KR102164977B1 - Thermoplastic resin composition comprising recycled ABS resin - Google Patents

Abstract

The present invention relates to a thermoplastic resin containing a recycled ABS resin, and more particularly, to a thermoplastic resin composition containing talc, a polyphenylene ether resin, an ionomer, a polyamide, and a flame retardant using recycled ABS as a base resin. About.
The thermoplastic resin composition comprising the recycled ABS resin of the present invention is environmentally friendly, has excellent molding processability, and improves mechanical properties such as flame retardancy and impact strength.

Description

Thermoplastic resin composition comprising recycled ABS resin

The present invention relates to a thermoplastic resin containing a recycled ABS resin, and more particularly, to a thermoplastic resin composition having improved mechanical properties such as tensile strength and moldability at the same time by using recycled ABS as a base resin.

Recently, advanced economies have introduced eco-friendly policies that limit the use of harmful substances that may cause environmental pollution problems and mandate the use of recycled products, and the development of eco-friendly resins is necessary accordingly.

By recycling plastic waste as a raw material for new plastic products without landfilling, it prevents various water and soil pollution caused by landfill, solves the difficulties associated with selecting a landfill, and a huge amount of imported plastic products It can save foreign currency by substituting plastic raw materials.

As a recycling method of plastic waste being attempted in this respect, there is a method of recycling the waste by making it in the form of small pieces and pellets.

On the other hand, the acrylonitrile-butadiene-styrene copolymer resin (ABS resin) is a matrix polymer in which a styrene monomer as an aromatic vinyl compound and an acrylonitrile monomer as a vinyl cyanide compound are grafted to a central butadiene rubber-like polymer. It is dispersed in phosphorus styrene-acrylonitrile copolymer resin (SAN resin).

The ABS resin thus prepared has excellent properties such as processability, impact resistance, strength, and melt strength, and is widely used in various electric, electronic, and miscellaneous goods parts that require a beautiful appearance due to excellent coloring and gloss. However, in the case of the interior and exterior materials of electrical and electronic products subjected to repetitive stress, it is necessary to have excellent impact resistance and to withstand strong chemicals such as acetic acid or industrial oil to some extent because it must withstand without breaking or breaking for a certain period of time. .

Registration Patent No. 10-0937473 describes a method of recycling ABS resin, but when ABS is recycled and used, melt processing characteristics are deteriorated due to aging of the material and mixing of foreign substances. Mechanical properties such as tensile strength were significantly reduced.

In the case of recycled ABS resin, research is needed to develop an optimal recycling method to make a composite material by mixing recycled ABS and additives in order to ensure that injection-molded products have optimal mechanical strength and processability at the same time.

Korean Patent Registration No. 10-0937473

The present invention aims to solve the problems of the prior art as described above, and provides an eco-friendly thermoplastic resin composition containing recycled ABS, having the same mechanical properties and melt processability as existing ABS resins.

An object of the present invention is to provide a thermoplastic resin composition in which processability, flame retardancy and mechanical strength are remarkably improved even when a recycled ABS resin is applied.

The present invention relates to a thermoplastic resin composition comprising a recycled ABS resin, talc, a polyphenylene ether resin, an ionomer, a polyamide, and a flame retardant.

The present invention relates to 100 parts by weight of recycled ABS resin, 10 to 50 parts by weight of talc, 1 to 30 parts by weight of polyphenylene ether resin, 1 to 5 parts by weight of ionomer, 1 to 5 parts by weight of polyamide, and 1 to 5 parts by weight of flame retardant. It relates to a thermoplastic resin composition containing parts by weight.

In addition, the present invention provides a resin molded article using the thermoplastic resin composition.

The thermoplastic resin composition comprising the recycled ABS resin of the present invention is excellent in molding processability, and mechanical properties such as flame retardancy and impact strength are greatly improved.

In particular, the thermoplastic resin composition according to the present invention is eco-friendly and has an effect of lowering the unit cost of the process by using a recycled ABS resin while maintaining the physical properties of the existing ABS resin.

Hereinafter, preferred embodiments and methods for measuring properties of the thermoplastic resin composition of the present invention will be described in detail. The following embodiments are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art. In addition, unless there are other definitions in the technical terms and scientific terms used, they have the meanings commonly understood by those of ordinary skill in the art to which this invention belongs, and the following description will unnecessarily obscure the subject matter of the present invention. Description of possible known functions and configurations will be omitted.

