KR100546792B1 - Flame Retardant Polypropylene Resin Composition comprising Nanoclay Masterbatch - Google Patents

Abstract

The present invention relates to a flame retardant polypropylene resin composition, more specifically, (A) 44 to 78.89% by weight polypropylene resin, (B) 18 to 28% by weight halogen-based flame retardant, (C) 3 to 15% by weight of antimony oxide A flame retardant polypropylene resin composition comprising: (D) 0.1 to 3% by weight of anti-dripping agent, (E) 0.01 to 10% by weight of nanoclay masterbatch, and 0.01 to 5% by weight of compatibilizer, if necessary will be. According to the present invention, it is possible to ensure excellent flame retardancy even when using a smaller amount of halogen-based flame retardant than the prior art, thereby improving the mechanical properties of the resin molded article, less amount of halides generated during incineration of the resin molded article used It is advantageous in terms of the environment, and mass production of the composition is also possible.

 Polypropylene, Nanoclay, Masterbatch, Flame Retardant

Description

Flame Retardant Polypropylene Resin Composition comprising Nanoclay Masterbatch}

The present invention relates to a polypropylene resin composition excellent in flame retardancy, and more particularly, to a polypropylene which is a basic resin, a halogen-based flame retardant, an antimony oxide, an anti-dripping agent, etc., which is a flame retardant component, is added, and a masterbatch nanoclay is added thereto. In addition, the present invention relates to a polypropylene resin composition having excellent flame retardancy and mechanical properties, which is low in environmental pollution and which can be mass produced.

Polypropylene resin is widely used in the fields of household appliances, building materials, interior decoration materials, and automobile parts due to its excellent processing characteristics, chemical resistance, mechanical strength, etc. • Application to electronic components is limited, and studies are being actively conducted to impart flame retardancy to polypropylene resins.

For example, Japanese Patent Laid-Open Publication Nos. 53-92855, 54-29350, 54-77658, 56-26954, 57-87462, and 60-110738 are magnesium hydroxide and aluminum hydroxide. Or a flame retardant polypropylene resin composition using an inorganic flame retardant such as hydrotalcite. However, in the case of the composition prepared by the above technique, an inorganic filler of 50% or more is required in order to obtain a flame retardant grade V-0, so that the workability is remarkably inferior, gas is generated in the product, and the impact strength is also rapidly decreased. have.

On the other hand, Japanese Patent Publication No. 55-30739 discloses a flame retardant polypropylene resin composition using decabromodiphenyl ether and dodecachloro-dodecahydromethanodibenzocyclooctene as a halogen compound which is an organic flame retardant. In addition to the compounds, tetrabromobisphenol A bis- (dibromopropyl ether), bis- (tribromophenoxyethyl) tetrabromobisphenol A ether, hexabromo cyclododecane, tetrabromobisphenol A, etc. are polypropylene. It is known to impart flame retardancy to the resin. However, in order to obtain satisfactory flame retardant properties in all of the above techniques, an excessive flame retardant is required. When an excess halogen-based flame retardant is added to the resin composition, the mechanical properties of the resin deteriorate, and generation of halides in the incineration process of the resin occurs. Increasingly, it is undesirable from an environmental point of view.

In order to solve the above problems, Korean Patent Laid-Open Publication No. 2002-0079005 discloses a resin composition obtained by nanocompositing by applying a lipophilic layered silicate to a polyolefin-based resin. It is not possible, so the value of realization is insufficient.

Therefore, there is a need for an environmentally friendly flame retardant polypropylene resin composition capable of reducing the amount of flame retardants used in conventional flame retardant polypropylene resin compositions and enabling mass production.

The present invention solves the problems of the prior art as described above, using a small amount of halogen-based flame retardant and has excellent flame retardancy, excellent mechanical properties of the resin and less amount of toxic gas generated during incineration, environmentally friendly polypropylene It is an object to provide a resin composition.

