AU738475B2 - Carbon black compositions and improved polymer compositions - Google Patents

Description

rVuu I 1 21&i91 Regulation 3.2(2)

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT *444b..

4 4e 4444*4 4* 4 4* a *4* *4 4* 4 *44 *44t 4444 44 4 44. 4* 4* Application Number: Lodged: Invention Title: CARBON BLACK COMPOSITIONS AND IMPROVED POLYMER

COMPOSTONS

The following statement Is a full description of this Invention, Including the best method of performing It known to us IP Australia CD Documents received on: 0 2 5MAY 1999

CD

Batch No:

(I,

1 CARBON BLACK COMPOSITIONS AND IMPROVED POLYMER

COMPOSITIONS

Field of the Invention The present invention relates to carbon black compositions comprising polyethers. The compositions may be produced by incorporating polyethers onto fluffy carbon black in a pelletizing process to produce free flowing, low dust, attrition resistant carbon black pellets which are easily dispersible in most polymeric systems and provide enhanced rheological and mechanical properties.

10 The present invention also relates to polymer compositions which ooooo incorporate the carbon black compositions of the present invention.

Background of the Art Carbon blacks produced by a furnace process generally have bulk densities ranging from 0.02 to 0.1 gram/cubic centimeter (g/cc) and are generally known as fluffy carbon blacks. Fluffy carbon blacks are generally easy to disperse in liquids, and in some polymeric systems. However, fluffy carbon blacks are generally cohesive and, hence difficult to handle for purposes such as conveying and weighing.

***Fluffy carbon blacks are agglomerated by various types of mechanical processes, either in the dry state, or with the aid of a liquid to produce pellets with improved handling characteristics. Common liquid pelletizing agents are .:oil and water. The process of agglomerating fluffy carbon blacks to form carbon black pellets is generally referred to as pelletizing.

Unfortunately, generally utilized densification or agglomeration (pelletizing) processes have detrimental effects on the dispersion characteristics of the carbon black. Therefore it is recognized in the art that in pelletizing carbon blacks there is a fine balance between acceptable handling characteristics and ease of dispersion.

A process for pelletizing carbon black is disclosed in U.S. Patent No.

2,065,371 which describes a typical wet pelletization process whereby the fluffy 2 carbon black and a liquid, typically water, are combined and agitated until spherical beads are formed. These beads are then dried to reduce the water content preferably to below 1% to form carbon black pellets.

Prior art patents also disclose the use of binder additives in a wet pelletization process to further improve the pellet handling characteristics.

U.S. Patent No. 2,850,403 discloses the use of carbohydrates e.g. sugar, molasses, soluble starches, saccharides and lignin derivatives as pellet binders in the range of 0.1% to by weight, based on the dry carbon black. The preferred drying temperature of the wet pellet is disclosed as 150 to 4250 C which together with the residence time is sufficient to carbonize the binder.

.ooooi U.S. Patent No. 2,908,586 discloses the use of a rosin emulsion as pellet 00o0 o ~.binders as an alternative to carbohydrates. The preferred level of rosin binder is in the range 0.5% to by weight, based on the dry carbon black.

U.S. Patent No. 2,639,225 discloses the use of sulphonate and sulphate anionic surfactants as pellet binders at levels of 0.1% to by weight, based on the dry carbon black.

S"U.S. Patent No. 3,565,658 discloses the use of a fatty amine ethoxylate nonionic surfactant where the level of ethoxylation ranges from 2 to 50 moles of ethylene oxide per fatty amine group. The preferred level of surfactant in the pelletizing water is in the range 0.05% to by weight, based on the dry carbon black.

Similarly, U.S. Patent No. 3,645,765 discloses the use of a fatty acid or rosin acid ethoxylate, non-ionic surfactant where the level of ethoxylation is 5 to moles ethylene per acid group. The preferred level of addition on the carbon black is in the range 0.1% to 10%, by weight, based on the dry carbon black.