The present invention relates to 100 parts by weight of recycled ABS resin, 10 to 50 parts by weight of talc, 1 to 30 parts by weight of polyphenylene ether resin, 1 to 5 parts by weight of ionomer, 1 to 5 parts by weight of polyamide, and 1 to 5 parts by weight of flame retardant. It provides a thermoplastic resin composition containing parts by weight.

The recycled ABS resin of the present invention refers to a recycled ABS resin obtained by sorting, pulverizing, washing and drying waste plastic parts. The pulverized recycled ABS resin is in the range of 0.1 to 10 mm in diameter, but is not limited thereto.

The ABS resin of the present invention is an acrylonitrile-butadiene-styrene copolymer, has excellent mechanical properties, thermal properties and processability, and can be prepared by various methods such as bulk polymerization, emulsion polymerization, and suspension polymerization.

The ABS resin is a vinyl cyanide compound (eg, acrylonitrile, methacrylonitrile, etc.) in the presence of a diene rubber (eg, polybutadiene, butadiene-styrene copolymer, butadiene-acrylic copolymer, etc.) and As a graft copolymer obtained by polymerizing an aromatic vinyl compound (styrene, alpha-methylstyrene, dimethylstyrene, vinyltoluene, etc.), conventional ABS resins known in the art may be used without limitation.

The recycled ABS resin of the present invention is preferably one having a weight average molecular weight of 15,000 to 300,000 in terms of excellent mechanical properties and molding processability, but is not limited thereto.

The thermoplastic resin composition of the present invention may contain talc to secure excellent heat resistance and mechanical properties. The formula of the talc is Mg ₃ (OH) ₂ Si ₄ O ₁₀ , which means talc, which is magnesium silicate hydrate as a kind of inorganic filler, and talc is preferably in the form of a plate and has an average particle diameter of 0.1 to 10 μm or less. It can be used, but is not limited thereto.

In the present invention, it is preferable to add 10 to 50 parts by weight of talc based on 100 parts by weight of the recycled ABS resin in terms of excellent mechanical properties and workability, but is not limited thereto.

The thermoplastic resin composition of the present invention may include a polyphenylene ether resin (hereinafter abbreviated as PPE) in order to impart heat resistance. PPE uses hindered phenol as a monomer, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2, 6-dipropyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) Ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,6-dimethyl-1,4 -Phenylene) ether and a copolymer of poly(2,3,6-trimethyl-1,4-phenylene) ether, and poly(2,6-diethyl-1,4-phenylene) ether and poly( Any one or two or more compounds selected from the group consisting of copolymers with 2,3,6-trimethyl-1,4-phenylene) ether may be used, and poly(2,6-dimethyl-1,4) -Phenylene)ether can be used.

The degree of polymerization of polyphenylene ether is not particularly limited, but it is preferable that the intrinsic viscosity measured in a chloroform solvent at 25° C. is 0.2 to 0.8 in consideration of thermal stability and workability of the resin composition, but is not limited thereto. The polyphenylene ether may be used alone or may be used by mixing two or more types in an appropriate ratio.

It is preferable that the polyphenylene ether-based resin contains 1 to 30 parts by weight based on 100 parts by weight of the recycled ABS resin because it can exhibit excellent molding processability and impact resistance.

The thermoplastic resin composition of the present invention may contain an ionomer. The ionomer means that a part of the carboxylic acid group of the copolymer of ethylene acrylic acid or ethylene methacrylic acid is substituted with a metal cation. Preferred ionomers used in the present invention include olefin copolymers such as ethylene and zinc. It contains carboxylic acid neutralized with metal ions such as (Zn), sodium (Na), magnesium (Mg) or lithium (Li), and unsaturated carboxylic acids such as acryl or methacryl acid. Copolymer can be used.

Commercially used ionomers include SURLYN 8140 as a grade neutralized by sodium, and SURLYN 9910 as a grade neutralized by zinc, but are not limited thereto.

The blending amount of the ionomer used in the present invention is preferably 1 to 5 parts by weight based on 100 parts by weight of the recycled ABS resin in order to improve interfacial compatibility.

In the present invention, polyamide may be included in order to improve mechanical properties. The blending amount of the polyamide is preferably 1 to 5 parts by weight per 100 parts by weight of the recycled ABS resin in order to exhibit excellent mechanical strength.

The polyamide is, for example, any one or two or more components selected from nylon 4.6, nylon 6, nylon 6.6, nylon 6.10, nylon 7, nylon 8, nylon 9, nylon 11, nylon 12, nylon 46 and amorphous polyamides. It is preferable to include a copolymerized polyamide or a mixture having

In particular, by using the ionomer and polyamide in the recycled ABS resin in the present invention, by overcoming inferior processability and mechanical properties, the cause is unknown but unpredictable as a surprising effect, and the miscibility at the interface can be maximized. As a result, there is an advantage of not only greatly improving workability, but also remarkably increasing mechanical properties.

