KR102308801B1 - Heat-resistant resin composition - Google Patents

Abstract

The present invention relates to a graft copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit; and a zeolite, wherein the zeolite has an average particle diameter of 0.5 to 1.5 μm and an average diameter of an inlet of 7.0 to 8.0 Å. It relates to a heat-resistant resin composition comprising pores.

Description

Heat-resistant resin composition {HEAT-RESISTANT RESIN COMPOSITION}

The present invention relates to a heat-resistant resin composition, and more particularly, to a heat-resistant resin composition having improved odor properties without lowering mechanical properties.

Conventionally, an emulsion-polymerized ABS graft copolymer and a copolymer obtained by polymerization of alpha methyl styrene and acrylonitrile are melt-mixed, or an emulsion-polymerized ABS graft copolymer, and n-phenyl maleimide with styrene and acrylonitrile The polymerized copolymer was melt-mixed to prepare a heat-resistant resin composition.

Conventional heat-resistant resin compositions have excellent impact strength or heat resistance, but there are many residues, so there is a large amount of gas generated during injection, which has a problem in that retention stability is lowered.

In order to improve this, a heat-resistant ABS copolymer has been developed in which the heat resistance of the ABS graft copolymer is improved by the application of a maleimide-based monomer, and the residue is significantly reduced by continuous bulk polymerization.

The heat-resistant ABS copolymer developed as described above has excellent heat resistance and processing characteristics as residues are remarkably reduced, but there is a limit to its application as an interior material for automobiles due to its unique odor.

KR2013-0051823A

An object of the present invention is to provide a heat-resistant resin composition having improved odor properties without deterioration of mechanical properties.

In order to solve the above problems, the present invention is a graft copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit; and a zeolite, wherein the zeolite has an average particle diameter of 0.5 to 1.5 μm, and provides a heat-resistant resin composition comprising pores having an average diameter of an inlet of 7.0 to 8.0 Å.

The heat-resistant resin composition according to the present invention has excellent odor properties and excellent mechanical properties because zeolite can easily adsorb and remove residual monomers in the graft copolymer.

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 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.

In the present invention, the average particle size of the graft copolymer 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.

The average particle diameter of the graft copolymer in the present invention can be measured by dissolving it in MEK (methyl ethyl ketone) using a laser diffraction particle size analyzer (trade name: Laser Diffraction Particle Size Analyzer (LS 13 320), manufacturer: BECKMAN COULTER). .

In the present invention, the average particle diameter of the zeolite can be measured using FE-SEM JSM-7500F (manufacturer: JEOL).

A heat-resistant resin composition according to an embodiment of the present invention comprises: 1. a graft copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit; and 2. zeolite, wherein the zeolite has an average particle diameter of 0.5 to 1.5 μm, and provides a heat-resistant resin composition comprising pores having an average diameter of an inlet of 7.0 to 8.0 Å.

Hereinafter, the description of the components of the heat-resistant resin composition according to an embodiment of the present invention will be described in detail.

One. graft copolymer

The graft copolymer 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 graft copolymer may impart excellent chemical resistance, mechanical properties, and processability to the heat-resistant resin composition.

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

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

The conjugated diene-based polymer may be included in an amount of 5 to 25 wt%, 7 to 20 wt%, or 10 to 15 wt%, based on the total weight of the graft copolymer, of which 10 to 15 wt% is preferable. do. If the above-mentioned range is satisfied, mechanical properties, chemical resistance, processability and surface gloss of the graft 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 80% by weight, 55 to 75% by weight, or 60 to 70% by weight, of which 60 to 70% by weight, based on the total weight of the graft copolymer. it is preferable When the above-described range is satisfied, the processability and moldability of the heat-resistant 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 35 wt%, 10 to 30 wt%, or 15 to 25 wt%, based on the total weight of the graft copolymer, of which 15 to 25 wt% it is preferable When the above-described range is satisfied, the chemical resistance of the heat-resistant resin composition may be improved.

The graft copolymer may have an average particle diameter of 1 to 2 μm, 1 to 1.8 μm, or 1 to 1.5 μm, of which 1 to 1.5 μm is preferable. When the above-mentioned range is satisfied, the mechanical properties of the graft copolymer can be remarkably improved.

The graft copolymer may further include a maleimide-based monomer-derived unit to improve heat resistance.

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 one or more derived units selected from the group consisting of maleimide and N-benzyl maleimide, among which, N-phenylmaleimide-derived units are preferable.

The maleimide-based monomer-derived unit may be included in an amount of 0.1 to 15% by weight, 1 to 10% by weight, or 3 to 7% by weight, based on the total weight of the graft copolymer, of which 3 to 7% by weight is included. desirable. When the above-described range is satisfied, the heat resistance of the graft copolymer can be further improved.

The graft copolymer may have a weight average molecular weight of 180,000 to 210,000 g/mol, 185,000 to 205,000 g/mol, or 190,000 to 200,000 g/mol, of which 190,000 to 200,000 g/mol is preferable. If the above-described range is satisfied, mechanical properties and processability may be further improved.