One aspect of the present invention for this purpose is (A) 44 to 78.89% by weight of polypropylene resin, (B) 18 to 28% by weight of halogen-based flame retardant, (C) 3 to 15% by weight of antimony oxide, (D) 0.1 to Dripping inhibitor It relates to a polypropylene resin composition comprising 3% by weight, (E) 0.01 to 10% by weight of a nanoclay masterbatch, and optionally (F) 0.01 to 5% by weight of a compatibilizer.

Hereinafter, the polypropylene resin composition of this invention is demonstrated in detail.

The polypropylene resin as component (A) of the present invention is a crystalline polypropylene homopolymer or ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene, 1-heptene, 1-octene and 1- A crystalline copolymer of at least one monomer selected from the group consisting of decene and propylene as a main component is used. Preferably crystalline polypropylene homopolymer is used, more preferably crystalline homopolypropylene having an isotactic pentad fraction of 0.80 to 0.99. The polypropylene resin of component (A) used in the present invention has a melt flow index of 4 to 40 g / 10 minutes, preferably 5 to 30 g / 10 minutes. The content of the polypropylene resin is 44 to 78.89% by weight, preferably 55 to 68.4% by weight based on the total resin composition.

As the halogen-based flame retardant as the component (B) of the present invention, decabromodiphenyl ether, ethylene-bis (tetrabromo phthalimide), bispentabromophenoxyethane, or a mixture thereof can be used. Examples of commercially available halogen flame retardants that can be used include, for example, decabromodiphenyl ether S-102E (trade name, manufactured by Albemarle Corporation), BT-93 (trade name, Albemarle), or ethylene-bis (tetrabromo phthalimide), or S-8010 (brand name, Albemarle) etc. are bispentabromo phenoxy ethane. The content of the halogen flame retardant is preferably 18 to 28% by weight. If the content of the flame retardant is less than 18% by weight, flame retardant grades of V-0 grade cannot be obtained at 1/32 inch thickness, and if the content of the flame retardant exceeds 28% by weight, the mechanical property retention is low, which is not preferable.

As antimony oxide which is (C) component of this invention, antimony trioxide, antimony pentoxide, a boron compound, or a mixture thereof can be used. (C) The antimony oxide is used in an amount of 3 to 15% by weight, preferably 5 to 12% by weight based on the total resin composition.

As the anti-dripping agent (D) component of the present invention, a granulated tetrafluoroethylene polymer may be used, and a polymer having a fluorine content of 70 to 76% by weight may be used. In addition to the above, copolymers of other fluorine-containing monomers with tetrafluoroethylene or copolymers of fluorine-free copolymerizable ethylenically unsaturated monomers and tetrafluoroethylene can also be used as anti-dripping agents. When the above component is added, tetrafluoroethylene is present in fibrillated form during molding of the resin composition, and there is an effect of preventing the melt from falling when the molded product is burned. The tetrafluoroethylene used in the present invention is preferably used in powder or solid form. As the anti-dripping agent, a granulated tetrafluoroethylene polymer is used, and the content thereof is preferably 0.1 to 3% by weight. If the amount is less than 0.1% by weight, it is impossible to express the anti-drip effect required for V-0 flame retardancy, and at thin thicknesses such as 1/32 ", the flame retardancy of V-0 grade due to the dripping property of the molten resin during combustion If it exceeds 3% by weight, the flowability of the resin becomes extremely poor, making it difficult to form and process.