The thermoplastic resin composition of the present invention may further include any one or two or more flame retardants selected from an aromatic phosphate ester flame retardant of a phenol structure, an ammonium polyphosphate flame retardant, or a pentaerythritol flame retardant.

The phenolic aromatic phosphate ester is triphenyl phosphate and the hindered phenolic aromatic phosphate ester, such as tri(2,6-dimethylphenyl)phosphate, and tri(2,6-ditertiary butylphenyl)phosphate. Although the above phosphate ester may be applied singly or in combination, it is preferable to apply a single phosphate ester, but is not limited thereto, since the application of a compound having a molecular weight of 1500 or more in the structure has little effect of imparting flame retardancy.

The ammonium polyphosphate flame retardant used in the present invention generates only non-flammable gases (water vapor, carbon dioxide, nitrogen, etc.) and carbonaceous residues at the time of decomposition due to high temperature or contact with flames, and prevents the generation of corrosive gases, halogen gases or toxic gases. It has advantages that are not accompanied by most, but specifically, the brand name Budit3076 (manufactured by Budenheim), the brand name SUMISAFE P (manufactured by Sumitomo Chemical Co., Ltd.), and the brand name Exolite 422 (manufactured by Hoechst Co., Ltd.) can be used, but are not limited thereto.

Pentaerythritol may be included as a compound having a polyhydric alcohol group used as a flame retardant in the present invention. This acts as a Char promoter that helps the generation of Char during combustion, and dipentaerythritol or tripentaerythritol may be used to give this role.

In the present invention, the flame retardant is preferably mixed in an amount of 1 to 5 parts by weight based on 100 parts by weight of the recycled ABS resin, and more preferably 1 to 3 parts by weight in the flame retardant synergistic effect.

The composition of the present invention may further include at least one additive selected from the group consisting of a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a lubricant, a release agent, a pigment, an antistatic agent, a dye, a crosslinking agent, and an antibacterial agent, if necessary.

In addition, the present invention can provide a resin molded article made of the thermoplastic resin composition. The resin molded article according to the present invention may have a shape such as a pellet, sheet, film, pipe, tube, fiber, etc., but is not limited thereto.

The method of molding the thermoplastic resin composition of the present invention can use techniques in the art. For example, injection molding, extrusion molding, rotational molding, calendar molding, compression molding, vacuum molding, and hollow molding may be used, but the present invention is not limited thereto.

In the examples and comparative examples of the thermoplastic resin of the present invention, the method of measuring physical properties is described in detail, and the composition of the thermoplastic resin and the measurement results of the properties are shown in Tables 1 and 2 below.

Physical property measurement

1) Izod impact strength: A test piece having a thickness of 3.2 mm was molded using an injection molding machine, and the Izod impact strength ((1/8", 23°C) was measured according to ASTM D256.

2) Tensile strength: Tensile strength was measured according to ASTM D638.

3) Flexural modulus: A specimen having a thickness of 6 mm according to ASTM D790, and was measured at a span of 100 mm and a speed of 10 mm/min.

4) Flame retardancy: It is based on performing the vertical combustion test in the vertical phase (V-0) among the "combustibility test of plastic materials for mechanical parts" of UL Subject 94 (Underrights Laboratories, Inc.). The thickness of the test piece is 1/12 inch.

5) Processability: ○ if no hot spots occurred during processing, △ if less than 1 to 5 occurred, and X if more than 5 occurred.

[Example 1]

After collecting the waste plastic, only the ABS material was recovered. Foreign matter on the surface

It was separated and removed, pulverized to an average size of 3 mm, and washed. The washed waste plastic pulverized product was dried and then extruded to obtain recycled ABS in a pellet state.

As shown in Table 1 below, recycled ABS resin 1 kg, talc 300 g, polyphenylene ether resin (P-401, Asahi Kasei, Japan) 200 g, ionomer (Surlyn 1601, DuPont) 20 g, nylon 6 (ZYTEL 7301, DuPont) 20 g , 20 g of a flame retardant (triphenyl phosphate, TPP, Daihachi, Japan) was stirred in a Henschel mixer for 30 minutes. The mixture was melt-extruded at 200 to 260° C. using an extruder having a diameter of 30 mm to prepare pellets. The obtained pellet was dried at 100° C. for 3 hours and prepared as a test piece for measuring physical properties using an injection molding machine with a maximum cylinder temperature fixed at 230° C., and then the physical properties were measured and the results are shown in Table 2 below. .