Soviet Union Patent No. 937,492 claims the benefits of using 0.1% to by weight, based on the dry carbon black, of an aqueous solution of a reaction product generated from urea and an ethoxylated alkylolamide. The preferred level of ethoxylation is 1 to 7 moles of ethylene oxide per alkylolamide molecule.

U.S. Patent No. 3,844,809 discloses the reduction in pellet dust levels by incorporating 0.4% to by weight, based on the dry carbon black of an aqueous solution containing 0.001% to by weight, of a nonionic surfactant containing randomly repeating poly(ethylene oxide) and poly (dimethyl silicone) groups. Molasses is also included at substantially higher concentration (up to by weight) as a co-binder and nitric acid (up to 15%, by weight) as an oxidizing source.

The use of carbohydrates, rosin or surface active agents as disclosed in the above patents is focused towards improving pellet handling qualities. The patents do not disclose that the pelletizing treatments affected the performance properties of the carbon black in the final product applications, which are typically rubber orientated.

Japanese Patent No. 1,201,369 discloses the use of a carboxylic acid oeeoo type amphoteric surfactant in a concentration range 0.001% to by weight, in the pelletizing water to produce carbon black pellets with low adhesion and excellent dispersibility.

U.S. Patent No. 3,014,810 discloses the benefits of wet pelletizing a range of pigments, including carbon blacks, with a blend of a quaternary ammonium compound and a bis(-2-hydroxyethyl)alkyl amine. Improvements in dispersion rate, viscosity stability and antistatic properties are disclosed for the blend of surface active agents.

Pelletizing with oil, in the presence and absence of water is disclosed in U.S. Patent No. 2,635,057, U.S. Patent No. 3,011,902 and U.S. Patent No.

4,102,967 as beneficial in improving the handling properties of carbon black pellets.

Several patents, including U.S. Patent No. 2,511,901, U.S. Patent No.

2,457,962, U.S. Patent No. 4,440,807, U.S. Patent No. 4,569,834, U.S. Patent No. 5,168,012 and Japanese Patent No. 77,130,481 disclose polymers in emulsion, organic solvent solutions and in molten form as means of modifying the pellet properties of carbon black.

U.S. Patent No. 4,277,288 discloses a fluidised granulation process for producing free-flowing dustless pigment granules in the absence of water. The organic component required to produce a dustless granule consists of two components, 5-20 phr of a non-aqueous granulating aid and a non-ionic surfactant for example sorbitan oleate ethoxylate as a second component. The bulk of the disclosure relates to producing freeflowing organic and inorganic pigments, including carbon black.

U.S. Patent No. 4,397,652 also discloses a process for producing negligible dust preparations of organic dyes and optical brighteners. The process involves the dry blending, between 30 and 800 C, of the dye, or optical brightener, with 2-10%, by weight, of an adhesive selected from the group consisting of polyhydric alcohol sorbitol); manitol; manitose; lactose; hydrated dextrose; neopentyl glycol; and polyethylene glycol with a molar mass above 3,000. Also included in the composition is 1-10% of a dusting aid selected from the group consisting of fatty acid ethanolamide; fatty acid amide; .oo.oi alkyl alcohol; substituted phenol; and polyethylene glycol with a molar mass between 200 and 1000.

U.S. Patent No. 4,230,501 discloses a pigment concentrate, dispersible in plastics, which is prepared by combining 51-85%, by weight, of a pigment and 14-49%, by weight, of a waxy component. The waxy component is disclosed as being predominantly a natural, petroleum or synthetic wax which has been blended with either polyethylene glycol or a hydrocarbon resin to reduce the melt viscosity and allow better incorporation of the pigments Polyethylene glycol is previously known as an additive for direct compounding into thermoplastic compositions.

U.S. Patent No. 4,013,622 discloses the incorporation of 100 to 600 ppm S•of polyethylene glycol in the molar mass range of 600 to 20,000 (preferably 1300 to 7500) to reduce the breakdown of polyethylene during blown film operations which is observed as gel formation.

