KR20140103700A - Poly(arylene ether) resin composition and covering material produced therefrom - Google Patents

Abstract

The present description relates to a poly(arylene ether) resin composition and a covering material produced therefrom, and more specifically, to a poly(arylene ether) resin composition comprising: i) a poly(arylene ether) resin; ii) a polyolefin block copolymer; and iii) a poly(arylene ether) resin including a styrene block copolymer. According to the present description, provided are the poly(arylene ether) resin composition which can substitute PVC that has a negative effect on the environment and which has excellent flame retardancy, flexibility, chemical resistance, processability, and impact resistance; and the covering material produced therefrom.

Description

POLY (ARYLENE ETHER) RESIN COMPOSITION AND COVERING MATERIAL PRODUCED THEREFROM BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a poly (arylene ether) resin composition and a coating material prepared therefrom, and more particularly to a poly (arylene ether) resin composition which can replace a polyvinyl chloride resin which adversely affects the environment and which is excellent in flame retardance, flexibility, (Arylene ether) resin composition excellent in impact resistance and flexibility, and a cover material made therefrom.

BACKGROUND ART Polyvinyl chloride resin (hereinafter referred to as PVC) has been used for a long time as a coating resin in coated conductors and cable industries. However, halogen-containing resins can generate dioxins in the manufacturing process, generate a large amount of smoke and toxic gases in the event of a fire, causing environmental pollution, and increasing life and property damage. Thus, there is a continuing increase in the need to limit or prohibit the use of halogen-containing resins due to these negative effects.

On the other hand, the poly (arylene ether) resin is a halogen-free amorphous resin having good dimensional stability, insulation property, heat resistance and rigidity. However, since it has low chemical resistance, it is easily decomposed when exposed to oils or organic solvents have.

Therefore, it is urgent to develop a plastic material that can replace PVC as a halogen-free resin.

In order to solve the problems of the prior art as described above, the present invention relates to a poly (arylene ether) resin composition which can replace PVC which adversely affects the environment and which is excellent in flame retardance, flexibility, chemical resistance, workability, impact resistance and flexibility And a coating material prepared therefrom.

These and other objects of the present disclosure can be achieved by all of the present invention described below.

In order to achieve the above object, the present invention provides a method for producing a polyurethane resin composition comprising: i) a poly (arylene ether) resin; Ii) polyolefin block copolymers; And (iii) a poly (arylene ether) resin composition comprising a styrene block copolymer and a coating material prepared therefrom.

As described above, according to the present invention, it is possible to provide a poly (arylene ether) resin composition which can replace PVC which adversely affects the environment and which is excellent in insulation, flame retardancy, flexibility, chemical resistance, processability, heat resistance, impact resistance and flexibility And a coating material prepared therefrom.

Hereinafter, the present invention will be described in detail.

The poly (arylene ether) resin composition of the present invention comprises: i) a poly (arylene ether) resin; Ii) olefin copolymers; And iii) a styrene block copolymer.

The i) poly (arylene ether) resin is used in an amount of 20 to 60% by weight, 30 to 50% by weight or 35 to 45% by weight based on 100% by weight of the total of the poly (arylene ether) And it has an effect of having both excellent flame retardancy and physical properties within this range.

The i) poly (arylene ether) resin may be, for example, a poly (phenylene ether) resin.

The i) poly (arylene ether) resin may have an intrinsic viscosity of 0.30 dl / g or more, 0.30 to 0.45 dl / g or 0.31 to 0.45 dl / g as measured at 25 ° C and chloroform, It has an effect of having high flame retardancy and physical properties in the inside.

The i) poly (arylene ether) resin may have a weight average molecular weight of 10000 to 100000, 30000 to 70000, or 30000 to 50000, for example.

The i) poly (arylene ether) resin may be at least one selected from the group consisting of homopolymers, copolymers, graft copolymers, ionomers and block copolymers.

The olefin copolymer may be contained in an amount of 15 to 50% by weight, 20 to 45% by weight or 25 to 40% by weight based on 100% by weight of the total of the poly (arylene ether) resin composition (i) Within this range, it is excellent in flexibility, flame retardancy, elongation and compatibility.

The ii) olefin copolymer may have a density of 0.92 g / cc or less, 0.85 to 0.92 g / cc or 0.86 to 0.91 g / cc as an example, and an effect of significantly improving heat resistance, workability and elasticity within this range .

