KR20160054741A - Polyolefin flame retardant resin composition and molded product - Google Patents

Abstract

The present invention relates to a polyolefin flame retardant resin composition and a molded article and, more specifically, to an eco-friendly polyolefin flame-retardant resin composition, which meets flame retardancy required for an extruded tubing molded product or the like for electricity/electronics and vehicle insulation and wiring, improved extrusion processability, and appearance quality, wherein the flame retardancy has UL94V V-2 grade and a self-extinguishing flame of 15 seconds or less, and to a molded product manufactured by the composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyolefin flame retardant resin composition and a molded article,

The present invention relates to a polyolefin flame retardant resin composition and a molded article, and more particularly, to a flame retardant polyolefin resin composition and a molded article thereof which are excellent in flame retardancy (particularly V-2 grade) required for applications such as electric / electronic, automotive insulation, And self-extinguishing property of less than 15 seconds / environment-friendly flame retardancy), improved extrusion processability and appearance quality, and a molded article made from the composition.

Examples of the material applied to the tube system in the automobile engine room are polyolefin resins such as polyamide, polyester, polyethylene resin and polypropylene resin.

These materials are exposed to high-temperature use conditions for a long period of time, and therefore materials having excellent flame retardancy and long-term heat resistance are essential. A material with a halogen flame retardant system containing / satisfying the above two characteristics is in use. However, the demand for eco-friendly materials and products that do not use harmful substances (halogens, heavy metals) has been greatly increased due to recent enforcement of environmental regulations, and materials researches are actively pursued accordingly.

In the environmentally friendly flame retardant system applicable to the polyolefin resin, metal hydroxide and phosphorus can be considered. In the case of metal hydroxide, it is necessary to input a flame retardant in an amount of 40% or more and the moldability, water resistance and mechanical performance are degraded. (Related Korean Patent Laid-Open Publication No. 2013-0048426).

For example, in the case of phosphorus, it is advantageous to realize physical properties without containing halogen and heavy metals with a dosage of 20% or more. However, it is still difficult to disperse flame retardant more effectively than the amount of flame retardant in comparison with conventional halogen system. It is urgently required to develop a polyolefin flame retardant resin composition which can solve this problem.

In order to solve the problems of the prior art as described above, the present invention relates to a polyolefin flame retardant resin composition used for applications such as electric / electronic, automobile insulation, and extrusion tube products for wiring, , Which is a flame-retarding mechanism of charcoal flame retardant, and a runaway effect of gas phase and dripping behavior together to improve flame retardancy, extrusion processability and appearance quality And to provide the above objects.

In order to achieve the above object, the present invention provides a phosphorus flame retardant comprising a polyolefin resin and a phosphorus-based flame retardant, wherein the phosphorus flame retardant has a phosphorus content of 30 wt% or more and a normal distribution average (D50) And 4 to 30% by weight of 100% by weight of the total components constituting the polyolefin flame retardant resin composition.

The present invention also provides a molded article which is molded from the composition.

As described above, according to the present invention, the environmentally flame retardant property of the polyolefin resin is realized as a phosphorus flame retardant, and as the phosphorus flame retardant, the dispersibility of the flame retardant is good and the thermal stability is observed in a high temperature range as a result of TGA It is difficult to disperse an effective flame retardant in excess of the input amount of a conventional phosphorus flame retardant while injecting a specific solid phosphorus flame retardant having excellent heat resistance in a relatively small amount, thereby improving the flame retardancy and extrusion processability and further improving the appearance quality. There is an effect to provide.

FIG. 1 is a graph showing a gentle dynamic TGA peak of the solid phosphorus flame retardant used in the example according to the present invention and a peak of the dynamic dynamic tensile dynamic analysis peak of the conventional solid phosphorus flame retardant used in the comparative example.

Hereinafter, the present invention will be described in detail.

The polyolefin flame retardant resin composition of the present invention comprises a polyolefin resin and a phosphorus flame retardant, wherein the phosphorus flame retardant comprises a solid phosphorus flame retardant having a phosphorus content of 30% by weight or more and a normal distribution average (D50) And 4 to 30% by weight of 100% by weight of the whole components.

