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WO1999033909A1 - Procede permettant de regler les caracteristiques de surface de thermoplastiques et produit associe - Google Patents

Procede permettant de regler les caracteristiques de surface de thermoplastiques et produit associe Download PDF

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Publication number
WO1999033909A1
WO1999033909A1 PCT/US1998/027464 US9827464W WO9933909A1 WO 1999033909 A1 WO1999033909 A1 WO 1999033909A1 US 9827464 W US9827464 W US 9827464W WO 9933909 A1 WO9933909 A1 WO 9933909A1
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WIPO (PCT)
Prior art keywords
particle size
microns
thermoplastic
micron
granules
Prior art date
Application number
PCT/US1998/027464
Other languages
English (en)
Inventor
David A. Skelhorn
Original Assignee
Ecc International Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ecc International Inc. filed Critical Ecc International Inc.
Priority to AU19460/99A priority Critical patent/AU1946099A/en
Publication of WO1999033909A1 publication Critical patent/WO1999033909A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
    • C04B18/022—Agglomerated materials, e.g. artificial aggregates agglomerated by an organic binder
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Definitions

  • the invention relates to the processing of a thermoplastic end product, and more particularly, to controlling the surface characteristics, such as “coarseness” or “smoothness” of a thermoplastic end product by using a thermoplastic granule by varying the particle size distribution of the mineral filler in the thermoplastic granules blended into the thermoplastic host material.
  • thermoplastic processing industry has long used inorganic materials, such as calcium carbonates, as fillers in the thermoplastic resins generally in order to recover the manufacturing costs for thermoplastics since inorganic materials are relatively inexpensive compared to resins.
  • these fillers may be blended directly into the thermoplastic host material or may be in the form of a pellet or granule which is added to the thermoplastic host material.
  • Such processing may use conventional methods such as injection molding, blow molding, or extrusion.
  • the manufacturing of these pellets and their introduction into the thermoplastic host material has traditionally been achieved using a number of techniques such as those discussed hereinbelow.
  • the polymer, inorganic material and other additives may be subjected to intensive mixing using mechanical systems designed to disperse the inorganic material and additives in the polymer at a temperature above the melting point of the polymer.
  • the proportion of inorganic material and additives in the mixture comprising the polymer, the inorganic material, and the additives is the same as that required in the end product.
  • Suitable mixing equipment includes internal mixers of the Banbury type, twin or single screw extruders, and continuous compounders .
  • the polymer, inorganic material and other additives are mixed similar to that described in paragraph (a) above, except that the inorganic material is surface treated with a hydrophobic material to render it compatible with organic polymers.
  • hydrophobic materials include organosilane coupling agents, organotitanates, zircoaluminates and carboxylic acids of moderate to high molecular weight such as butyric acid, lauric acid, oleic acid and stearic acid.
  • the proportion of inorganic material and other additives in the mixture comprising the polymer, the inorganic material and the additives is much higher than is required in the end product. Inorganic material concentrations in the order of 75 to 80 weight percent may be produced using this technique.
  • thermoplastic polymer host material immediately prior to entering the final processing operation in such a ratio as to produce a mixture with a lower inorganic material content which is uniformly distributed and dispersed throughout the thermoplastic polymer host material, and thus, the thermoplastic end product.
  • U.S. Patent No. 4,803,231 describes a highly concentrated, redispersible inorganic material composition where the inorganic material contents are in excess of 75 to 80% by weight.
  • This patent describes a three component composition comprising : (1) a polyolefin polymer or blend of polymer between 19.99 and 4.05 percent of the composition; (2) 80 to 95 percent inorganic material; and (3) an agent which renders the mixture fluid (a fluidifacient) included at 0.01 to 0.95 percent.
  • This composition may be blended with the thermoplastic polymer host material prior to the final processing operation in such a ratio as to produce a mixture with a lower inorganic material content which is uniformly distributed and dispersed throughout the thermoplastic polymer host material, and thus, the thermoplastic end product.