The graft copolymer may be prepared by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer in one or more methods consisting of suspension polymerization, emulsion polymerization and bulk polymerization in the presence of a conjugated diene-based polymer, of which bulk polymerization It is preferably made with

2. Zeolite

The zeolite has an average particle diameter of 0.5 to 1.5 μm, and includes pores having an average diameter of an inlet of 7.0 to 8.0 Å.

The zeolite preferably has an average particle diameter of 0.8 to 1.2 μm.

When the above-mentioned range is satisfied, the mechanical properties of the heat-resistant resin composition are excellent, and since it has a large surface area, the odor reduction effect can be excellent.

If it is less than the above range, it is difficult to process the zeolite, and it is difficult to control the process such as the zeolite powder flying during the production of the heat-resistant resin composition. Moreover, when it exceeds the above-mentioned range, the mechanical property of a heat-resistant resin composition will fall remarkably.

Here, the inlet of the pore may mean a passage between the surface of the zeolite and the pore.

The zeolite preferably has an average pore inlet diameter of 7.2 to 7.6 Å. Since the above-described average diameter of the inlet is satisfied, residual monomers and odor-causing substances in the graft copolymer can easily move into the zeolite to reduce odor.

The average internal depth of the pores in the zeolite may be 11 to 15 Å, preferably 12 to 14 Å. Since the above-described average depth is satisfied, a large amount of residual monomers of the graft copolymer can be adsorbed, and thus the odor reduction effect can be further improved.

The average internal depth of the pores may mean the internal average diameter of the pores.

On the other hand, since zeolite A has an average pore inlet diameter of 3 to 5 Å, it is difficult for residual monomers in the graft copolymer having a large particle size to move into zeolite A. Accordingly, even if the zeolite A has the same particle size as the zeolite Y, the odor reduction effect is insufficient compared to the zeolite Y.

The zeolite may be zeolite Y having a molar ratio of Si to Al (Si/Al) of 1.6 to 5.0.

Since it satisfies the above-mentioned molar ratio, it exhibits hydrophobicity, and thus, it is possible to adsorb residual monomers and odor-causing substances rather than moisture, so that the odor reduction effect is excellent. It is also stable against acids and heat.

The zeolite may be included in 1 to 3 parts by weight or 2 to 3 parts by weight based on 100 parts by weight of the graft copolymer, and is preferably included in 2 to 3 parts by weight. When the above-mentioned range is satisfied, the content of residual monomers in the graft copolymer can be significantly reduced, so that the odor characteristic is excellent, and the deterioration of the mechanical properties of the heat-resistant resin composition due to zeolite Y can be minimized.

When the heat-resistant resin composition according to an embodiment of the present invention is extruded once, the impact strength (1/4") according to ASTM D256 is 10 kg cm/cm or more, and the content of the residual monomer can be 295 ppm or less. have.

When the above-described impact strength and content of residual monomer are satisfied, both mechanical properties and odor properties may be excellent.

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

Example 1 to Example 5

Heat-resistant ABS graft copolymer (trade name: XR410, manufacturer: LG Chem, Vicat: 101°C) 100 parts by weight of zeolite Y having an average particle diameter of 1.0 μm in a twin-screw extruder set at 240°C with the content shown in Table 1 below (trade name: ZSE 27 MAXX-40D, manufacturer: Leistriz, 28Φ) to prepare a heat-resistant resin composition in a pellet state.

division Example 1 Example 2 Example 3 Example 4 Example 5 Zeolite Y (parts by weight) One 2 3 0.5 4

comparative example One

A heat-resistant resin composition was prepared in the same manner as in Example 1, except that zeolite Y was not used.

comparative example 2

A heat-resistant resin composition was prepared in the same manner as in Example 1, except that zeolite Y was not used and stripping was performed by adding 1 part by weight of water to the side feeder of the extruder during extrusion.

comparative example 3

A heat-resistant resin composition was prepared in the same manner as in Example 1, except that extrusion was performed three times without using zeolite Y.

comparative example 4

100 parts by weight of heat-resistant ABS graft (product name: XR410, manufacturer: LG Chem, Vicat: 101℃), 3 parts by weight of zeolite Y having an average particle diameter of 3.0㎛ twin screw extruder set at 240℃ (product name: ZSE 27 MAXX-40D, manufacturer) : Leistriz, 28Φ) to prepare a heat-resistant resin composition in a pellet state

comparative example 5

A heat-resistant resin composition was prepared in the same manner as in Example 1, except that zeolite A was used instead of zeolite Y.

test example One

The heat-resistant resin compositions of Examples and Comparative Examples were injected and physical properties were measured in the following manner. And, the results are shown in Table 3 below.

1) Impact strength (1/4", kg·cm/cm): Measured by ASTM D256 method. (Izod Impact)

2) Tensile strength (TS, kg/cm2): Measured according to ASTM D638.

3) Heat resistance (HDT, °C): measured according to ASTM D648.