The ii) olefin copolymer may have a melting point of 100 ° C or higher, 100-130 ° C or 120-130 ° C, and the heat resistance, workability, and elasticity of the olefin copolymer are greatly improved within this range.

The ii) olefin copolymer may have a weight average molecular weight of 50,000 to 200,000, 50,000 to 200,000, 50,000 to 150,000, or 60,000 to 120,000, for example.

The ii) olefin copolymer may have an H-index value of less than 20, less than 15, 2 to 11, or 4.5 to 9, for example.

The ii) olefin copolymer may be, for example, TMA (Thermal Mechanical Analysis) at 70 ° C or higher, 70-130 ° C or 100-130 ° C.

The ii) olefin copolymer may have an ethylene content of 40 to 85% by weight or 50 to 80% by weight, for example.

The ii) olefin copolymer may have a molecular weight distribution (PDI) of 2.0 to 4.5, 2.2 to 4.5, or 2.3 to 2.9, for example. Within this range, heat resistance, workability and elasticity are greatly improved.

The ethylene content associated with the present olefin copolymer is measured using < 1 > H-NMR and the H-index is calculated using a Bruker Minispec 20 MHz, ) Was subjected to a 180 ° C press mold to prepare a sheet having a thickness of 3 mm and a radius of 2 cm and cooled at 10 ° C / min and measured on a Mettler scale.

Further, the melting point (Tm) related to the olefin copolymer of the present invention was measured using a DSC (Differential Scanning Calorimeter) 2920 manufactured by TA Corporation (the temperature was increased to 200 DEG C and then maintained at that temperature for 5 minutes The temperature is then ramped down to 30 ° C and the temperature is again raised to the melting point of the top of the DSC curve, where the rate of temperature rise and fall is 10 ° C / min and the melting point is obtained And the molecular weight distribution (PDI) is calculated by measuring the number average molecular weight and the weight average molecular weight by gel permeation chromatography (GPC), and then dividing the weight average molecular weight by the number average molecular weight.

Further, the TMA (Thermal Mechanical Analysis) relating to the present olefin copolymer was subjected to a sample penetration test with a force of 1 N using a TMA Q400 manufactured by TA Corporation, and the temperature increase rate was 25 ° C to 5 ° C / min The probe penetration distance is measured by a temperature function, and the probe is calculated as an experimental value when the probe penetrates 1 mm of the sample.

Examples of the olefin copolymer (ii) include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-hexene, 1-hexene, 1-hexene, 1-hexene, 1-hexene, 1-hexene, , 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like.

As another example, the ii) olefin copolymer may be a copolymer of ethylene and an alpha olefin.

The alpha olefins may be at least one selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.

The ii) olefin copolymer may be, for example, an olefin random copolymer or an olefin block copolymer, and another example may be an ethylene-alpha olefin random copolymer or an ethylene-alpha olefin block copolymer.

The styrene block copolymer may be 15 to 40% by weight, 20 to 35% by weight or 25 to 30% by weight based on 100% by weight of the total of the poly (arylene ether) resin composition (i) have.

The styrene block copolymer may be a styrene block copolymer having a styrene content of 10% by weight or more, 10-50% by weight or 20-45% by weight, and within this range, an interface between the poly (arylene ether) resin and the polypropylene resin The tensile strength is reduced to greatly improve the compatibility, and further, the useful property possessed by each resin is exhibited.

The iii) styrene block copolymer may be, for example, a copolymer comprising at least one block (A) composed of repeating arylalkylene units and at least one block (B) composed of repeating alkylene units.

The iii) styrene block copolymer may be a linear structure, for example, an A-B diblock copolymer or an A-B-A triblock copolymer.

Each block A may independently have the same or different molecular weight, and likewise each block B may independently have the same or different molecular weights.

The A block can be obtained, for example, from the polymerization of aryl alkylene monomers such as styrene.

The B block can be obtained, for example, by polymerization of an olefin having 2 to 15 carbon atoms or a conjugated diene monomer.

The olefin monomer may be at least one selected from the group consisting of ethylene, propylene and butylene.

The conjugated diene monomer may be, for example, butadiene.

The B block may include, for example, some unsaturated carbon-carbon bonds or vinyl groups.

The iii) styrene block copolymer may have a molecular weight, styrene content, or a mixture of two or more different styrene block copolymers. In this case, the balance of compatibility, flame retardancy and physical properties can be easily controlled.

