WO2019132304A2 - Thermoplastic resin composition and molded product using same - Google Patents

Abstract

The present disclosure relates to a thermoplastic resin composition containing (A) 60-85 wt% of a (meth)acryl-based resin, (B) 10-30 wt% of an acryl-based graft copolymer, and (C) 5-10 wt% of a maleimide-based heat-resistant copolymer, and to a molded product using the same.

Description

Thermoplastic resin composition and molded article using the same

The present invention relates to a thermoplastic resin composition and a molded article using the same.

Due to the eco-friendly trend, the demand for unpainted materials for automobile exterior materials is on the rise. In addition, as the required level of heat resistance of the unpainted material also increases, it is also possible to use an acrylonitrile-styrene-acrylate copolymer (ASA) / polymethyl methacrylate (PMMA) alloy material excellent in coloring property and heat resistance Has been developed.

However, the impact strength and heat resistance of the acrylonitrile-styrene-acrylate copolymer are low compared to the acrylonitrile-styrene-acrylate copolymer used as a conventional exterior material due to the properties of the polymethylmethacrylate material. When a heat- There is a disadvantage in that transparency is reduced while causing a difference in refractive index between polymethyl methacrylate (PMMA) and styrene-acrylonitrile-styrene-acrylate copolymer (ASA) and polymethylmethacrylate (PMMA), which leads to reduction in colorability and a large amount of colorant.

Therefore, research on a thermoplastic resin composition having excellent heat resistance and coloring property is required.

To provide a thermoplastic resin composition capable of realizing excellent impact resistance, coloring property and heat resistance, and a molded article using the same.

(A) 60 to 85% by weight of a (meth) acrylic resin, (B) 10 to 30% by weight of an acrylic graft copolymer, and (C) 5 to 10% by weight of a maleimide- And a thermoplastic resin composition.

Another embodiment provides a molded article using the above-mentioned thermoplastic resin composition.

The thermoplastic resin composition according to one embodiment makes it possible to produce a molded article having excellent impact resistance, coloring property and heat resistance.

Hereinafter, embodiments of the present invention will be described in detail. In the following description of the present invention, the well-known functions or constructions will not be described in order to clarify the present invention.

The thermoplastic resin composition according to one embodiment of the present invention comprises 60 to 85% by weight of (A) a (meth) acrylic resin, 10 to 30% by weight of an acrylic graft copolymer (B), and (C) a maleimide- 5 to 10% by weight.

(A) a (meth) acrylic resin

The (A) (meth) acrylic resin is excellent in coloring property so that the thermoplastic resin composition according to one embodiment can be applied to unpainted materials.

In addition, the (A) (meth) acrylic resin has a glass transition temperature (Tg) of 110 ° C or more, which can improve the heat resistance characteristics of the thermoplastic resin composition. The glass transition temperature of the (A) (meth) acrylic resin may be, for example, from 110 to 130 ° C, for example, from 110 to 125 ° C, for example, have. Within this range, the flowability of the thermoplastic resin composition can be enhanced, compatibility with other components and stress applied during processing can be reduced, and the heat resistance and colorability of the thermoplastic resin composition can be improved.

The (A) (meth) acrylic resin may have a weight average molecular weight of 50,000 to 300,000 g / mol. For example, the (A) (meth) acrylic resin may have a weight average molecular weight of 70,000 to 250,000 g / mol, for example, 100,000 to 200,000 g / mol. Within this range, compatibility with other components is excellent, and the fluidity and moldability of the thermoplastic resin composition can be improved.

The (A) (meth) acrylic resin may be a polymer of a (meth) acrylate-based monomer containing a C1 to C10 alkyl group. When the (A) (meth) acrylic resin is a polymer of a (meth) acrylate monomer, the compatibility with other constituents, the flowability of the thermoplastic resin composition and the molding processability can be further improved.

The (A) (meth) acrylic resin may be, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl (meth) acrylate, hexyl acrylate, Acrylate, n-pentyl acrylate, vinyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate And lauryl methacrylate. The term " (meth) acrylate monomer "

For example, the (A) (meth) acrylic resin may be polymethyl methacrylate (PMMA).

The (A) (meth) acrylic resin can be prepared by conventional bulk, emulsion or suspension polymerization methods using the above-described monomers using a solvent and a polymerization initiator, and is not limited to these methods. Examples of the solvent include methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propyleneglycol monomethyl ether acetate, methylcellosolve acetate, ethylcellosolve acetate, diethylene glycol monomethyl ether, di Ethers such as ethylene glycol monoethyl ether, and combinations thereof. Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy 2, 4-dimethylvaleronitrile) and the like can be used.