[Example 2]

As shown in Table 1 below, it was prepared in the same manner as in Example 1, except that 400 g of talc was added.

[Example 3]

As shown in Table 1 below, it was prepared in the same manner as in Example 1, except that 200 g of talc was added.

[Example 4]

As shown in Table 1 below, it was prepared in the same manner as in Example 1, except that 100 g of a polyphenylene ether resin was added.

[Comparative Example 1]

As shown in Table 1 below, it was prepared in the same manner as in Example 1, except that 700 g of talc was added.

[Comparative Example 2]

As shown in Table 1 below, it was prepared in the same manner as in Example 1, except that only recycled ABS resin and talc were used.

[Comparative Example 3]

As shown in Table 1 below, it was prepared in the same manner as in Example 1, except that only recycled ABS resin, talc, and polyphenylene ether resin were used.

[Comparative Example 4]

As shown in Table 1 below, it was prepared in the same manner as in Example 1, except that a flame retardant was not used.

(unit:
Parts by weight) Play ABS Talc Polyphenylene ether Ionomer Polyamide Flame retardant Example 1 100 30 20 2 2 2 Example 2 100 40 20 2 2 2 Example 3 100 20 20 2 2 2 Example 4 100 30 10 2 2 2 Comparative Example 1 100 70 20 2 2 2 Comparative Example 2 100 30 - - - - Comparative Example 3 100 30 20 - - - Comparative Example 4 100 30 20 2 2 -

Izod impact strength
(kgfcm/cm) The tensile strength
(kgf/㎠) Flexural modulus
(kgf/㎠) Flame retardant
(VO) Processability Example 1 11.3 499 18200 pass ○ Example 2 13.1 548 19410 pass ○ Example 3 10.3 403 17900 pass ○ Example 4 10.7 407 17600 pass ○ Comparative Example 1 6.3 495 16100 pass X Comparative Example 2 6.7 497 15900 Combustion X Comparative Example 3 7.0 495 16200 Combustion X Comparative Example 4 10.7 505 17500 Combustion ○

As shown in Table 2, Comparative Examples 1 to 3 can be seen that the impact strength and workability are significantly inferior to the Example.

Comparative Example 1 using an excessive amount of talc showed a result of poor impact strength and poor workability by using 70 parts by weight of talc.

In addition, it can be seen that the addition of the ionomer and the polyamide improves the miscibility between the resins and suppresses hot spots that may occur during processing, thereby improving the processability.

It can be seen that the thermoplastic resins of Examples 1 to 4 of the present invention exhibit excellent flame retardancy, excellent mechanical strength such as impact strength, tensile strength, and flexural modulus, and very improved workability.

Although the preferred embodiment of the present invention has been described above, it is clear that various changes and equivalents can be used in the present invention, and the same can be applied by appropriately modifying the above embodiment. Therefore, the above description is not intended to limit the scope of the present invention determined by the limits of the following claims.

Claims (7)

10 to 50 parts by weight of talc, 1 to 30 parts by weight of polyphenylene ether resin, 1 to 5 parts by weight of ionomer, 1 to 5 parts by weight of polyamide and 1 to 5 parts by weight of flame retardant,
The talc is talc, which is a plate-shaped magnesium silicate hydrate,
The ionomer is an olefin copolymer containing methacrylic acid or acrylic acid, an agent for improving melt processability of recycled ABS resin. The method of claim 1,
The polyphenylene ether resin is poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2,6-di Propyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether and poly(2,6-diphenyl-1,4-phenylene) ether, selected from any one or two or more of recycled ABS resin melt processability improver . delete The method of claim 1,
The polyamide is any one or two or more selected from nylon 4.6, nylon 6, nylon 6.6, nylon 6.10, nylon 7, nylon 8, nylon 9, nylon 11, nylon 12, nylon 46, and amorphous polyamide. Melt processability improver. The method of claim 1,
The flame retardant is any one or two or more selected from a phenolic aromatic phosphate flame retardant, an ammonium polyphosphate flame retardant, and a pentaerythritol-based flame retardant. The method of claim 1,
A plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a lubricant, a release agent, a pigment, an antistatic agent, a dye, a crosslinking agent, an agent for improving melt processability of a recycled ABS resin further comprising at least one additive selected from the group consisting of an antibacterial agent. delete