U.S. Patent No. 4,812,505, U.S. Patent No. 4,440,671 and U.S. Patent No. 4,305,849 disclose the use of polyethylene glycols in the molar mass range 1,000 to 20,000 as beneficial for reducing the heat and water-treeing characteristics in polyolefin compositions for electrical insulation. Similarly U.S.

Patent No. 4,612,139 extends this concept of water-tree reduction to include the polyethylene glycol in semiconductive polyolefin compositions containing carbon black.

Similar compositions are claimed in German Patent DE 27 23 488 where polyethylene glycol and other mobile additives are disclosed as being beneficial to reduce the interlaminar adhesion between the insulation layer and outer conductive layer in an electric cable construction. Polyethylene glycol and branched ethoxylate molecules are disclosed as plasticisers for ethylene-acrylic acid copolymers in U.S. Patent No. 3,361,702.

United Kingdom Patent GB 975,847 discloses the use of polyethylene glycol, or an aliphatic derivative, in an aqueous solution as a means of producing agglomerates of organic rubber chemicals. A dough is formed as an intermediate which is then converted into pellets and dried at low temperatures.

SUMMARY OF THE INVENTION The present invention comprises carbon black compositions that in their 0 dry form have improved handling characteristics and that impart enhanced performance characteristics to polymer compositions. The carbon black 15 compositions comprise: carbon black and 0: 0.1% to 50%, preferably 1 to 20%, by weight, of at least one binder which is a polyethylene oxide polypropylene oxide polyethylene oxide block copo!ymer.

20 It is also preferred that the polyether binder have an HLB value of 8.0 to 30. HLB value refers to hydrophile-lipophile balance value which may be determined by the method described in Non-ionic Surfactants Volume 23, edited by Martin Schick (Marcel Dekker Inc. (New York) 1987; ISBN 0-8247-7530-9), page 440. Non-ionic Surfactants Volume 23 provides equations relating the structure of the surfactant molecule to HLB value. HLB value is also discussed in the following journal articles: Griffin J. Soc. Cosmetic Chemist, Vol. 1, page 311 et seq. (1949) and Vol. 5, page 249 et seq. (1954). From data relating to the weight percentage of ethylene oxide in the molecule, saponification number of the ester linkage and acid value of the "fatty" acid, HLB value may be directly calculated from one of the following equations: for polyhydric fatty acid esters: I 6 HLB 20 where S saponification number of the ester and A acid number of the acid; and for ethoxylated polyhydric alcohols: HLB (E where E weight of percent ethylene oxide and P weight pigment of polyhydric alcohol.

While any carbon black may be utilized in the compositions of the present invention, preferably the carbon black component of the carbon black composition has a nitrogen surface area (N 2 SA) of 15 to 1800 m 2 a fluffy dibutyl phthalate absorption value (DBP) of 50 to 350 cc/100g and a cetyl 10 trimethylammonium bromide absorption value (CTAB) of 15 to 1500 m 2 /g.

.:oooi The carbon black compositions may be produced in any manner known oooo in the art, such as by physically blending the components, melt mixing the components or combining the components while pelletizing the carbon black.

Preferably the carbon black compositions are obtained by pretreating the carbon black with the binder.

"The carbon black compositions may also be produced by a pelletizing process by: 0:0: contacting a fluffy carbon black in a pin pelletizer with an aqueous S. solution containing a binder selected from the foregoing groups of compounds wherein the preferred level of binder in the pelletizing water is from 0.5% to 50%; more preferably 20-40%, by weight; and heating the wet pellets under controlled temperature and time parameters such that the water is removed from the pellets but the binder does not undergo substantial decomposition, and the final binder level on the dry carbon black is from 0.1%to The present invention also includes new polymer compositions comprising: a polymer component and 0.1-65%, preferably 0.1-20%, by weight, of a composition comprising a carbon black and 0.1-50%, preferably 1-20%, of at least one polyether binder component. Preferably, the carbon black is pretreated with the binder component. The preferred carbon blacks, and binder components are as set forth above with respect to the carbon black S 'I' 7 compositions of the present invention. The polymer compositions may include other conventional additives such as pigments, reinforcing agents and the like.