  • Canadian Patent Application No. 2016447 describes a redispersible pellet for use in a thermoplastic system and consisting of 92.1 to 96.1% by weight mineral additives; 0.1 to 3.0% by weight of a hydrophobic surface coating agent for the mineral additives, and 3.8 to 4.9% by weight of a hydrophobic binder system.
  • the examples of this 47 reference use a calcium carbonate having a mean particle size of 3 microns or 6 microns with the upper section of the grain distribution being 15 or 30 microns, and the relatively low binder amount is used in order to obtain an additive which does not affect the flame retardant properties of the polymer composition to which the additive is added.
  • This range of percentages for the calcium carbonate particles in the granule is achieved by using the following Andreasen-Furnas Equation as a vehicle to attain a particle size distribution which optimizes the amount of calcium carbonate particles in a thermoplastic granule:
  • D s range from 10 micron to 0.1 micron and preferably 0.5 micron to 0.1 micron; those for D range from 100 micron to 1.0 micron, and preferably 44 microns to 2 microns; and n has a value appropriate for carbonate particles assumed to be approximately spherical and is about 0.37.
  • the resultant product is presently manufactured and available from ECC International Inc., the assignee of the present invention, ZYTOCAL , which is classified as being a calcium carbonate additive for particular use in the manufacture of thermoplastics.
  • thermoplastic end product there is presently available a highly concentrated inorganic material composite which redisperses easily in thermoplastic polymers, however, none of the prior art discussed hereinabove provides a method for controlling the surface characteristics of a thermoplastic end product.
  • Conventional use of minerals, such as calcium carbonates, in thermoplastics has been known to influence some surface phenomena, such as gloss.
  • ECC International Inc. the assignee of this present patent application, had found back in 1995 that there is a direct correlation between gloss and the particle size of the mineral in molded polyolefin materials.
  • prior to the present invention it has not been known to use high solids concentrates in molding applications to control gloss and/or surface roughness in the thermoplastic end product.
  • thermoplastic end product There is a need, therefore, to provide a method for controlling the surface characteristics of a thermoplastic end product.
  • the surface characteristics, such as appearance and/or texture of a thermoplastic end product can be controlled by varying the particle size distribution of a particulate carbonate filler of a thermoplastic granule and varying the loading of the particulate carbonate filler in the thermoplastic end product.
  • the granule may contain a high proportion of the carbonate filler which is at least 85 to 92% by weight, which carbonate filler may be coated with a fatty acid or blend of fatty acids having a carbon chain length of from 12 to 20 carbon atoms.
  • the balance of the granule by weight may be a thermoplastic polymer binder which is solid at ambient temperature and which is compatible with the end product thermoplastic in which the carbonate filler is to be dispersed.
  • the polymeric binder may be selected from one or more members of the group consisting of amorphous polyolefins and highly branched polyethylene waxes.
  • the range of percentages, which is 82 to 95% by weight, for the carbonate particles based on the weight of the granule is achieved by using the aforementioned Andreasen-Furnas Equation in a manner discussed hereinabove as a vehicle to attain an actual particle size distribution for optimizing the amount of calcium carbonate particles in the thermoplastic granule. Both the amounts for the largest and the smallest particle sizes can be varied to produce a surface texture spectra ranging from "coarse" to "smooth".
  • the largest particle size can range from about 10 microns to about 44 microns, and preferably about 15 microns to about 23 microns with a smallest particle size range from 0.25 to 1 micron and, preferably, 0.3 to 0.4 micron.
  • the largest particle size can range from about 1 micron to about 9.9 microns and, preferably, 3.5 to 4.3 microns with a smallest particle size range from 0.1 to 0.5 micron and, preferably, 0.15 to 0.25 micron.
  • the loading of the carbonate filler can be varied from about 5% to 50% by weight of polymer mineral composition for the thermoplastic end product to effect the engineering properties, such as stiffness (flexural modulus) of the end product.
  • stiffness flexural modulus
  • 0%, 10%, 20% or 30% loading of carbonate filler in the polymer during the manufacturing process of the thermoplastic end product can produce a flexural modulus value of 696 mPa, 779 Pa, 841 mPa, and 901 mPa, respectively.