The (A) (meth) acrylic resin may be contained in an amount of 60 to 85% by weight based on the total weight of the components (A) to (C). Within the above range, the thermoplastic resin composition according to one embodiment has an advantage that the balance of physical properties of fluidity, impact resistance and heat resistance is excellent, and heat resistance and coloring property are improved.

(B) an acryl-based graft copolymer

The (B) acrylic graft copolymer can be prepared by graft-polymerizing an acrylic rubber-like polymer with a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound.

As the above-mentioned polymerization method, usual production methods such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization can be used.

The acrylic rubber-like polymer may be an alkyl acrylate rubber, preferably a C2 to C10 alkyl acrylate rubber. For example, butyl acrylate rubber, ethylhexyl acrylate rubber and mixtures thereof can be used, but are not necessarily limited thereto.

The acrylic rubber-like polymer may be contained in an amount of 40 to 65% by weight (based on the solid content) based on the total weight of the acrylic graft copolymer (B). At this time, the average particle diameter of the acrylic rubber-like polymer may be 150 to 400 nm. For example, the average particle size of the acrylic rubber-like polymer may be from 150 to 400 nm, for example, from 200 to 400 nm, for example, from 300 to 400 nm.

The average particle diameter is a volume average diameter, which means a Z-average particle diameter measured using a dynamic light scattering analyzer.

The copolymer of the aromatic vinyl compound and the vinyl cyanide compound graft-polymerized to the rubbery polymer may be an aromatic vinyl compound and a vinyl cyanide compound copolymerized in a weight ratio of 6: 4 to 8: 2.

Examples of the aromatic vinyl compound include styrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene and vinylnaphthalene. These aromatic vinyl compounds may be used alone or in combination . In one embodiment of these, styrene is preferably used.

Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, and fumaronitrile, which may be used alone or in combination. Acrylonitrile may preferably be used in one of these embodiments.

The (B) acrylic graft copolymer may be, for example, an acrylonitrile-styrene-acrylate graft copolymer (g-ASA).

The acrylonitrile-styrene-acrylate graft copolymer may be prepared by graft copolymerization of an alkyl acrylate rubber with acrylonitrile and styrene to an alkyl acrylate rubber.

The acrylic graft copolymer (B) may be contained in an amount of 10 to 30% by weight based on the total weight of the components (A) to (C). Within the above range, the impact resistance, heat resistance and coloring property of the thermoplastic resin composition according to one embodiment can be improved.

(C) a maleimide-based heat-resistant copolymer

The thermoplastic resin composition may include (C) a maleimide-based heat-resistant copolymer. The (C) maleimide-based heat-resistant copolymer may be, for example, a N-phenyl maleimide (PMI) based copolymer. The (C) maleimide-based heat-resistant copolymer may be added to further improve the heat resistance of the thermoplastic resin composition.

The (C) maleimide-based heat-resistant copolymer may be a terpolymer of N-phenylmaleimide, styrene and maleic anhydride. When the component derived from N-phenylmaleimide is included, the heat resistance of the thermoplastic resin composition can be further improved, and if it contains a component derived from styrene and maleic anhydride, the colorability of the thermoplastic resin composition can be improved .

According to one embodiment, the terpolymer of N-phenylmaleimide, maleic anhydride and styrene can be prepared through imidization of styrene and maleic anhydride copolymer, and the (C) maleimide-based heat resistant air Based on the total weight of the maleimide-based heat-resistant copolymer, 15 to 25% by weight of the component derived from the N-phenylmaleimide, 65 to 75% by weight of the component derived from the styrene, Component may be a copolymer of 5 to 10% by weight. Within the above range, the heat resistance of the thermoplastic resin composition can be uniformly improved, and the decrease in coloring property can be minimized.

The glass transition temperature (Tg) of the (C) maleimide-based heat-resistant copolymer may be 150 ° C to 220 ° C. For example, the glass transition temperature (Tg) of the (C) maleimide-based heat-resistant copolymer may be 160 ° C to 200 ° C, for example, 180 ° C to 200 ° C.

The weight average molecular weight of the (C) maleimide-based heat-resistant copolymer may be 80,000 to 200,000 g / mol. For example, the weight average molecular weight of the (C) maleimide-based heat-resistant copolymer may be 100,000 to 180,000 g / mol, for example, 130,000 to 160,000 g / mol.

The (C) maleimide-based heat-resistant copolymer has an advantage of exhibiting excellent heat resistance and coloring property in the range of the glass transition temperature and the weight average molecular weight, and has excellent extrusion processability and fluidity.

