KR100744008B1 - Composition of multi-purpose carbon master batch - Google Patents

Abstract

Provided is a multi-purpose carbon master batch, which is applicable to general plastics and engineering plastics, has excellent dispersibility, good workability, and superior blackness, and hardly causes a decline in mechanical properties of plastics. The multi-purpose carbon master batch is obtained by adding 88-90 parts by weight of a carbon black inorganic filler, 10-30 parts by weight of a compatibilizer, 5-20 parts by weight of a polyethylene wax type dispersant, 0.5-3 parts by weight of an activator, and 0.5-3 parts by weight of a resin stabilizer to 100 parts by weight of a polyethylene mixture consisting of polyethylene and ethylene-alpha-olefin copolymer.

Description

Multifunctional black master batch composition {COMPOSITION OF MULTI-PURPOSE CARBON MASTER BATCH}

The present invention relates to a black master batch composition used in a product that requires a UV stabilizing effect and coloring of the polymer material at the same time, more specifically, excellent dispersibility applicable from general purpose plastics to engineering plastics, workability in manufacturing It relates to a multi-Purpose black master batch composition that is good, excellent in blackness when added, no deterioration in mechanical properties, excellent compatibility with dilution resins, and moldability.

In general, the black master batch is used in a product which simultaneously requires a UV stabilizing effect and coloring of the polymer material, and a black master batch for general purpose plastics such as polyethylene, polypropylene, and polyvinyl chloride; Black master batches for engineering plastics such as ABS, polystyrene, polycarbonate, polyester, etc. are used.

In general, in the case of using a general-purpose polyolefin resin as a dilution resin, if shear stress is applied during mixing, melt viscosity decreases, making it difficult to fill a large amount of carbon black, and also Dispersion is difficult, making it difficult to create a master batch with high blackness.

The black master batch used in the prior art has a disadvantage in that blackness and mechanical properties are poor when added, and a wax-type polymer added to improve the dispersibility of carbon black, which is a black pigment, is decomposed during molding and decomposed in a molded article. There was a disadvantage of impaired appearance and paintability.

In general, the performance evaluation of a blackmaster batch is usually evaluated in the following five items. -Color Strength (the degree to which the dilution resin is colored); Blue Tone (a blue color should be visible and the blackness is high); Masterbatch Compatability (Pigment should be well-dissolved in the master batch base resin and finally dispensed in diluent resin); Dispersability (pigment should be well distributed in dilution resin without clumping); UV Stability (must be long to maintain 50% of initial elongation during UV irradiation).

The smaller the carbon black particles in the blackmaster batch, the higher the blue tone and blackness in the texture, and the less dispersed. In general, the carbon black particle size of 23nm is used a lot, but it is most preferable to maintain the particle size of about 15 ~ 17nm, and the larger the particle size, the higher the color power and blackness is necessary to properly balance (Balance).

The present invention is proposed to solve the above disadvantages, excellent dispersibility applicable to general-purpose plastics to engineering plastics, good workability during manufacturing, excellent blackness when added, there is no degradation of mechanical properties, It is an object of the present invention to provide a multi-purpose black master batch composition having excellent compatibility with dilution resin and molding processability.

Multifunctional black master batch composition of the present invention to achieve the above object,

88 to 90 parts by weight of carbon black inorganic filler, 10 to 30 parts by weight of a compatibilizer, 5 to 20 parts by weight of a dispersing agent in the form of polyethylene wax, and a lubricant, in 100 parts by weight of a polyethylene mixture composed of polyethylene and an ethylene-α-olefin copolymer. 0.5-3 weight part and 0.5-3 weight part of resin stabilizers are added,

It is usually prepared by mixing at a temperature of 160 ~ 230 ℃ using a conventional mixing equipment such as extruder, Kneader, Banbury Mixe.

In addition, additives such as heat aging agents, ultraviolet absorbers, pigments, etc. may be appropriately mixed at any stage during mixing.