  • the present invention uses a high solids (>85%) concentrate granule in thermoplastic molding and/or extrusion applications to provide different surface roughness which impart tactile qualities or surface roughening effects to the inner or outer surfaces of a thermoplastic end product.
  • the granules used in the present invention are capable of providing these qualities, and the extent of these qualities are controllable by varying the particle size distribution of the particulate mineral, preferably calcium carbonate, used in the granule, and the amount of loading of the particulate mineral used in the granule, and thus, used in the thermoplastic end product in a molding or extrusion process.
  • Figure 1 is a graph showing curves for actual and theoretical particle size distributions of the particle packing equation for the carbonate with a D L of 18 microns and a D s of 0.35 micron, a 5 micron mean diameter, used to produce a 90% by weight carbonate granule of the invention for a "coarse" surface.
  • Figure 2 is a graph showing curves for actual and theoretical size distribution of the particle packing equation for the carbonate with a D L of 3.8 microns and a D s of 0.2 micron, and a 1.2 micron mean diameter used to produce an 85% by weight carbonate granule of the invention for a "smooth" surface.
  • Figure 3 is a paperscape showing the inside surface of an unfilled resin of a comparative bottle sample.
  • Figure 4 is a paperscape showing the outside surface of an unfilled resin of a comparative bottle sample.
  • Figure 5 is a paperscape showing the outside surface of a filled resin of a third bottle sample incorporating the teachings of the present invention.
  • Figure 6 is a paperscape showing the inside surface of a filled resin of a third bottle sample incorporating the teachings of the present invention.
  • Figure 7 is a paperscape showing the inside surface of a filled resin of a second bottle sample incorporating the teachings of the present invention.
  • Figure 8 is a paperscape showing the outside surface of a filled resin of a second bottle sample incorporating the teachings of the present invention.
  • thermoplastic granules are dispersed into the thermoplastic host material which in a plasticized state is brought through an injection molding apparatus, a blow-molding apparatus, or an extrusion apparatus to produce a desired form or shape for the thermoplastic end product.
  • the granule used in the present invention preferably is produced according to the teachings of the aforesaid patent application U.S. Serial No. 08/639,309 filed April 25, 1996, which is incorporated herein by reference.
  • This Andreasen-Furnas Equation also known as the optimum particle packing equation produces a theoretical curve for a particle size distribution which for the invention must be closely met by an actual particle size distribution of the carbonate particles in a granule.
  • D s is 0.35 microns and D L is 18 microns and if D is selected at frequent points between 0.35 micron and 18 microns, e.g., 0.3, 0.5, 0.7, 1.0, 2,0, 4.0, 6.0, 8.0, 10.0, 12.0, 14.0 and 18.0 microns, then by use of the Andreasen-Furnas Equation, the particle size distribution for each of these selected points from 0.35 microns to 18.0 microns for the carbonate particles in the granule in equivalent spherical diameter will be as follows: 100 weight percent ⁇ 18 microns 94.4 weight percent ⁇ 16 microns
  • Calcium carbonate which has been crushed, washed, and sorted (for color) is introduced with water, in a ratio of approximately 30% mineral and 70% water, into a tube mill.
  • a tube mill is a long cylindrical vessel which is rotated on its longitudinal axis. The output end is partially dammed to retain water and mineral and allows autogenous grinding to occur where the mineral also acts as the grinding medium. This mill is kept partially filled. The mill fill level is controlled by measuring the energy used in the motor which drives the mill. As the power consumption of the motor drops to a predetermined value, additional mineral is allowed to enter the mill periodically. This process establishes an actual particle size distribution which is in equilibrium and constant and which ranges from 100 microns to 0.4 microns.
  • a top size and a bottom size which closely meets at least part of the theoretical curve of the packing equation of the claimed invention.
  • the SNOWFLAKE PE product discussed hereinabove a top size of 40 microns and a bottom size of 0.4 microns closely meets the criteria given by the particle packing equation.