While any polymer may be utilized in the polymer composition of the present invention, preferred polymers for use in the polymer compositions of the present invention include, but are not limited to: a) homo or copolymers and graft polymers of ethylene where the comonomers are selected from butene, hexene, propene, octene, vinyl acetate, acrylic acid, methacrylic acid, esters of acrylic acid, esters of methacrylic acid, maleic anhydride, half ester of maleic anhydride, and carbon monoxide; b) elastomers selected from natural rubber, polybutadiene, polyisoprene, random styrene butadiene rubber (SBR), polychloroprene, acrylonitrile butadiene, ethylene propylene co and terpolymers; o: c) homo and copolymers of styrene, including styrene butadiene styrene linear and radial polymer, acrylonitrile butadiene styrene (ABS) and styrene acrylonitrile (SAN); d) linear and branched polyether or polyester polyols; e) crystalline and amorphous polyesters and polyamides; f) alkyd resins, rosin acids or rosin esters, hydrocarbon resins produced from thermal or Friedel Crafts polymerization of cyclic diene monomers such as dicyclopentadiene, indene, cumene; and g) hydrocarbon oils such as parafinnic oil, naphthenic oil and hydrogenated naphthenic oil.

The polymer compositions of the present invention may be produced in any manner known to the art for combining polymers and dry or aqueous components.

The present invention further includes articles of manufacture produced from the polymer compositions of the present invention.

For use in semiconductive wire and cable applications, a typical formulation of the present invention preferably comprises: 25-55%, by weight, of a composition comprising carbon black and 0.5 to parts per 100 parts of carbon black of at least one polyether binder component; 0 to by weight a stabilizer or antioxidant 0 to by weight an organic peroxide, preferably dicumyl peroxide; 0 to 10%, by weight a vinyl silane; the remainder being a polymer, or a blend of polymers, selected from the following group: ethylene homopolymer; ethylene copolymerized with one or more alpha olefins, such as propylene, butene, or hexene; ethylene copolymerized with propylene and a diene monomer, preferably norbomene; and ethylene copolymer with one or more monomers selected from vinyl acetate, acrylic acid, methacrylic acid, esters of acrylic or methacrylic acid containing 1 to 8 carbon atoms, maleic anhydride or a monoester derived from fumaric or maleic acid, vinyl chloride or vinylidene chloride.

The curable semi-conductive composition of the present invention may additionally include an additive polymer such as acrylonitrile butadiene t elastomer containing 25-55%, by weight acrylonitrile.

For use as a masterbatch composition, a typical formulation of the present invention preferably comprises: 30-60%, by weight, of a composition comprising a carbon black and 0.1 to 50%, preferably 1-20%, of at least one binder component; and 70-40%, by weight of an ethylene homopolymer or copolymer, where the comonomer is preferably selected from hexene, propene, butene, octene or vinyl acetate. Preferably, the polymer composition is polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene or a polyethylene wax. The masterbatch composition may additionally include antioxidants, peroxide decomposers, hindered amine light stabilizers, substituted benzophenone UV adsorbers or process aids.

An advantage of the carbon black compositions of the present invention is that in dry form the carbon black compositions of the present invention have improved handling properties in comparison with conventional fluffy or pelleted carbon blacks.

An advantage of the polymer compositions of the present invention is that the polymer compositions exhibit enhanced rheological, processing or mechanical properties.

Further advantages of the carbon black compositions, and the polymer compositions, of the present invention will become apparent from the following detailed description.

DETAILED DESCRIPTION OF THE INVENTION The present invention includes carbon black compositions which in dry form have improved handling characteristics and impart enhanced performance characteristics to polymer compositions.

The carbon black compositions comprise: carbon black and 0.1% to 50%, preferably 1 to 20%, by weight, of at least one binder which is a polyethylene oxide polypropylene oxide polyethylene oxide block S 15 copolymer.