The nanoclay masterbatch which is the component (E) of the present invention is used in an amount of 10 wt% or less, preferably 0.01 wt% to 10 wt%, more preferably 0.5 to 10 wt%. When the amount of the use of the nanoclay master batch (E) exceeds 10% by weight, (B) the effect of expressing other mechanical properties including impact resistance is lowered, and the cost-saving effect on the reduction of flame retardant is also canceled. In the case where the master batch nanoclay is used as in the present invention, it is possible to reduce the amount of halogen-based flame retardant while maintaining excellent flame retardancy, thereby realizing eco-friendly properties and improving heat resistance and impact resistance based on light weight. This effect is also superior to applying the nanoclay to the simple mixing method by mechanical means. The nanoclay masterbatch to be introduced into the resin composition of the present invention can be produced in an easy operation, rather than a laboratory scale production through complex apparatus and steps such as a conventional solution method, so that a large amount of the flame retardant polypropylene composition can be produced. Production is possible. The nanoclay master batch is kneaded and extruded from 0 to 30% by weight of polypropylene-maleic anhydride graft copolymer having a graft ratio in the range of 0.2 to 2.0, 30 to 90% by weight of polypropylene resin and 10 to 70% by weight of nanoclay. It is preferable to prepare. According to one preferred embodiment of the present invention, the polypropylene-maleic anhydride graft copolymer comprises 94.5 to 99.6 wt% of polypropylene resin and 0.3 to 3.0 wt% maleic anhydride, graft having a melt flow index of 1 to 10 g / 10 min. 0.1 to 2.5% by weight of initiator and other stabilizers can be prepared by polymerization in a conventional twin screw extruder. Instead of the polypropylene-maleic anhydride graft copolymer, terminal carboxylated polyethylene (COOH-PE), terminal carboxylated polypropylene (COOH-PP), terminal maleic anhydride polypropylene (MAH-PP), Poly (styrene-acrylic acid) (P (St-AA)), polystyrene-polyimide block copolymer (PS-PI), polystyrene-polyethylene block copolymer (PS-PE), styrene-ethylene-butadiene-styrene block copolymer (SEBS), polystyrene-polymethylmethacrylate block copolymer (PS-PMMA), polystyrene-polybutyladipate block copolymer (PS-PBA), polystyrene-polycaprolactone block copolymer (PS-PCL), poly Propylene-polyamide graft copolymer (PP-g-PA), polybutylene terephthalate-polyamide graft copolymer (PBT-g-PA), polyethylene-maleic anhydride graft copolymer (PE-g -MA), ethylene propylene rubber-maleic acid graft copolymer (EPR -g-MA), ethylene propylene diene monomer-maleic acid graft copolymer (EPDM-g-MA), syndiotactic polystyrene-maleic anhydride graft copolymer (sPS-g-MA), or styrene-ethylene- Butadiene-styrene-maleic anhydride graft copolymer (SEBS-g-MA) and the like can also be used. It is preferable to prepare a masterbatch directly by selecting a suitable polypropylene resin for maximum physical expression corresponding to the use of the final resin composition. According to one preferred embodiment of the present invention, the nanoclay may be used montmorillonite (organic) chlorinated with organic phosphate or organic ammonium salt substituted with an alkyl or aromatic group having 12 to 36 carbon atoms. In this case, since hydrophilic montmorillonite is substituted with hydrophobicity, it is further advantageous in that it has good affinity with hydrophobic polypropylene and shows excellent dispersibility and maximum physical properties.

The resin composition according to the present invention may optionally include 0.01 to 5 wt% or less of a compatibilizer (F) to further increase the hydrophilicity of the polypropylene. The types of compatibilizers that can be used are polypropylene-maleic anhydride graft copolymer (PP-g-MA), polyethylene-maleic anhydride graft copolymer (PE-g-MA), ethylene propylene rubber-maleic acid graft Copolymer (EPR-g-MA), ethylene propylene diene monomer-maleic acid graft copolymer (EPDM-g-MA), and styrene-ethylene-butadiene-styrene-maleic anhydride graft copolymer (SEBS-g- MA).

The resin composition of the present invention is selectively primary and secondary oxidation in addition to the component (A), the component (B), the component (C), the component (D) and the component (E), and optionally the component (F). One or two or more additives selected from the group consisting of an inhibitor, a lubricant, a slip agent, and a neutralizing agent may be further included within the range of 0.05 to 5.0% by weight relative to 100% by weight of the final resin composition, A plasticizer, a heat stabilizer, a light stabilizer, an organic or inorganic pigment, a dye, and the like may be further included in a range of 0.05 to 5.0 wt% with respect to 100 parts by weight of the final resin composition within a range that does not impair the purpose.