The (C) maleimide-based heat-resistant copolymer may be contained in an amount of 5 to 10% by weight based on the total weight of the components (A) to (C). When the (C) maleimide-based heat-resistant copolymer is contained in the above range, the heat resistance and coloring property of the thermoplastic resin composition can be improved evenly.

(D) Other additives

The thermoplastic resin composition may further comprise one or more other additives in order to balance physical properties or, depending on the needs of the end use. Specific examples of the additives include flame retardants, surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, antioxidants, inorganic additives, colorants, lubricants, antistatic agents, pigments, A heat stabilizer, a UV stabilizer, an ultraviolet screening agent, a nucleating agent, an adhesive, and the like may be used alone or in combination of two or more.

The other additives may be appropriately contained within a range that does not impair the physical properties of the thermoplastic resin composition and specifically may be included in an amount of 50 parts by weight or less based on 100 parts by weight of the components (A) to (C) 0.1 part by weight to 30 parts by weight.

The above-mentioned thermoplastic resin composition can be produced by a known production method. For example, the components and other additives according to one embodiment may be simultaneously mixed and then melted / kneaded in an extruder to form a pellet.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples and comparative examples are for illustrative purposes only and are not intended to limit the present invention.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

Examples 1 to 5 and Comparative Examples 1 to 8

The thermoplastic resin compositions of Examples 1 to 5 and Comparative Examples 1 to 8 were produced in accordance with the ingredient content ratios described in Table 1 below.

In Table 1, the components (A), (B) and (C) of the thermoplastic resin composition are expressed as% by weight based on the total weight of the components (A) to (C).

0.3 parts by weight of a hindered phenol type heat stabilizer, 0.02 parts by weight of a silicone-based impact modifier as other additive, 100 parts by weight of a silicone-based impact modifier, 100 parts by weight of the components (A) to (C) And 0.8 part by weight of a HALS-based ultraviolet stabilizer, respectively, followed by melting / kneading to prepare pellets. Extrusion was carried out using a twin-screw extruder having an L / D of 29 and a diameter of 45 mm, and the barrel temperature was set at 230 ° C.

The prepared pellets were dried at 80 ° C for 4 hours, and then a specimen for measurement of physical properties and a specimen of 100 mm × 100 mm × 3.2 mm size were prepared. At this time, a 6 oz injection molding machine was used, and the cylinder temperature was set at 220 ° C and the mold temperature was set at 60 ° C.

		Example					Comparative Example
		One	2	3	4	5	One	2	3	4	5	6	7	8
(A) a (meth) acrylic resin	PMMA	65	64	63	62	61	70	68	66	64	62	68	60	58
(B) an acryl-based graft copolymer	g-ASA	30	30	30	30	30	30	30	30	30	30	30	30	30
(C) a maleimide-based heat-resistant copolymer	PMI-MAH-SM (C)	5	6	7	8	9	-	-	-	-	-	2	10	12
	PMI-MAH-SM (C ')	-	-	-	-	-	-	2	4	6	8	-	-	-

The configurations shown in Table 1 are as follows. (A) Polymethyl methacrylate resin (manufacturer: Arkema, product name: V40)

A polymethyl methacrylate (PMMA) resin having a glass transition temperature of about 120 占 폚 and a weight average molecular weight of about 100,000 g / mol was used.

(B) Acrylonitrile-styrene-acrylate graft copolymer (Manufacturer: Lotte Hidan Material)

Styrene-acrylate graft copolymer (g-ASA) comprising about 60% by weight of butyl acrylate rubber having an average particle size of about 300 nm, wherein the copolymer of styrene and acrylonitrile is selected from butyl acrylate And a rubber copolymerized at a weight ratio of about 7: 3.

(C) N-phenylmaleimide-maleic anhydride-styrene copolymer (manufacturer: Polyscope, product name: IZ0721M)

N-phenylmaleimide-maleic anhydride-styrene (PMI-MAH-SM) copolymer having a weight average molecular weight of about 150,000 g / mol and a glass transition temperature of about 177 DEG C was used. The copolymer comprises about 21% by weight of the component derived from N-phenylmaleimide, about 7% by weight of the component derived from maleic anhydride, and about 72% by weight of the component derived from styrene.

(C ') N-phenylmaleimide-maleic anhydride-styrene copolymer (manufacturer: Denka, product name: MS-NB)

N-phenylmaleimide-maleic anhydride-styrene (PMI-MAH-SM) copolymer having a weight average molecular weight of about 125,000 g / mol and a glass transition temperature of about 206 ° C was used. The copolymer comprises about 49% by weight of the component derived from N-phenylmaleimide, about 2% by weight of the component derived from maleic anhydride, and about 49% of the component derived from styrene.