As another example, the iii) styrene block copolymer may be a mixture of a diblock copolymer and a triblock copolymer.

As another example, the iii) styrene block copolymer may be a styrene block copolymer having a styrene content of 10 to 30% by weight or 10 to 20% by weight and a styrene block copolymer having a styrene content of 30 to 55% by weight or 35 to 45% Lt; / RTI > copolymer.

The poly (arylene ether) resin composition of the present invention may further include, for example, iv) a mineral oil. In this case, the styrene block copolymer is effectively plasticized to obtain a poly (arylene ether) And the workability is improved.

The iv) mineral oil may be, for example, an aliphatic oil or an aromatic oil. In another example, the viscosity (measured at 100 ° C) may be 2 to 8 cSt, 2 to 6 cSt, or 4 to 6 cSt.

The iv) mineral oil may be, for example, 10 to 100 parts by weight, 10 to 50 parts by weight, 15 to 40 parts by weight, or 17 to 35 parts by weight, based on 100 parts by weight of the styrene block copolymer, The poly (arylene ether) resin composition has excellent dispersibility, flexibility and processability.

The iv) mineral oil may be used in an amount of 0.1 to 20 wt%, 1 to 15 wt%, 2 to 10 wt%, or 2 to 8 wt% based on 100 wt% of the total of the poly (arylene ether) %, And within this range, the workability and flexibility of the product are improved.

The poly (arylene ether) resin composition of the present invention may further include, for example, v) a polypropylene resin (however, the poly (arylene ether) resin composition is not the same as the polyolefin block copolymer).

The v) polypropylene resin may contain, for example, from 0 to 30% by weight, from 0 to 30% by weight, from 5 to 25% by weight, from 5 to 25% by weight, based on 100% by weight of the total of the poly (arylene ether) 20% by weight or 8 to 15% by weight, and within this range, heat resistance, flame retardancy, appearance and impact strength are excellent.

The v) polypropylene resin has a flow index (MFI) of 0.1 to 20 g / 10 min, 0.1 to 15 g / 10 min, or 0.1 to 12 g / 10 min, measured at 230 캜 and 2.16 kgf load in accordance with ASTM- . Within this range, there is an effect of excellent processability and compatibility.

The v) polypropylene resin may be, for example, a homopolymer of propylene or an aliphatic alpha (alpha) -olefin having 2 to 20 carbon atoms (excluding 3 carbon atoms), an aromatic olefin, or a copolymer in which both of them are copolymerized with propylene have.

As another example, the v) polypropylene resin may be an aliphatic alpha-olefin having 2 to 8 carbon atoms (excluding 3 carbon atoms), an aromatic olefin, or a copolymer in which both of them are copolymerized with propylene.

The aliphatic alpha (alpha) -olefin may be at least one selected from the group consisting of ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.

As another example, the v.) Polypropylene resin may be a block polypropylene, a random polypropylene, a propylene-alpha-olefin copolymer, a propylene-ethylene copolymer, a propylene-butene copolymer and a propylene- Lt; / RTI >

The poly (arylene ether) resin composition of the present invention may further include, for example, vi) a flame retardant.

The vi) flame retardant may be, for example, a phosphorus-based flame retardant, and in this case, it is environment-friendly and has an effect of replacing the halogen-based flame retardant.

The above vi) flame retardant includes, for example, melamine phosphate, melamine orthophosphate, ammonium polyphosphate, diammonium phosphate, phosphoric acid amide, aluminum diadyl phosphate, polyphosphoric acid amide, resorcinol bis-diphenylphosphate, bis-phenol A diphenylphosphate , Tris (isopropenylphenyl) phosphate, and triphenylphosphate may be used alone or in combination of two or more.

The vi) flame retardant may be, for example, 5 to 30% by weight or 10 to 25% by weight based on 100% by weight of the total of the poly (arylene ether) resin composition (i) to (vi).

The poly (arylene ether) resin composition of the present invention includes, for example, i) 20 to 50% by weight of a poly (arylene ether) resin; Ii) from 15 to 50% by weight of an olefin copolymer; Iii) from 15 to 40% by weight of a styrene block copolymer; Iv) 0.1 to 20% by weight of mineral oil; V) polypropylene resin (however, not the same as the above-mentioned ii) polypropylene resin) 0 to 30% by weight; And (vi) 5 to 30% by weight of a flame retardant; within this range, there is an effect of being excellent in elongation, flame retardancy, impact resistance, chemical resistance, flexibility and workability, and particularly in balance of physical properties.