  • particle size distribution may deviate significantly from the theoretical curve of the packing equation. In some industrial applications, this larger, coarser type particle may not be acceptable due to abrasiveness, surface roughness, etc. in the end product.
  • the output of the tube mill producing the SNOWFLAKE PE ® product may be modified by removal of the fraction above 44 microns.
  • Equivalent calcium carbonate products may be commercially available to the plastic industry from different mineral pigment producers. These products generally compete in the marketplace on an equal footing and can be produced by entirely different methods. Once a desired distribution is known for a product, the step remaining is identification on how to achieve it. It is well known to those skilled in the pigment industry the manner in which to obtain a desired particle size distribution for a certain pigment product.
  • the methods may include wet grinding in a ball mill; wet grinding in a wet vertical media mill; wet grinding in a wet horizontal media mill; wet classification by means of a wet centrifugal classifier; or wet grinding in a autogenous tube mill.
  • a dry ground calcium carbonate particle can be prepared by conventional grinding and classifying techniques, e.g., jaw crushing followed by roller milling or hammer milling and air classifying. Calcium carbonate can also be precipitated through methods of which are well know to those skilled in the art.
  • the optimum particle packing equation is used as a tool to manipulate a particle size distribution for a calcium carbonate for use in a thermoplastic pellet which, in turn, is a thermoplastic end product. If a precipitated or ground calcium carbonate has an actual particle size distribution curve not conforming to the packing equation then the calcium carbonate can be screened and/or further processed to attain the required size limits, D L and D s in order to meet the theoretical curve. Alternatively, two or more calcium carbonate products can be blended in certain ratios to produce a particle size distribution which would closely meet the theoretical curve of the Andreasen-Furnas Equation. For example, 65% of one calcium carbonate product having a particular particle size distribution can be combined with 35% of a second calcium carbonate product having a particle size distribution differing from that of the first which would attain a curve closely meeting the theoretical curve of the equation.
  • the particle packing equation provides a means for gauging whether a precipitated or ground calcium carbonate can be used for a desired application, and also establishes a suitable particle size distribution which will effectively achieve an optimum particle packing necessary for producing the pellet used in the thermoplastic end product. If a calcium carbonate does not conform to the particle packing equation, then it can be further processed through means known to those skilled in the art so that it does conform.
  • the particle packing equation produces a theoretical particle size distribution which acts as a guideline in providing an optimum particle packing of the calcium carbonate in the pellet.
  • the process calcium carbonate may or may not have a particle size distribution conforming to the theoretical one represented by the particle packing equation of the claimed invention. If the actual particle size distribution of the calcium carbonate does not conform to the theoretical one, then the calcium carbonate may be further processed so that it does conform to the theoretical particle size distribution.
  • thermoplastic granule used in the invention contains a high proportion of a particulate carbonate filler in a thermoplastic binder, for blending with an end product thermoplastic in which the carbonate filler is to be dispersed.
  • the granule comprises at least 85% by weight (and preferably 85 to 92% by weight) of a particulate carbonate which is coated with a fatty acid or blend of fatty acids having a carbonate chain length of from 12 to 20 carbon atoms.
  • the balance of the granule by weight is a thermoplastic polymeric binder which is solid at ambient temperature and is compatible with the end product thermoplastic in which the carbonate filler is to be dispersed.
  • the polymeric binder is selected from one or more members of the group consisting of amorphous polyolefins and highly branched polyethylene waxes .
  • granule as used herein is intended to refer to the individual discrete components which in total comprise a particulate which as such is in use blended with the aforementioned end product thermoplastic. These discrete components can have irregular surface characteristics as commonly results from granulation, or can have smooth continuous surfaces as a result of pelletization. Both of these discrete types of assemblages are intended to be encompassed herein by the term "granule”.
  • D L should be in the range of 100 to 1.0 ⁇ m; D s in the range of 10 to 0.1 ⁇ m; and n is accorded a value appropriate for particles assumed to be approximately spherical.