As the polyolefin resin, a polypropylene resin can be used as a specific example.

Further, the polyolefin flame retardant resin composition of the present invention corresponds to a so-called environmentally friendly flame retardant resin composition containing no halogen, or substantially no halogen.

The term " solid phosphorus flame retardant " used in the present invention is a solid type at room temperature, unless otherwise specified, and is a conventional flame retardant of conventional phosphate flame retardant Refers to a phosphorus-containing flame retardant in the form of a particular phosphate which together with the runaway effect of gas phase and dripping behavior.

For example, the solid phosphorus flame retardant has a content range of phosphorus (P) measured by ICP-OES diluted with sulfuric acid and nitric acid using ICP-OES (PERKIN-ELMER, OPTIMA 7300DV) 30 to 35 wt%, 30 to 32 wt%, or 30.5 to 31.5 wt%.

The solid phosphorus flame retardant may have a normal distribution average (D50) of 7 microns or less as measured using a Malvern Mastersizer 2000 instrument.

Displayed in another example, the solid phosphorus-based flame retardant is formula [H2PO-O] _n M ^{n +} (a, where n is an integer from 1 to 3, M is at least one selected from Al, Ca, Na, Zn, Ba, Mg) ≪ / RTI >

The M may be at least one kind selected from Al, Ca and Zn, and it is more preferable that Al alone or Al contains the synergistic effect to the flame retardancy.

As another example, the solid phosphorus flame retardant has a dynamic thermal peaks (dynamic TGA peak-self-ignition temperature auto ignition Temp.) At a gentle pyrolysis at 275 to 300 ° C (see the embodiment of FIG. 1) The comparative pyrolysis degree / weight loss is less, and for example, the physical properties can be maintained without external strain / crack up to 135 ° C x 3000 hr.

For reference, the content of phosphorus (P) measured by ICP-OES was diluted by treatment with sulfuric acid or nitric acid using a device of ICP-OES (PERKIN-ELMER, OPTIMA 7300DV) among the solid phosphorus flame retardants, The flame retardant exhibited a rapid thermal decomposition at a dynamic TGA peak of about 250 ° C (see Comparative Example of FIG. 1), and the weight loss was large and the properties of the flame retardant were abruptly deteriorated during hygroscopicity, heat resistance and long-term reliability test .

The solid phosphorus flame retardant constituting the composition may include a processing aid.

Preferably, the processing aid is a material capable of providing a maximum processing temperature of 290 ° C when provided with a solid phosphorus flame retardant having an auto ignition temperature of 400 ° C or higher.

The processing aid may include, for example, a phosphate-based compound such as di-2,6-dimethylphenyl phosphate, and PX-200 is a commercially available product.

The processing aid may be 0.1 to 20% or 0.1 to 10% of the content of the solid phosphorus flame retardant constituting the composition, and is effective for increasing the dispersibility within the above range.

The polyolefin resin may be 70 to 96 wt% or 80 to 95 wt% of the total composition 100 wt%, and the solid phosphorus flame retardant may be 4 to 30 wt%, or 5 to 20 wt% And has an effect of providing self-extinguishing property within 15 seconds, extrusion workability, and appearance quality such as gloss and roughness while maintaining the flame retardancy grade V-2 measured by the UL 94 method within the above range.

As an example of the polyolefin resin, the polypropylene resin has an isotactic propylene homopolymer having a melt index (MI) of 0.1 to 30 g / 10 min (ASTM D1238, 230 DEG C) and crystallinity, an ethylene- Coalescent, or a mixture thereof.

Specific examples of the polypropylene resin include an isotactic propylene homopolymer having a melt index (MI) of 0.1 to 8 g / 10 min (ASTM D1238, 230 DEG C) and having crystallinity, an ethylene-propylene block or a random copolymer More than; And a mixture of at least one of an isotactic propylene homopolymer having crystallinity and an ethylene-propylene block or a random copolymer having a melt index (MI) of more than 8 g / 10 min (ASTM D1238, 230 DEG C) .