It is preferred that the at least one binder have an HLB value of 8.0 to HLB value may be determined in the manner set forth above.

While any carbon black may be utilised in the compositions of the present invention, preferably the carbon black component of the carbon black composition 20 has a nitrogen surface area (N 2 SA) of 15 to 1800 m 2 a fluffy dibutyl phthalate absorption value (DBP) of 50 to 250 cc/100g and a cetyl triamethylammonium bromide absorption value (CTAB) of 15 to 1500 m 2 /g.

The carbon black compositions may be produced by any conventional technique for combining carbon black with dry or aqueous components.

Preferably the carbon black compositions are produced by pretreating the carbon black with the binder. The carbon black compositions may be produced, in dry form, by a conventional pelletising process. For example, the carbon black compositions of the present invention may be produced by contacting a fluffy carbon black in a pin pelletiser with an aqueous solution containing a binder selected from the foregoing groups of compounds wherein the level of binder in the pelletising water is from 05.% to 50%; and heating the wet pellets under controlled temperature and time parameters such that the water is removed from the pellets but the binder does not undergo substantial decomposition, and the final binder level on the dry carbon black is from 0.1% to The preparation of aqueous solutions containing the binder compositions used in the present invention is within the skill of one of ordinary skill in the art.

Pin pelletizers which may be utilized to produce the compositions of the present invention are known in the art and include the pin pelletizer described in U.S. Patent No. 3,528,785, the disclosure of which is hereby incorporated by reference. U.S. Patent No. 3,528,785 also describes a conventional pelletizing 10 process which may be utilized to produce the compositions of the present S. invention.

The present invention also includes new polymer compositions comprising: a polymer component and 0.1-65%, preferably 0.1-20%, by weight, of a 15 composition comprising a carbon black and 0.1-50%, preferably 1-20%, of at least one binder which is a polyethylene oxide polypropylene oxide polyethylene oxide block copolymer.

Preferably, the carbon black is pretreated with the binder component. The preferred carbon blacks, and binder components are as set forth above with 20 respect to the carbon black compositions of the present invention. For example, it is preferred that the binder component have an HLB value of 8.0 to 30. The polymer compositions may include other conventional additives such as pigments, reinforcing agents and the like.

While any polymer may be utilized in the polymer composition of the present invention, preferred polymers for use in the polymer compositions of the present invention include, but are not limited to: a) homo or copolymers and graft polymers of ethylene where the comonomers are selected from butene, hexene, propene, octene, vinyl acetate, acrylic acid, methacrylic acid, esters of acrylic acid, esters of methacrylic acid, maleic anhydride, half ester of maleic anhydride, and carbon monoxide; 11 b) elastomers selected from natural rubber, polybutadiene, polyisoprene, random styrene butadiene rubber (SBR), polychloroprene, acrylonitrile butadiene, ethylene propylene co and terpolymers; c) homo and copolymers of styrene, including styrene butadiene styrene linear and radial polymer, acrylonitrile butadiene styrene (ABS) and styrene acrylonitrile (SAN); d) linear and branched polyether or polyester polyols; e) crystalline and amorphous polyesters and polyamides; f) alkyd resins, rosin acids or rosin esters, hydrocarbon resins produced from thermal or Friedel Crafts polymerization of cyclic diene S. monomers such as dicyclopentadiene, indene, cumene; and g) hydrocarbon oils such as parafinic oil, naphthenic oil and hydrogenated naphthenic oil.

The polymer compositions of the present invention may be produced in 15 any manner known to the art for combining polymers and dry or aqueous components.

The present invention further includes articles of manufacture produced from the polymer compositions of the present invention.