As another example, the present invention provides a resin composition comprising i) 20 to 40% by weight of a poly (arylene ether) resin; Ii) from 20 to 45% by weight of an olefin copolymer; Iii) from 20 to 35% by weight of a styrene block copolymer; Iv) 1 to 15% by weight of mineral oil; V) 5 to 25% by weight of a polypropylene resin (not the same as the above-mentioned ii) polypropylene resin; And vi) 10 to 25% by weight of a flame retardant; within this range, there is an effect of being excellent in elongation, flame retardancy, impact resistance, chemical resistance, flexibility and processability, and particularly in balance of physical properties.

The poly (arylene ether) resin composition of the present invention may have a Shore A hardness of 60 or more, 70 to 95, or 80 to 90 as measured by ASTM D 2240 using, for example, a test piece having a thickness of 3 mm.

Examples of the poly (arylene ether) resin composition of the present invention include a lubricant, an antioxidant, a light stabilizer, a hydrolysis stabilizer, a chain extender, a reaction catalyst, a release agent, a pigment, a dye, an antistatic agent, a crosslinking agent, Further comprises at least one additive selected from the group consisting of an inactivating agent, an opacifying agent, a fluorine-based antistatic agent, an inorganic filler, a glass fiber, a conductivity imparting agent, an EMI shielding agent, a magnetic property imparting agent, .

The additive may be used within a range that does not adversely affect the physical properties of the poly (arylene ether) resin composition of the present invention.

The coating material of the present invention is characterized by being produced from the poly (arylene ether) resin composition of the present invention.

The covering material is excellent in flexibility and flame retardancy, and can be usefully used for a covering material for a conductor.

The coating material of the present invention can be obtained by, for example, primary mixing the poly (arylene ether) resin composition together with the above additives in a mixer or a super mixer, followed by a twin-screw extruder, a single-screw extruder Kneaded in a temperature range of 200 to 290 ° C by using one of various mixing processing devices such as kneader, roll-mill, kneader or banbury mixer and then extruded to form a pellet, And this pellet is sufficiently dried by using a dehumidifying dryer or a hot air dryer and then injection-processed.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention within the scope and spirit of the following claims, Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example  1 to 5

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 Followed by extrusion processing (using a pelletizer) to obtain pellets. The pellets were dried at 80 ° C for 4 hours or more, injection molded, and left for 1 day at room temperature.

Comparative Example  1 to 2

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.

Poly (phenylene ether) (MEP MEP 100F, MI (300 DEG C / 5 kg): 8 to 12, weight average molecular weight 30,000 to 33,000, Tg: 215 DEG C) Resin (PPE1)

* Random polypropylene resin (PP1): Polymirae H5416K (MI (230 DEG C / 5 kg): 12, Elongation: 500%)

Styrene block copolymer (SBC1): Crayton G1657 (styrene content: 13 wt%, MI (230 DEG C / 5 kg): 22, Shore A: 47, elongation: 750%

Styrene block copolymer (SBC2): Crayton A1536 (styrene content: 42 wt%, MI (260 DEG C / 5 kg): 7, Shore A: 65, Elongation: 660%

* High heat resistant polyolefin block copolymer (PBC): LG Chem HT170 (density: 0.875 g / cm3, melting point: 123 占 폚, TMA: 100 占 폚, elongation 800%, Shore A 77, ° C / 2.16 kg): 1.0 to 1.4, ethylene content: 65 to 70%

Flame retardant 1: melamine polyphosphate (Ciba Melapur 200, nitrogen content 43 wt.%, Phosphor content 13 wt.%)

Flame retardant 2: Organophosphate (Clariant OP1230, Phosphorus content of 24% by weight, particle size: 20 to 40 탆)

* Mineral oil: GS Caltex 150N

[Test Example]

The properties of the poly (arylene ether) resin composition specimens prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were measured by the following methods, and the results are shown in Table 1 below.

* Tensile strength and elongation: measured according to ASTM D638 method.

Flexural Modulus: Measured according to ASTM D790 method.

* Shore A: Measured according to ASTM D 2240 method.