The polyethylene has a melt flow index (190 ° C./2.16 kg) measured by ASTM D-1238 method of 40.0 to 50.0 g / 10 minutes, and a density measured by ASTM D-792 method of 0.910 to 0.925 g / cm 3. ,

The ethylene-α-olefin copolymer has a Mooney viscosity (ML1 + 4, 121 ° C measurement) measured by ASTM D-1646 method is 10 to 50, the density measured by ASTM D-792 is 0.850 ~ 0.920 g / Cm3 is used,

The ethylene-α-olefin copolymer uses ethylene-propylene, ethylene-butene, ethylene-hexene, ethylene-octene or a mixture thereof in which the content of α-olefin monomer is 10 to 50% by weight.

When the content of the α-olefin monomer is less than 10% by weight, the tensile and impact resistance is not good when a large amount of carbon black is added. When the content of the α-olefin monomer is more than 50% by weight, the elongation is improved.

The polyethylene mixture composed of the polyethylene and the ethylene-α-olefin copolymer is composed of 40 to 60% by weight of polyethylene and 40 to 60% by weight of the ethylene-α-olefin copolymer.

The carbon black has an average particle diameter of about 15 to 20.0 nm. If the average particle diameter is less than 15 nm, the dispersibility with the substrate (Base Resin, Co., Ltd.) is poor, the tensile properties are poor, and if the average particle diameter is more than 20.0 nm, it is difficult to obtain the desired blackness, and there is a problem of poor impact resistance.

The compatibilizer is added to improve the compatibility of a large amount of carbon black and the base (Base Resin),

As the compatibilizer, a polar monomer is introduced into the polyolefin main chain and then mixed with general polyethylene or polypropylene for improving dispersibility. In this case, an unsaturated carboxylic acid or anhydride is used as the polar monomer, and the anhydride is usually acrylic acid, methacrylic acid or maleic anhydride. Maleopymarinic acid and tetrahydrophthalic anhydride are used.

The polyolefin compatibilizer is usually prepared by a polyolefin melting reaction method in which a polar monomer and a polymerization initiator are melt kneaded together with a polyolefin in an extruder to obtain a copolymer.

The lubricant is added to improve the extrudability of the composition and to prevent adhesion, and is usually used by mixing calcium stearate and zinc stearate.

The resin stabilizer is to give an antioxidant effect of the composition during molding processing, usually pentaerythryl-tetrakis (3- (3,5-tetrabutyl-4-hydroxyphenyl) -propionate, 4,4 '-Thio-bis (6-t-butyl-3-methylphenol), phenol, 2,4-bis (1,1-dimethylethyl) -phosphite or mixtures of two or more thereof are used.

The polyethylene wax is added to improve the dispersion of carbon black, and it is preferable to use a non-emulsified polyethylene wax having a specific gravity of 0.89 to 0.94, a softening point of about 150 ° C, and a number average molecular weight of 1,500 to 1,900.

Hereinafter, described in more detail through an embodiment of the present invention,

EXAMPLE

88 to 90 parts by weight of carbon black inorganic filler, 10 to 30 parts by weight of a compatibilizer, 5 to 20 parts by weight of a dispersing agent in the form of polyethylene wax, and a lubricant, in 100 parts by weight of a polyethylene mixture composed of polyethylene and an ethylene-α-olefin copolymer. It is to add 0.5 to 3 parts by weight and 0.5 to 3 parts by weight of the resin stabilizer,

It is usually prepared by mixing at a temperature of 160 ~ 230 ℃ using a conventional mixing equipment such as extruder, Kneader, Banbury Mixe.

In addition, additives such as heat aging agents, ultraviolet absorbers, pigments, etc. may be appropriately mixed at any stage during mixing.

50 wt% of polyethylene having a melt flow index (190 ° C./2.16 kg) measured by ASTM D-1238 method, 45.0 g / 10 min, and a density of 0.92 g / cm 3 measured by ASTM D-792 method, and α-olefin. A polyethylene mixture was prepared by mixing 50% by weight of an ethylene-α-olefin copolymer of ethylene-propylene having a monomer content of 40% by weight,

88 parts by weight of carbon black inorganic filler having an average particle diameter of 17.0 nm, 15 parts by weight of a compatibilizer, 15 parts by weight of a dispersant in the form of polyethylene wax, calcium stearate and zinc stearate were mixed 2 parts by weight of the lubricant and 2 parts by weight of the resin stabilizer were added and mixed at 200 ° C. using a conventional mixer to form a multifunctional blackmaster batch composition.