For use in semiconductive wire and cable applications, a typical 20 formulation of the present invention comprises: 25-55%, by weight, of a composition comprising a carbon black and to 10 parts, per 100 parts of carbon black, of at least one binder which is a polyethylene oxide polypropylene oxide polyethylene oxide block copolymer; 0 to by weight a stabilizer or antioxidant; 0 to by weight an organic peroxide, preferably dicumyl peroxide; 0 to 10%, by weight a vinyl silane; the remainder being a polymer, or a blend of polymers, selected from the following group: ethylene homopolymer; ethylene copolymerized with one or more alpha olefins, such as propylene, butene, or hexene; ethylene copolymerized with propylene and a diene monomer, preferably norbornene; and ethylene copolymer with one or more monomers selected from vinyl acetate, acrylic acid, methacrylic acid, esters of acrylic or methacrylic acid containing 1 to 8 carbon atoms, maleic anhydride or a monoester derived from fumaric or maleic acid, vinyl chloride or vinylidene chloride.

The curable semi-conductive composition of the present invention may additionally include an additive polymer such as acrylonitrile butadiene elastomer containing 25-55%, by weight acrylonitrile.

For use as a masterbatch composition, a typical formulation of the present invention preferably comprises: 70-40%, by weight of an ethylene homopolymer or copolymer, where the comonomer is preferably selected from hexene, propene, butene, octene or vinyl acetate; and 15 30-60%, by weight, of a composition comprising a carbon black and 0.1 to 50%, preferably 1-20%, a binder component which is a polyethylene oxide polypropylene oxide polyethylene oxide block copolymer.

Preferably, the polymer composition is polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene or a 20 polyethylene wax. The masterbatch composition may additionally include I antioxidants, peroxide decomposers, hindered amine light stabilizers, substituted benzophenone UV adsorbers or process aids.

The effectiveness and advantages of various aspects and embodiments of the present invention will be further illustrated by the following examples wherein the following testing procedures were utilized.

The following testing procedures were utilized in the determination and evaluation of the analytical properties of the carbon blacks utilized in the following examples. The DBP (dibutyl phthalate adsorption value) of the carbon blacks utilized in the examples, expressed as cubic centimeters DBP per 100 grams carbon black (cc/100g), was determined according to the procedure set 13 forth in ASTM D2414. The nitrogen surface area (N 2 SA) of the carbon blacks utilized in the examples, expressed as square meters per gram (m 2 was determined according to ASTM test procedure D3037 Method A.

The carbon blacks pellets described in the following examples were evaluated utilizing the following testing procedures. The pellets were assessed for mass pellet strength using ASTM D1937. Pellet attrition was evaluated using a modified version of ASTM D 4324, wherein the ASTM test procedure was modified to generate the level of dust after shaking samples for 5 minutes.

The moisture content of the pellets was determined by drying the sample 10 to constant mass in an air circulating oven at 1500 C and then calculating •eel moisture percentage by comparing the weight prior to drying to the weight after drying.

The polymer compositions, including the polymer masterbatch compositions, described in the following examples were evaluated utilizing the following test procedures.

Melt index was determined by ASTM D 1238.

Pressure rise of the masterbatch compositions was determined by Sintroducing a 325 mesh (47 micron hole size) screen pack behind the breaker plate of a 0.025 meter (1 inch) single screw extruder fitted with a pressure 20 transducer to measure the pressure change in the region of the screen pack.

S"Viscosity of the polymer compositions was measured utilizing a Carri- Med CS viscometer, produced and sold by TA Instruments of Wilmington, Delaware, at the temperature, and utilizing the shear rate specified in the particular example.

Triple roll mill passes were evaluated by passing the polymer compositions through a triple roll mill and recording the number of passes required to generate zero scratches on a Hegman gauge, and also recording the residual background "sand" value.

Dispersion of the diluted samples in the following examples was determined by diluting the masterbatch composition down to a loading of by weight, carbon black with the EVA resin in a Brabender mixer operating at 850 C and 50 rpm. The mixing time was 2 minutes. Samples were then pressed 14 between microscope slides and dispersion at 100X magnification was determined by the Cabot Corporation rating method wherein the number (1-6) refers to the size of the undispersed particles, with 1 being small and 6 being large; and the letter refers to the number of particles per field of view, with A being 1-2 particles and E being greater than 50 particles. Lower numbers and earlier letters indicate better dispersion, with 1A rating indicating good dispersion and a 6E rating poor dispersion.