The polypropylene resin composition of this invention is manufactured by melt-mixing under normal conditions, for example using a twin screw extruder. The polypropylene resin composition thus prepared may be processed for the purpose of molding various products requiring flame retardancy by a conventional injection molding method after being sufficiently dried.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but these Examples are only for the purpose of explanation and are not intended to limit the present invention.

Property evaluation method

According to the following method, the mechanical properties and flame retardancy of the resin composition of this invention were evaluated.

1) Melt Flow Index: According to ASTM D1238 method, the flowability of the resin was measured in g / 10min under a load of 2.16kg at 230 ° C.

2) Specific gravity: It was measured using buoyancy in the liquid according to ASTM D1505 method.

3) Tensile strength: Using a test specimen of 2 ± 0.5mm thickness in accordance with the American standard test standard (ASTM D412) was measured by a tensile tester under the conditions of 50mm / min tensile speed.

4) Flexural modulus: The value calculated with the slope of the initial straight line on the flexural load curve at the speed of 5mm / min according to ASTM D790 method is indicated.

5) Izod impact strength: measured by using a 3.2mm thick injection molded specimen in accordance with the American standard test standard (ASTM D256).

6) HDT (Heat Deflection Temperature): The test specimens of length 127mm, width 12.7mm and thickness 6.4mm are molded by injection molding machine and carried out under the load of 4.6kgf / cm2 of ASTM D648 test standard. As a reference.

7) Flame retardancy: The vertical burning test of "Combustibility test of plastic material for mechanical parts" in UL (Underwriters Laboratories Incorpoartion) Subject 94 was based on the vertical phase (V0). The thickness of the test pieces used was 1/16 inch.

Preparation of Nanoclay Masterbatches

95% by weight polypropylene resin and 10% maleic anhydride with melt flow index Polypropylene-maleic anhydride graft copolymer was prepared by polymerizing 2.0 wt%, 2.0 wt% Dicumylpeoxide as initiator and 1.0 wt% Calciumstearate as stabilizer in a conventional twin screw extruder, 25 wt% of the copolymer, 25 wt% of polypropylene resin, and 50 wt% of nanoclay were kneaded and extruded with a kneader to prepare a masterbatch.

Examples 1-2

In a twin screw extruder rotating in the same direction, a nanoclay master batch, a polypropylene resin, a flame retardant, a flame retardant aid, and other additives prepared in the above production example were added, followed by melt mixing and extrusion to prepare a resin pallet, and at 80 ° C. It was dried in vacuo. Injection molding the dried resin composition to evaluate the mechanical properties and flame retardancy according to the above-described method, the results are shown in Table 1.

Comparative Examples 1 and 2

The composition was prepared using a polypropylene, flame retardant, flame retardant aid, anti-dripping agent, and optionally inorganic filler, in the composition shown in Table 1, without using nanoclay masterbatches. The composition was injection molded to evaluate its mechanical properties and flame retardancy, and is shown in Table 1.

ingredient Kinds Example 1 Example 2 Comparative Example 1 Comparative Example 2 Polypropylene Resin (A) PP 1) 61.5 62.5 64.5  59.5 Flame retardant (B) Halogen-based 2) 25.0 22.0 28.0  18.0 Flame retardant additive (C) Antimony trioxide 3)  6.0  5.0  7.0   7.0 Dripping Preventer (D) F-based polymer 4)  0.5  0.5  0.5   0.5 Nanoclay M / B (E) I.44PA M / B 5)  7.0 10.0    -    - Inorganic filler Talc 6)    -    -    -  15.0 Other additives (parts by weight based on 100 parts by weight of the composition) Primary Antioxidant 7)   0.1   0.1  0.1   0.1 Secondary antioxidant 8)  0.1  0.1  0.1   0.1 Calcium stearate 9)  0.1  0.1  0.1   0.1 Mechanical properties Melt flow index 10.5 10.1 11.7 11.2 importance 1.00 1.01 1.04 1.14 The tensile strength 365 395 345 390 Flexural modulus 29,500 32,500 29,000 31,000 Izod impact strength 3.8 3.5 3.1 2.5 H.D.T. 118 122 110 134 Flame retardant UL94 rating V-0 V-0 V-0 V-0 Total combustion time 43 sec 49 sec 31 sec 18 sec

 [Note] (Unit: wt%)

1) PP: Homo polypropylene resin with melt flow index of 10 ~ 15g / 10min

(HJ500 (trade name); Samsung General Chemical Co., Ltd.)