* Flammability (UL-94): Measured using 1/16 inch thick specimens

division Example Comparative Example One 2 3 4 5 One 2 Furtherance
(%) PPE1 30 28 31 30 30 10 30 PP 4 9 9 9 - 20 20 PBC 20 19 20 20 29 - - SBC1 - - - 5 - 20 20 SBC2 20 18 21 15 20 20 - Flame Retardant 1 13 13 10 10 10 20 10 Flame Retardant 2 7 7 5 5 5 10 5 Mineral oil 6 6 4 6 6 - 15 Properties Tensile strength (Kgf / cm ² ) 143 150 175 150 130 71 130 Tensile elongation (%) 142 140 162 151 250 300 210 Flexural modulus
(Kgf / cm ² ) 860 1100 911 831 750 696 613 Hardness (Shore A) 88 90 89 88 84 88 85 UL94 (1.6 mm) V-1 V-1 V-1 V-1 V-1 BO BO

As shown in Table 1, in the case of the poly (arylene ether) resin composition according to the present invention (Examples 1 to 5) and the poly (arylene ether) resin composition not containing the high heat resistant olefin copolymer It was confirmed that the balance of physical properties was excellent and the tensile strength and flame retardancy were particularly excellent as compared with Comparative Examples 1 and 2.

Claims (18)

I) poly (arylene ether) resins; Ii) olefin copolymers; And iii) a styrene block copolymer.
Poly (arylene ether) resin composition. The method according to claim 1,
The poly (arylene ether) resin composition comprises i) 20 to 60% by weight of a poly (arylene ether) resin; Ii) from 15 to 50% by weight of an olefin copolymer; And iii) 15 to 40% by weight of a styrene block copolymer.
Poly (arylene ether) resin composition. The method according to claim 1,
Wherein the i) poly (arylene ether) resin has an intrinsic viscosity of 0.35 dl / g or more
Poly (arylene ether) resin composition. The method according to claim 1,
The olefin copolymer (ii) has a melting point of 100 ° C or more
Poly (arylene ether) resin composition. The method according to claim 1,
The ii) olefin copolymer is characterized by having a TMA (Thermal Mechanical Analysis) of 70 ° C or higher
Poly (arylene ether) resin composition. The method according to claim 1,
The ii) olefin copolymer is characterized in that the H-index is less than 20
Poly (arylene ether) resin composition. The method according to claim 1,
The ii) olefin copolymer has a molecular weight distribution (PDI) of 2.0 to 4.5
Poly (arylene ether) resin composition. The method according to claim 1,
The iii) styrene block copolymer is characterized in that the styrene content is 10 to 50% by weight
Poly (arylene ether) resin composition. The method according to claim 1,
The poly (arylene ether) resin composition is characterized by further comprising a mineral oil
Poly (arylene ether) resin composition. 10. The method of claim 9,
Wherein the mineral oil is contained in an amount of 0.1 to 20% by weight based on 100% by weight of the total of the poly (arylene ether) resin composition
Poly (arylene ether) resin composition. 10. The method of claim 9,
Wherein the mineral oil is contained in an amount of 10 to 100 parts by weight based on 100 parts by weight of the total of the styrene copolymer
Poly (arylene ether) resin composition. The method according to claim 1,
Wherein the poly (arylene ether) resin composition further comprises a polypropylene resin (however, the olefin copolymer is not the same as the above-mentioned (ii) olefin copolymer)
Poly (arylene ether) resin composition. 13. The method of claim 12,
Characterized in that the polypropylene resin is contained in an amount of 30% by weight or less based on 100% by weight of the total of the poly (arylene ether) resin composition
Poly (arylene ether) resin composition. The method according to claim 1,
Wherein the poly (arylene ether) resin composition further comprises a flame retardant
Poly (arylene ether) resin composition. The method according to claim 1,
Characterized in that the flame retardant is a phosphorus flame retardant
Poly (arylene ether) resin composition. The method according to claim 1,
The flame retardant is contained in an amount of 5 to 30% by weight based on 100% by weight of the total of the poly (arylene ether) resin composition
Poly (arylene ether) resin composition. The method according to claim 1,
The poly (arylene ether) resin composition comprises i) 20 to 50% by weight of a poly (arylene ether) resin; Ii) from 15 to 50% by weight of an olefin copolymer; Iii) from 15 to 40% by weight of a styrene block copolymer; Iv) 0.1 to 20% by weight of mineral oil; V) polypropylene resin (however, not the same as the above-mentioned ii) polypropylene resin) 0 to 30% by weight; And vi) from 5 to 30% by weight of a flame retardant;
Poly (arylene ether) resin composition. A poly (arylene ether) resin composition according to any one of claims 1 to 17,
clothing material.