Experimental Example

The results of the experiment are shown in Table 2 below.

(1) Colorability (%): The transmittance was measured using a GNH Tech NDH-7000 instrument with a size of 100 mm × 100 mm with a thickness of 3.2 mm. It was determined that the higher the transmittance, the better the colorability because it was transparent.

(2) Impact resistance (kgf · cm / cm): Notched Izod impact strength was measured according to ASTM D256 standard for 1/4 "thick specimens.

(3) Heat resistance (占 폚): Vicat softening temperature (VST) was measured according to ASTM D1525 standard.

	Example					Comparative Example
	One	2	3	4	5	One	2	3	4	5	6	7	8
Transmittance	45.03	43.42	41.86	40.29	39.36	58.17	46.12	35.18	27.83	21.85	52.62	38.02	33.21
Izod impact strength	7.1	7.1	7.2	7.5	7.3	7.3	7.4	6.9	6.7	6.3	7.5	7.0	6.8
VST	99.0	99.1	99.7	100.2	100.5	96.8	98.0	100.4	101.6	103.7	97.7	101.0	101.8

From the above Tables 1 and 2, it can be seen that the thermoplastic resin composition according to the embodiments of the present invention exhibits an Izod impact strength of 7 kgf · cm / cm or more while simultaneously satisfying a VST of 99 ° C or higher and a transmittance of 40% have. Accordingly, by using the (A) (meth) acrylic resin, the (B) acryl-based graft copolymer and the (C) maleimide-based heat resistant copolymer in an optimum amount, an excellent transmittance can be ensured, And a thermoplastic resin composition excellent in heat resistance can be realized.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It is obvious to those who have. Accordingly, it should be understood that such modifications or alterations should not be understood individually from the technical spirit and viewpoint of the present invention, and that modified embodiments fall within the scope of the claims of the present invention.

Claims (14)

1. (A) 60 to 85% by weight of a (meth) acrylic resin;

   (B) 10 to 30% by weight of an acrylic graft copolymer; And

   (C) 5 to 10% by weight of a maleimide-based heat-resistant copolymer.
2. The method of claim 1,

   Wherein the (A) (meth) acrylic resin has a glass transition temperature (Tg) of 110 ° C or more.
3. 3. The method according to claim 1 or 2,

   The (A) (meth) acrylic resin has a weight average molecular weight of 50,000 to 300,000 g / mol.
4. 4. The method according to any one of claims 1 to 3,

   The (A) (meth) acrylic resin is a polymer of a (meth) acrylate monomer containing a C1 to C10 alkyl group.
5. The method of claim 1,

   Wherein the (A) (meth) acrylic resin is polymethyl methacrylate (PMMA).
6. 6. The method according to any one of claims 1 to 5,

   The acrylic graft copolymer (B)

   Based on the total weight of the (B) acrylic graft copolymer,

   And 40 to 65% by weight of an acrylic rubber-like polymer.
7. The method of claim 6,

   Wherein the acrylic rubber-like polymer is an alkyl acrylate-based rubber.
8. 8. The method according to any one of claims 1 to 7,

   The acrylic graft copolymer (B)

   Acrylonitrile-styrene-acrylate graft copolymer (g-ASA).
9. 9. The method according to any one of claims 1 to 8,

   The thermoplastic resin composition (C) is a terpolymer of N-phenylmaleimide, maleic anhydride, and styrene.
10. The method of claim 9,

    The (C) maleimide-based heat-resistant copolymer

    Based on the total weight of the (C) maleimide-based heat-resistant copolymer,

    15 to 25% by weight of a component derived from the N-phenylmaleimide;

    From 65 to 75% by weight of the component derived from the styrene; And

    And 5 to 10% by weight of a component derived from the maleic anhydride.
11. 11. The method according to any one of claims 1 to 10,

    Wherein said thermoplastic copolymer (C) has a glass transition temperature of from 150 캜 to 220 캜.
12. 12. The method according to any one of claims 1 to 11,

    The thermoplastic resin composition (C) has a weight average molecular weight of 80,000 to 200,000 g / mol.
13. A molded article using the thermoplastic resin composition according to any one of claims 1 to 12.
14. The method of claim 13,

    The above-

    A beet softening temperature of 99 ° C or higher;

    A transmittance of 40% or more; And

    An Izod impact strength of at least 7 kgf cm / cm.