The polyolefin flame retardant resin composition may further contain additives such as a lubricant, an antioxidant, a light stabilizer, a chain extender, a catalyst, a releasing agent, a pigment, a dye, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, An antiwear agent, an antiwear agent, an antiwear agent, and a coupling agent. The additive can be used, for example, within a range not adversely affecting the physical properties of the polyolefin flame retardant resin composition of the present invention.

The polyolefin flame retardant resin composition of the present invention may be optionally mixed with the above additives in a mixer or a super mixer, and thereafter mixed with one of various blending machines such as a biaxial extruder, a single screw extruder, a roll mill, a kneader or a Banbury mixer, Kneaded in a temperature zone of 300 ° C, extruded to obtain pellets, and the extruded tubing product is obtained therefrom. Alternatively, the pellets can be sufficiently dried using a dehumidifying dryer or a hot-air dryer and then injection-processed to produce injection molded articles .

For example, the UL94V V-2 grade and self-extinguishing properties required for extruded tubing molded applications for electrical / electronic, automotive insulation and wiring under non-anti-dripping agent conditions and flame retardant, Extrusion processability, and appearance quality, and as another example, an injection molded article may be provided. The term " non-dropping agent " refers to an agent other than the anti-drip agent, unless otherwise specified.

The extruded tubing may be, for example, an industrial fluid transport tube, a drug transport tube, a fuel gas supply tube, an automobile fuel tube, an automobile cable protector, a wire cable, a cable sheath, , Or a cable tie.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention, but the present invention is not limited thereto.

[Example]

Examples 1 to 4

The components shown in the following Table 1 were put into a super mixer in the stated amounts and mixed well. The mixture was melt-kneaded in a temperature range of 200 to 290 ° C using a twin-screw extruder And then pellets were obtained.

These pellets were used as test specimens for the physical property test and the actual product tube was blown or vacuum molded so as to have a size of 5 to 40. The individual pieces were obtained according to the size and the properties were evaluated according to the workability (extrusion processability), appearance, MS single item evaluation (combustibility, heat resistance, cold resistance, pressure resistance neutralization, etc.).

Comparative Examples 1 to 4

A specimen was prepared in the same manner as in Example 1, except that the ingredients shown in Table 1 were used in the stated amounts.

* (A) Polypropylene resin:

(A-1) A polypropylene resin having an MI of 0.35 measured at a temperature of 230 DEG C and a load of 2.16 kg for 10 minutes in accordance with ASTM D1238.

(A-2) A polypropylene resin having an MI of 10 measured at a temperature of 230 DEG C and a load of 2.16 kg for 10 minutes in accordance with ASTM D1238.

* (B) Solid phase flame retardant:

( P) having a phosphorus content of 16 to 20 wt% measured by ICP-OES by diluting with sulfuric acid or nitric acid using an apparatus of ICP-OES (PERKIN-ELMER, OPTIMA 7300DV) As a system, a dynamic flame retardant having a dynamic annealing copper peak of 250 ° C.

(B-2) expression [H2PO-O] ₃ Al has a ^3+, ICP-OES (PERKIN-ELMER, OPTIMA 7300DV) of the device by using a dilute sulfuric acid, nitric acid after processing of measuring ICP-OES (P) (D50) of 7 microns, a dynamic thermal dynamic analysis peak of 275 to 300 占 폚, and PX-200 as a processing aid.

division
(wt%) Example Comparative Example One 2 3 4 One 2 3 4 A-1 95 90 70 60 97 90 70 40 A-2 0 0 20 20 0 0 0 20 B-1 0 0 0 0 0 10 30 40 B-2 5 10 10 20 3 0 0 0

[Test Example]

The properties of the specimens prepared from the polypropylene flame retardant resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were measured by the following methods, and the results are shown in Table 2 below.

[Property measurement test]

* Flame retardancy: measured at a thickness of 1.6 mm by the UL94 vertical method.

* Self-extinguishing: One 300 mm tube specimen was hanging at a 45-degree angle from the air, and the flame of an alcohol lamp or gas burner was burned at about 20 mm below the specimen, and the time until the flame was turned off was measured. Pass criteria is less than 15 seconds.