  • D is in the range of 44 to 2 ⁇ m, D ⁇ is in the range of 0.5 to 0.1 ⁇ m, and n is about 0.37.
  • the carbonate used in the pellet may be an alkaline earth metal carbonate, such as a calcium carbonate, dolomite, magnesite or strontium carbonate, and is preferably a ground and precipitated calcium carbonate or a mixture of ground and precipitated calcium carbonates. In many applications a ground marble is found to be particularly advantageous.
  • the method of producing desired particle sizes may be by comminution of naturally occurring carbonate minerals by a dry or a wet process, or by precipitation from an aqueous medium. They may be produced by blending of components having different PSD' s or from a production process which generates them naturally.
  • thermoplastic granules used in the invention are typically in the size range of from 5 to 10 mesh, and the end product thermoplastic with which the granules are to be blended may comprise granules in the same 5 to 10 mesh range .
  • the granule does not require the use of additional chemical materials for its preparation or its re- dispersion in a thermoplastic composition, and, thus, the granules are preferably substantially free of a dispersing or fluidifacient additive.
  • the granules may, however, include any additional functional additives which may be desired in the final thermoplastic formulation.
  • the hydrophobic material should be selected to render the surface of the inorganic material surface hydrophobic and compatible with organic polymers.
  • hydrophobic materials include carboxylic acids, or their salts, having from 3 to 20 carbon atoms in their hydrocarbon chain such as butyric, lauric, oleic and stearic acid, organosilane coupling agents, organotitanates and zircoaluminates .
  • Other hydrophobic coating agents may be utilized.
  • Binders for use in the granule preferably comprise an amorphous polyolefin or a highly branched polyethylene wax.
  • Typical such binders are polypropylene homopolymers and amorphous copolymers of propylene and ethylene or butylene. It should be appreciated that the binders of the granule differ markedly from conventional prior art binders used in pellets of the present type. These conventional binders are typically polyolefins and polyolefin waxes, which are thereby highly compatible with polyolefin polymers.
  • the binders for the granules should be chemically and physically compatible with the host or matrix thermoplastic so that the resulting end product is not significantly weakened or discolored by the presence of the binder, and does not exhibit surface bloom from migration of the granule binder to the product surface.
  • amorphous polyolefins utilizable as binders in the granules of the invention are amorphous polypropylene homopolymers. These differ from conventional polyolefins which are highly crystalline.
  • the viscosities of useful such amorphous homopolymers are in the range of 1000-2300 cps at 190°C. This translates to a theoretical Melt Flow Index of ca 90,000-40,000 g/10 minutes. Conventional polypropylene and polyethylene polymers have Melt Flow Indices in the range 200 down to 0.1.
  • Other less preferred grades of such homopolymers for use in the invention have a viscosity of 200 cps at 190°C (equivalent to 500,000 g/10 minutes MFI ) .
  • a viscosity of 200 to 20,000 cps is preferred (equivalent to 500,000- 5,000 g/10 minutes MFI); a viscosity of 500 to 5,000 cps is more preferred (equivalent to 200,000-15,000 g/10 minutes MFI); and a viscosity of 1,000 to 2,500 cps is most preferred (equivalent to 90,000-35,000 g/10 minutes MFI) .
  • Amorphous copolymers of propylene and ethylene, and mixtures of copolymer with homopolymer are also effective for use in the invention.
  • the highly branched polyethylene waxes for use in the invention are preferably saturated, non-polar, synthetic hydrocarbon waxes which have been chemically neutralized.
  • the special HULS/VEBA modification of the Ziegler low pressure polymerization of ethylene is typically used to produce the unique characteristics of this group of materials. The process confers branched- chain iso-paraffinic configurations.
  • the grade particularly preferred for use in the invention has a very high iso-paraffin (branched) configuration and is predominantly branched chain.
  • a typical such product has 70% branching, a molecular weight of 3,500 (by osmometry) , an ASTM D-566 drop point at 102-110°C, density is 0.92, and a viscosity at 150°C of 300-380 cps.