4) Residual monomer (ppm): It was measured as an area ratio using Gel Chromatography (G/C) in the extruded pellets.

5) Odor characteristics: 11 kinds of STD solutions were prepared by adding n-butyl alcohol at the content shown in Table 2 to 1 liter of pure water, and the measurement sample (injection specimen) was kept in an oven at 80° C. for 2 hours based on the odor intensity. The odor grade was measured by comparison. The lower the odor grade, the better the odor characteristic.

Odor grade (grade) Amount of n-butyl alcohol added (ml/ℓ) note 1.0 - not aware 1.5 0.2 2.0 0.6 slightly perceptible 2.5 1.2 3.0 2.4 intensely perceptible 3.5 3.6 4.0 6.0 stinging smell 4.5 9.0 5.0 18.0 5.5 22.7 6.0 100% n-butyl alcohol unbearable

division impact strength tensile strength heat resistance residual monomer odor grade Example 1 11.8 476 95.3 295 3.0~3.5 Example 2 10.9 478 95.7 230 2.5~3.0 Example 3 10.3 480 96.1 198 2.5~3.0 Example 4 11.9 473 94.8 372 3.5~4.0 Example 5 8.4 481 96.4 186 2.5~3.0 Comparative Example 1 12.8 470 94.3 401 3.5~4.0 Comparative Example 2 12.7 471 94.8 285 3.5~4.0 Comparative Example 3 9.3 479 96.4 226 4.0~4.5 Comparative Example 4 7.4 475 95.7 272 3.0~3.5 Comparative Example 5 11.7 478 95.1 352 3.5~4.0

Referring to Table 3, in the case of Examples 1 to 3, the impact strength is 10 kg · cm / cm or more, so the impact resistance is excellent, and since the amount of the residual monomer is 480 ppm or less, the odor grade is 3.5 or less, and for automobiles It was confirmed that it was suitable as an interior material.

In the case of Example 4, in which a small amount of zeolite Y was added, the residual monomer was removed compared to Comparative Example 1, but it was confirmed that it was difficult to use as an interior material for automobiles because the odor grade was 3.5 to 4.0. In the case of Example 5, in which the zeolite Y was added in excess, the amount of residual monomer was significantly reduced, but the impact strength was also reduced, so it was confirmed that it was not suitable as an interior material for automobiles.

In the case of Comparative Example 1 in which zeolite Y was not used, the content of residual monomer was too high and the odor grade was 3.5 to 4.0, so it was not suitable as an interior material for automobiles.

In Comparative Example 2, in which stripping was performed without using zeolite Y, the content of residual monomer was reduced, but zeolite was not present and thus did not adsorb odor-causing substances, so the odor grade was high. Therefore, it was not suitable as an interior material for automobiles.

In Comparative Example 3, in which extrusion was performed three times without using zeolite Y, the content of residual monomer was reduced, but zeolite was not present and thus did not adsorb odor-causing substances, so the odor rating was high. Therefore, it was not suitable as an interior material for automobiles.

In the case of Comparative Example 4, in which zeolite Y having a large average particle diameter was added, residual monomers were reduced and an odor grade of 3.5 or less was realized, but it was confirmed that the impact strength was lowered and thus not suitable as an interior material for automobiles.

In Comparative Example 5, in which zeolite A having a small pore size was added, residual monomers and odor-causing substances were not sufficiently adsorbed, and thus the odor rating was high. Therefore, it was not suitable as an interior material for automobiles.

Claims (9)

a graft copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit; and
Contains 1 to 3 parts by weight of zeolite based on 100 parts by weight of the graft copolymer,
The zeolite has an average particle diameter of 0.5 to 1.5 μm,
A heat-resistant resin composition comprising pores having an average inlet diameter of 7.0 to 8.0 Å.
The method according to claim 1,
The zeolite is a heat-resistant resin composition having a molar ratio of Si to Al (Si/Al) of 1.6 to 5.0.
The method according to claim 1,
The heat-resistant resin composition of the zeolite will have an average internal depth of pores of 11 to 15 Å.
delete The method according to claim 1,
The graft copolymer is
with respect to the total weight,
5 to 25% by weight of the conjugated diene-based polymer;
50 to 80% by weight of the aromatic vinyl-based monomer-derived unit; and
A heat-resistant resin composition comprising 5 to 35 wt% of the vinyl cyan-based monomer-derived unit.
The method according to claim 1,
The heat-resistant resin composition of the graft copolymer further comprising a maleimide-based monomer-derived unit.
7. The method of claim 6,
The graft copolymer is a heat-resistant resin composition comprising 0.1 to 15% by weight of a maleimide-based monomer-derived unit based on the total weight.
The method according to claim 1,
The heat-resistant resin composition of the graft copolymer having an average particle diameter of 1.0 to 2.0 μm.
It is prepared from the heat-resistant resin composition according to any one of claims 1 to 3 and 5 to 8,
A heat-resistant resin molded article having an impact strength (1/4") of 10 kg·cm/cm or more and a residual monomer content of 295 ppm or less according to ASTM D256.