* Extrusion workability of the tube: Visually evaluated according to the method specified in UL 1581. For reference, very good flame retardant does not have fine dispersion residue, does not have die hole carbide, good appearance, good flame retardant has very little occurrence of fine dispersion residue and can be found with naked eye. (Poor appearance), poor flame retardancy of the product, and molding for extrusion tubing, but the flame retardant residue is generated in a state where the continuous operation is difficult at the time of production of the actual product, And the surfaces were also subjected to evaluation of states in which molding and production were impossible due to a large amount of micro-dispersed flame retardant residues.

* Appearance quality (gloss, roughness) of the tube: It was evaluated with visual quality and emotional quality. For reference, edges / edges must be alive (symmetry / line), and surface roughness is low so that it is smooth. For reference, the symbols in the table apply the following criteria respectively:

◎ The loading amount of flame retardant, filler and other additives is very small, so it is possible to obtain a clean product with almost base resin (Virgin PP raw material) level.

○ (No flame retardant / filler is firmly reinforced.) It is suitable for mass production with perfect gloss and good surface smoothness without partial molding of corrugated tube corrugated tubes.

△ Flame retardant and other additive are slightly increased, resulting in partial unforming, roughness due to surface protrusion and fine dispersion during visual inspection of the tube, and a decrease in gloss. Mass production is difficult.

X Continuous Flame Retardant The micro-dispersion and die drool phenomenon cause the flame retardant to come out periodically, resulting in a noticeable drop in extrusion workability. Evaluation of workability / mass production is judged impossible.

Example Comparative Example One 2 3 4 One 2 3 4 UL94 (1.6t) V-2 V-2 V-2 V-2 Not measurable Not measurable V-0 V-0 The tube (0.3t)
Self-extinguishing 9 seconds 4 seconds 4 seconds 3 seconds More than 30 seconds
(Measurement impossible) More than 30 seconds
(Measurement impossible) 10 seconds 5 seconds Extrusion workability Very good good good good Very good Good Bad Bad Exterior quality ◎ ◎ ◎ ○ ◎ ○ X X

* Note: Corrugated tube specification: [UL 94] V-2 @ 1.6mm,

[Self-extinguishing property] Extruded tubing molded article Self-extinguishing requirement within 15 seconds @ 0.2 ~ 0.4mm.

As shown in Table 2, in the case of the extruded tube specimen made from the polyolefin flame retardant resin composition according to the present invention (Examples 1 to 4), the flame retardancy of the polypropylene resin and the flame retardant of the solid phase, , Self-extinguishing properties, especially tube extrusion processability and appearance quality were improved.

In addition, in the case of the extruded tube specimen made of the polyolefin flame retardant resin composition according to the present invention (Examples 1 to 4), flame retardancy compared with Comparative Example 2 in which self-extinguishing properties were not effectively exerted by dispersion of the solid flame retardant powder having a low phosphorus content The self-extinguishing property of the tube, the extrusion processability of the tube and the appearance quality were improved.

Further, in the case of the extruded tube specimen made from the polyolefin flame retardant resin composition according to the present invention (Examples 1 to 4), the content of the solid phase flame retardant powder with a low phosphorus content was increased to 3 times as compared with Comparative Example 2, While improving the extrusion workability and appearance quality, while maintaining the level of self-extinguishing properties.

Further, in the case of the extruded tube specimens prepared from the polyolefin flame retardant resin composition according to the present invention (Examples 1 to 4), it was found that the two types of polypropylene resins having different melt indexes and the comparative Example 4 using the phosphorus flame retardant having a low phosphorus content The extrusion workability and the appearance quality were improved, while maintaining the self-extinguishing properties.