The polymer compositions were evaluated for strippability utilising the following technique. The compositions containing 40% carbon black in the ethylene vinyl acetate resin were compounded in a Brabender mixer with 1% dicumyl peroxide while maintaining the mixing temperature below 150 0 C. The material was transferred to a heated hydraulic press (temperature 130 0 C) and Sa plaque 1.2 mm thick produced. A 2 mm polyethylene plaque containing 1% dicumyl peroxide was produced in a similar manner. The two plaques were laminated together under a pressure of 7.030 kg/cm 2 (100 psi) and exposed to a curing cycle of 180 0 C for 15 minutes. The laminate was allowed to cool to .ooooi ambient temperature under pressure. The delamination force under a peeling angle of 180 degrees and a separation speed of 0.10 meter/minute (3.94 inches/minute) was recorded; the results provided are an average of 28 peel S 20 tests.

The modulus, tensile and elongation of the polymer compositions were measured by the procedure set forth in ASTM D 412.

The Shore A Hardness of the rubber compounds was determined according to the procedure set forth in ASTM D-2240-86.

The maximum torque was determined from the peak of the motor load versus time profile from the Brabender mixer.

The dump torque (Nm) was determined from the final torque value at the end of the mixing cycle.

The total energy (Nm) was determined by calculating from the area under the full mixing curve.

The MDR 170°C T50 and T90 was determined according to the procedure set forth in ASTM 2084.

The Mooney viscosity (ML(1+4)@1000C was determined according to the procedure set forth in ASTM 1646.

The IRHD (hardness) was determined according to the procedure set forth in ASTM D1415.

The effectiveness and advantages of the present invention will be further illustrated by the following examples.

EXAMPLES

These examples illustrate the use of binder compositions to produce carbon black compositions of the present invention, and the advantages of using the carbon black compositions of the present invention in ethyl vinyl acetate (EVA) applications.

Carbon black compositions, HH, NN, 00, PP, QQ and RR were produced by combining 400 g of a fluffy carbon black having a DBP of 128 cc/100g and a nitrogen surface area of 68 m 2 designated herein as CB-12, together with 8 g of binder dissolved in 500 g of water, in a batch pin pelletiser. The binder utilised in each composition was as follows: Composition Binder 20 HH water NN SYNPERONIC PE/L61 surfactant 00 SYNPERONIC PE/85 surfactant PP SYNPERONIC PE/F127E surfactant QQ SYNPERONIC PE/38E surfactant RR SYNPERONIC PE/108E surfactant SYNPERONIC is a trade name for surfactants produced and sold by ICI Chemical Polymers and comprise ethylene oxide propylene oxide copolymers. SYNPERONIC PE grade surfactants as described in "Surfactants Europe", 2nd Ed. (edited by G.L. Hollis and published by Tergo Data, Darlington, UK, ISBN 0 9505473 1X) as polyethylene oxidepolypropylene oxide polyethylene oxide copolymers.

i f S ~Fe

S

vs-Z 16 This mix was agitated at 800 rpm for 2 minutes to produce a pelletised carbon black. The carbon black pellets were dried at 1250C until the moisture content was below 1%.

Mass pellet strength of the carbon black compositions was determined according to the procedures described herein. The results are set forth in Table 1 below.

Each of the carbon black compositions was combined with an ethylene vinyl acetate copolymer containing 40% vinyl acetate and a melt index of 3 in a Brabender mixer conditioned at 650C. The compound was masticated for 6 minutes at 50 rpm to produce a fully dispersed compound containing carbon black. These compounds were assessed for melt index (MI) at 190°C using a 21.6 kg load, according to the procedures described herein. The results are also set forth in Table 1 below, which also shows the HLB of each Sbinder.