2) Flame retardant: High melting point halogen flame retardant, bispentabromophenoxy ethane

(S-8010 (trade name); manufactured by Albermalre)

3) Flame retardant aid: antimony trioxide (SW (brand name); Ilsung antimony)

4) Anti-dripping agent: Granulated tetrafluoroethylene polymer

(Teflon 800J (trade name); manufactured by Dupont)

5) Nanoclay master batch: Nanoclay master batch containing 50% of Nanomer's Nanomer I.44PA (manufactured by Samsung General Chemical Co., Ltd.)

6) Talc (KCM-5200 (trade name); Korea-China Trade)

7) Primary Antioxidant: S-1010 (Songwon Industry)

8) Secondary Antioxidant: S-1200 (Songwon Industry)

9) Calcium Stearate: Ca-St (Songwon Industry)

As can be seen from the results of Table 1, the resin composition to which the nanoclay masterbatch was applied was able to satisfy the UL94 V-0 grade while using a relatively small amount of flame retardant compared to Comparative Example 1. By reducing the amount of flame retardants, which are relatively expensive, by reducing the flame retardant, it is possible to pursue not only environmentally friendly characteristics but also cost reduction effects. In addition, Examples 1 and 2 also showed excellent characteristics in terms of other mechanical properties. Comparative Example 2, which applied talc as an inorganic filler, showed excellent properties in terms of flame retardancy and heat resistance, but was markedly different in weight and relatively inferior in impact characteristics.

As described in detail above, the polypropylene resin composition according to the present invention can secure excellent flame retardant properties even when using a small amount of flame retardant by master batching a layered clay mineral such as nanoclay. The mechanical properties of the resin molded article produced therefrom are improved, and the generation of halides upon incineration of the resin molded article is preferable in terms of environmental aspects. In addition, with economics through the reduction of flame retardants, it is commercially available because it is possible to mass-produce rather than the application of lab scale nanoclays by complex processes.

Claims (6)

 (A) 44 to 78.89 wt% of polypropylene resin, (B) 18 to 28 wt% of halogen flame retardant, (C) 3 to 15 wt% of antimony oxide, (D) 0.1 to 3 wt% of anti-dripping agent, (E) nano A flame retardant polypropylene resin composition comprising 0.01 to 10 wt% of a nanoclay masterbatch, The polypropylene resin is a crystalline homopolypropylene having an isotactic pentad fraction of 0.80 to 0.99, wherein the nanoclay masterbatch is a polypropylene-maleic anhydride graft copolymer having a graft ratio in the range of 0.2 to 2.0. To 30% by weight, polypropylene resin 30 to 90% by weight and nano-clay 10 to 70% by weight of the flame retardant polypropylene resin composition prepared by kneading. The flame retardant polypropylene resin composition according to claim 1, further comprising (F) 0.01 to 5 wt% or less of a compatibilizer. The resin composition according to claim 1 or 2, wherein the resin composition is selected from the group consisting of primary and secondary antioxidants, lubricants, slip agents and neutralizing agents as additional components within the range of 0.1 to 5.0 parts by weight relative to 100 parts by weight of the total composition. A flame retardant polypropylene resin composition comprising at least one additive. delete delete       The flame retardant polypropylene resin composition according to claim 1 or 2, wherein the nanoclay is organicized with an organophosphate or organoammonium salt substituted with an alkyl group or an aromatic group having 12 to 36 carbon atoms.