<Reference example>

In Example 1, the same procedure as in Example 1 was repeated except that polytetrafluoroethylene (without pretreatment) as the (C) anti-drip agent was further included as follows.

division
(wt%) Reference example One 2 A-1 64.5 58.8 A-2 20 20 B-1 0 20 B-2 15 0 C 0.5 0.2

The physical properties of Reference Examples 1 and 2 were measured in the same manner as in Example 1, and the results are summarized in Table 4 below.

division Reference example One 2 UL94 (1.6t) Not measurable V-1 The tube (0.3t)
Self-extinguishing More than 30 seconds
(Measurement impossible) More than 30 seconds
(Measurement impossible) Extrusion workability Inadequate Inadequate Exterior quality △ X

As can be seen from Table 4, Examples 1 to 4 described above rapidly improve the self-extinguishing properties by rapidly increasing the dropping rate. In contrast, the extruded tube specimen made of the polyolefin flame retardant resin composition (Reference Examples 1 and 2), all were inferior to those of Examples 1 to 4 in terms of flame retardancy, self-extinguishing ability, extrusion workability, and appearance quality.

As a result, according to the present invention, the flame retardancy, improved extrusion processability, and appearance quality of less than 15 seconds of UL94V V-2 grade and self-etching required for applications such as extrusion tubing molded parts for electric / The present invention relates to an environmentally friendly polyolefin flame retardant resin composition comprising a polyolefin resin and a phosphorus-based flame retardant, wherein a specific phosphorus flame retardant is used as the phosphorus-based flame retardant in a relatively small amount to achieve flame retardancy, extrusion processability, It is possible to provide a polyolefin flame retardant resin composition and a molded article produced from the composition.

Claims (11)

A polyolefin resin and a phosphorus flame retardant,
Characterized in that the phosphorus flame retardant comprises a solid phosphorus flame retardant having a phosphorus content of 30 wt% or more and a normal distribution average (D50) of 7 microns or less in an amount of 4 to 30 wt% of 100 wt% To
Polyolefin flame retardant resin composition, The method according to claim 1,
The solid phosphorus-based flame retardant is formula [H2PO-O] _n M ^{n +} is a compound represented by (wherein n is an integer from 1 to 3, M is at least one selected from Al, Ca, Na, Zn, Ba, Mg) Characterized by
Polyolefin flame retardant resin composition. 3. The method of claim 2,
Wherein the solid phosphorus flame retardant contains 0.1 to 20% of the processing aid in the amount of the solid phosphorus flame retardant and the dynamic TGA peak exhibits gentle pyrolysis at 275 to 300 ° C.
Polyolefin flame retardant resin composition. The method of claim 3,
Wherein the processing aid is an aromatic phosphate-based compound which provides a maximum processing temperature of 290 ° C when provided with a solid phosphorus flame retardant at an autoignition temperature of 400 ° C or higher
Polyolefin flame retardant resin composition. The method of claim 3,
Characterized in that the processing aid is di-2,6-dimethylphenylphosphate
Polyolefin flame retardant resin composition. The method according to claim 1,
The polyolefin resin is an isotactic propylene homopolymer having crystallinity, an ethylene-propylene block or a random copolymer, or a mixture thereof, having a melt index (MI) of 0.1 to 30 g / 10 min (ASTM D1238, 230 DEG C)
Featured
Polyolefin flame retardant resin composition. The method according to claim 1,
The resin composition can be used as a lubricant, an antioxidant, a light stabilizer, a chain extender, a catalyst, a releasing agent, a pigment, a dye, an antistatic agent, an antimicrobial agent, a processing aid, a metal deactivator, a fuming inhibitor, an inorganic filler, And at least one additive selected from a coupling agent
Polyolefin flame retardant resin composition. The method according to claim 1,
The polyolefin flame retardant resin composition is characterized by having a flame retardancy of UV94V V-2 grade and self-extinguishing property within 15 seconds under the condition of non-anti-dripping agent
Polyolefin flame retardant resin composition. A molded article molded from the polyolefin flame retardant resin composition according to claim 1. 10. The method of claim 9,
Wherein the molded article is an extruded tubing molded article or an injection molded article
Shaped article. 11. The method of claim 10,
Characterized in that the extruded tubing product is an industrial fluid transport tube, a drug transport tube, a fuel gas supply tube, an automotive fuel tube, an automotive cable protector, a wire cable, a cable sheath, or a cable tie.

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