15 TABLE 1 i Comp Binder HLB MPS MI Disp. Of (kg) (g/10m) Dil.

Samples HH water 0.72 6.58 2C (1.6 Ibs.) NN SYNPERONIC PE/L61 surfactant 16.0 4.26 10.34 1B (9.4 Ibs.) 00 SYNPERONIC PE/85 surfactant 16.0 1.31 10.55 1C (2.9 Ibs.) PP SYNPERONIC PE/F127E surfactant 22.0 1.18 6.70 1E (2.6 Ibs.) QQ SYNPERONIC PP/38E surfactant 30.5 1.40 7.90 1B (3.1 Ibs.) RR SYNPERONIC PE/108E surfactant 27.0 1.59 7.97 1E Ibs.) rn. Comp. Composition; Disp. Of Dil. Samples Dispersion of Diluted Samples These examples illustrate the improvement in dispersion quality and reduction in viscosity with improved pellet handling qualities, in a commercial system. These results would relate to shorter mixing cycles and improved extrusion characteristics.

It should be clearly understood that the forms of the present invention herein described are illustrative only and are not intended to limit the scope of the invention.

"Comprises/comprising" when used in this specification is taken to specify the presence of stated features, integers, steps or components, but does not preclude the presence of addition of one or more other features, integers, steps, components or groups thereof.

S 2 THE NEXT PAGE IS PAGE

Claims (10)

1. A carbon black composition comprising: carbon black and 0.1% to 50%, by weight, of at least one binder which is a polyethylene oxide polypropylene oxide polyethylene oxide block copolymer.

2. The carbon black composition of claim 1 wherein the binder has an HLB value from 8.0 to

3. The carbon black composition of claim 1 wherein the binder is present in amount of 1.0 to 20 percent by weight

4. The carbon black composition of claim 1 wherein the carbon black is treated with the binder. A polymer composition comprising: a polymer component and 0.1-65%, by weight, of a composition comprising a carbon black and 0.1% to 50%, by weight of at least one binder component which is a polyethylene oxide polypropylene oxide polyethylene oxide block copolymer.

6. The polymer composition of claim 5 wherein the binder has an HLB value from 8.0 to

7. The polymer composition of claim 5 wherein the composition of carbon black and binder is present in an amount of 1.0 to 20 percent by weight.

8. The polymer composition of claim 5 wherein the carbon black is treated with the binder component. 31

9. An semi-conductive composition comprising:

25-55%, by weight, of a composition comprising a carbon black and to 10 parts per 100 parts of carbon black of at least one binder component which is a polyethylene oxide polypropylene oxide polyethylene oxide block copolymer; 0 to by weight a stabilizer or antioxidant 0 to by weight an organic peroxide, preferably dicumyl peroxide; 0 to 10%, by weight a vinyl silane; the remainder being a polymer, or a blend of polymers, selected from the following group: S. ethylene homopolymer; Sethylene copolymerized with one or more alpha olefins; ethylene copolymerized with propylene and a diene monomer; and ethylene copolymer with one or more monomers selected from vinyl acetate, acrylic acid, methacrylic acid, esters of acrylic or methacrylic acid containing 1 to 8 carbon atoms, maleic anhydride or a monoester derived from fumaric or maleic acid, vinyl chloride or vinylidene chloride. 10. The semiconductive composition of claim 9 wherein the carbon black is treated with the binder. 11. A masterbatch composition comprising:

70-40%, by weight of an ethylene homopolymer or copolymer, where the comonomer is selected from hexene, propene, butene, octene or vinyl acetate; and 30-60%, by weight, of a composition comprising a carbon black and 0.1- by weight, of at least one binder component which is a polyethylene oxide polypropylene oxide polyethylene oxide block copolymer. 12. The masterbatch composition of claim 11 wherein the carbon black is treated with the binder. -I b 32 13. An article of manufacture formed from the composition of claim 14. The carbon black composition of claim 1 further comprising 0.1% to by weight, sucrose distearate. DATED this 25th day of May, 1999. CABOT CORPORATION WATERMARK PATENT TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA oKJS:RBP:JL VAX doc 027 AU003131.WPC SO *o 0 0 9