As the compatibilizer, general polyethylene was used to introduce a polar monomer into the polyolefin main chain and to improve dispersibility, and acrylic acid was used as the polar monomer.

The resin stabilizer used phenol.

The product using the multifunctional black master batch, a composition prepared as described above, was compared with a product using a base black resin and a conventional black master batch applied to general-purpose plastics and engineering plastics. The chemical properties are shown in Table 5.

1. Physical Properties

[Table 1] Promoting weather resistance before (dilution resin: Polyethylene)

 division Melt-Hmm Index (g / 10min) Tensile Strength (MPa) Elongation at Break (%) Flexural Strength (MPa) Izod impact strength (J / m)  Test Methods BaseResin (PE) 12.0 8.08 1.7 x 102 5.45 Not broken Tensile Strength: ASTM D 638 Flexural Strength: ASTM D 790 Impact Strength ASTM D 256 Traditional Blackmaster Batch (PE) 2.4 12.0 1.4x102 6.51 Not broken Multifunctional Blackmaster Batch (PE) 11.0 11.6 1.4x102 6.82 Not broken

[Table 2] After accelerated weathering resistance (dilution resin: Polyethylene)

division Tensile Strength (MPa) Elongation at Break (%) Flexural Strength (MPa) Izod impact strength (J / m) Test Methods BaseResin (PE) 8.44 1.6 x 102 6.04 Not broken  Accelerated weathering KS F 2274 (WS-A type X 100h) Traditional Blackmaster Batch (PE) 12.2 1.4x102 6.40 Not broken Multifunctional Blackmaster Batch (PE) 12.0 1.3 x 102 6.53 Not broken

[Table 3] Promoting weather resistance before (dilution resin: ABS)

 division Melt-Hmm Index (g / 10min) Tensile Strength (MPa) Elongation at Break (%) Flexural Strength (MPa) Izod impact strength (J / m)  Test Methods ABS (Base Resin) 9.0 39.8 9.5 60.6 118 Tensile Strength: ASTM D 638 Flexural Strength: ASTM D 790 Impact Strength ASTM D 256 Traditional Blackmaster Batch (ABS) 7 38.7 7.4 57.7 95 Multifunctional Blackmaster Batch (ABS) 15.0 46.4 61 63.3 339

[Table 4] After accelerated weather resistance (dilution resin: ABS)

 division Tensile Strength (MPa) Elongation at Break (%) Flexural Strength (MPa) Izod impact strength (J / m)  Test Methods ABS (Base Resin) 39.2 3.8 60.9 106 Accelerated weathering KS F 2274 (WS-A type X 100h) Traditional Blackmaster Batch (ABS) 37.8 4.5 61.0 89 Multifunctional Blackmaster Batch (ABS) 47.1 10 66.3 288

2. Chemical Properties

[Table 5] Chemical Characterization Results

division  Reference value Conventional Blackmaster Batch (PE) (g / m2) Multifunctional Blackmaster Batch (PE) (g / m2) Test Methods Sodium chloride (10%) ± 0.5 0.21 0.14  KS M 3407 Sulfuric acid (30%) ± 0.5 0.12 0.14 Nitric Acid (40%) ± 1.0 0.27 0.29 Sodium hydroxide (40%) ± 0.5 -0.05 -0.06 Ethyl alcohol (50%) ± 4.0 1.14 1.00

Heavy metal (ROHS) analysis results of the product using the multifunctional blackmaster batch of the present invention are shown in Table 6 below.

Table 6 Results of Heavy Metals (ROHS) Analysis

division unit content Test Methods Pb mg / kg 5.5 ISO 6101-2 Cadmium (Cd) mg / kg 3.8 EN 1122 Hexavalent chromium (Cr ⁺⁶ ) mg / kg Not detected EPA 3060A, 7196A Mercury (Hg) mg / kg Not detected EPA 3052, 7471A

Regulatory concentrations for heavy metals are shown in Table 7 below.

