y and z are the same as or different from each other, and each independently is 1 to 100.
delete The method according to claim 1,
In Formula 1, x is 20 to 100 of the thermoplastic resin composition.
The method according to claim 1,
The compound represented by Formula 1 is a thermoplastic resin composition having a weight average molecular weight of 1,000 to 5,000 g/mol.
The method according to claim 1,
In Formula 2, y and z are the same as or different from each other, and each independently, 1 to 50 of the thermoplastic resin composition.
The method according to claim 1,
The compound represented by Formula 2 has a weight average molecular weight of 1,000 to 3,000 g/mol of a thermoplastic resin composition.
delete delete delete The method according to claim 1,
Based on 100 parts by weight of the sum of the first copolymer and the second copolymer,
The thermoplastic resin composition comprising the additive in an amount of 0.5 to 5 parts by weight.
The method according to claim 1,
The thermoplastic resin composition further comprises a third copolymer,
The third copolymer includes a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit,
The thermoplastic resin composition of the first copolymer and the average particle diameter of the conjugated diene-based polymer is different from each other.
The method according to claim 1,
The thermoplastic resin composition further comprises a fourth copolymer,
The fourth copolymer is a thermoplastic resin composition comprising a unit derived from a maleimide-based monomer and a unit derived from an aromatic vinyl-based polymer.