[Table 7] Regulation of Heavy Metals

Target substance Regulatory Concentration (ppm) Remarks Cadmium (Cd) 100  Concentration Determination by European Commission on 18 August 2005 Pb 1,000 Mercury (Hg) 1,000 Hexavalent chromium (Cr ⁺⁶ ) 1,000

[Table 8] Dissolution test analysis

division Potassium Permanganate Consumption (mg / L) Heavy metals (mg / L) Evaporation residue (mg / L) Acrylonitrile (mg / L) Test Methods PE (Base resin) 1.6 1.0 or less 4.0 - Food Code Existing Product (PE) 1.3 1.0 or less 6.5 - Product Development (PE) 1.0 1.0 or less 2.0 - ABS resin 5.7 1.0 or less 4.5 0.012 Existing Product (ABS) 2.2 1.0 or less 2.0 0.010 Development product (ABS) 1.1 1.0 or less 1.5 0.007 Reference value below 10 1.0 or less 30 or less 0.02 or less

In addition, as a result of measuring carbon black dispersibility and blackness and carbon black content of the product using the multifunctional black master batch of the present invention, the carbon black dispersibility was about 4.5grading, the blackness was about 5.0%, and the carbon black content was about 47.2%. Was measured.

Excellent dispersibility applicable from general purpose plastics to engineering plastics as described above, good workability during manufacturing, good blackness when added, no deterioration of mechanical properties, compatibility with dilution resin and It is possible to provide a multi-purpose blackmaster batch composition having excellent molding processability.

In addition, heavy metals of hexavalent chromium (Cr ⁺⁶ ) and mercury (Hg) were not emitted from the products manufactured using the Multi-Purpose blackmaster batch composition. It was detected as follows.

Claims (10)

88 to 90 parts by weight of carbon black inorganic filler, 10 to 30 parts by weight of a compatibilizer, 5 to 20 parts by weight of a dispersing agent in the form of polyethylene wax, and a lubricant, in 100 parts by weight of a polyethylene mixture composed of polyethylene and an ethylene-α-olefin copolymer. A multifunctional black master batch composition, comprising 0.5 to 3 parts by weight and 0.5 to 3 parts by weight of a resin stabilizer. The method of claim 1, The polyethylene mixture is a multi-functional black master batch composition, characterized in that 40 to 60% by weight of polyethylene and 40 to 60% by weight of ethylene-α-olefin copolymer. The method according to claim 1 or 2, The polyethylene has a melt flow index (190 ° C./2.16 kg) of 40.0 to 50.0 g / 10 minutes as measured by ASTM D-1238, and a density of 0.910 to 0.925 g / cm 3 measured by ASTM D-792. Multifunctional blackmaster batch composition, characterized in that. The method according to claim 1 or 2, The ethylene-α-olefin copolymer, The pattern viscosity measured by ASTM D-1646 method is 10-50, and the density measured by ASTM D-792 is 0.850-0.920 g / cm3, A multifunctional blackmaster batch composition characterized in that ethylene-propylene, ethylene-butene, ethylene-hexene, ethylene-octene or mixtures thereof are used in which the content of α-olefin monomer is 10 to 50% by weight. The method of claim 1, The carbon black has a multi-functional black master batch composition, characterized in that the average particle diameter is 15 ~ 20.0nm. The method of claim 1, The compatibilizer is a multi-functional black master batch composition, characterized in that mixed with a general polyethylene or polypropylene for introducing a polar monomer into the polyolefin backbone to improve dispersibility. The method of claim 6, As the polar monomer, unsaturated carboxylic acid or anhydride is used, The anhydride is acrylic acid, methacrylic acid, maleic anhydride. Multifunctional blackmaster batch composition, characterized in that maleopimarinic acid, tetrahydrophthalic anhydride is used. The method of claim 1, The lubricant is a multifunctional black master batch composition, characterized in that using a mixture of calcium stearate and zinc stearate. The method of claim 1, Resin stabilizers were pentaerythryl-tetrakis (3- (3,5-tetrabutyl-4-hydroxyphenyl) -propionate, 4,4'-thio-bis (6-t-butyl-3-methyl Phenol), phenol, 2,4-bis (1,1-dimethylethyl) -phosphite or a mixture of two or more thereof. delete