  • the granulated product thus produced was blended with conventional polypropylene homopolymer with a melt flow index of 4.0 in the ratio of 88.9:11.1 polypropylene: granules.
  • the blend was metered into a Kawaguchi reciprocating screw injection molding machine containing a screw with no mixing elements.
  • the very high calcium carbonate-containing granules (92% CaC0 3 ) dispersed readily into the blend and produced visually homogeneous molded parts .
  • the granulated product thus produced was blended with conventional polypropylene homopolymer with a melt flow index of 4.0 in the ratio of 88.9:11.1 polypropylene : granules .
  • the blend was metered into a Kawaguchi reciprocating screw injection molding machine containing a screw with no mixing elements. The granules dispersed readily into the blend, and visually homogeneous calcium carbonate filled parts were molded.
  • EXAMPLE 3 Calcium carbonate with a D of 18 micrometers and a D ⁇ of 0.35 micrometers (Figure 1) was treated with 1.0 percent of stearic acid in a high speed mixer running at 400 rpm for 5 minutes at a temperature of 150°C. This product was then placed in an internal mixer at a temperature of 160°C with polypropylene homopolymer in the ratio of 90:10 of treated calcium carbonate : polypropylene and was kneaded to form a homogeneous mixture. The resultant mixture was formed into granules by passing through a granulator and screening the resultant granules between 5 mesh and 10 mesh screens.
  • the granulated product thus produced was blended with linear low density polyethylene with a melt flow index of 50 in the ratio of 88.9:11.1 poyethylene : granules .
  • the blend was metered into an Arburg All-rounder 35 ton reciprocating screw injection molding machine containing a screw with no mixing elements.
  • Homogeneous calcium carbonate filled parts were molded with desired properties, as taught in the aforesaid patent application, U.S. Serial No. 08/639,309. Where it is evident that the strength properties of the filled parts have not been substantially reduced.
  • EXAMPLE 4 Calcium carbonate with a D L of 18 micrometers and a
  • D s of 0.35 micrometers (Figure 1) was treated with 1.0 percent of stearic acid in a high speed mixer running at 400 rpm for 5 minutes at a temperature of 150°C. This product was then mixed using a two roll mill at a temperature of 160°C with a highly branched polyethylene wax in the ratio of 90:10 of treated calcium carbonate : wax to form a homogeneous mixture. The resultant mixture was formed into granules by passing through a granulator and screening the resultant granulate between 5 mesh and 10 mesh screens. The granulated produce thus produced was blended with high density polyethylene with a melt flow index of 30 in the ratio of 88.9:11.1 polyethylene : granules .
  • the blend was metered into an Arburg All-rounder 35 ton reciprocating screw injection molding machine containing a screw with no mixing elements. Homogeneous calcium carbonate filled parts were molded with desired properties, as taught in the aforesaid patent application, U.S. Serial No. 08/639,309.
  • Examples 1-4 used a D L of 18 microns and a D s of 0.35 micron to obtain an actual curve (A) as shown in Figure 1 which closely meets the theoretical curve (B) for the optimum particle packing equation.
  • Figure 2 shows an actual curve (C) for a particle size distribution where D L is 3.8 microns and D s is 0.2 micron and which actual curve (C) closely meets the theoretical curve (D) of the optimum particle packing equation.
  • the present invention uses a high solids concentrate of between 85% and 92% by weight with different particle size carbonate additives in the granule of U.S. Serial No. 08/639,309 to control the surface characteristics, such as texture and appearance, in molded thermoplastics during processes such as injection and blow molding, and in other thermoplastic processes, such as extrusion. This is done particularly by varying the particle size distribution of the particular carbonate in the granule. To effect structural properties of the end product, such as stiffness, the loading of the granules in the host thermoplastic material can be varied.
  • the surface appearance of such thermoplastic end products are influenced by the particle size distribution of the carbonate pigment in the granule or pellet, and in particular, the mean particle size of the carbonate pigment.
  • a concentrate of carbonate filler with a mean diameter of about 5 to about 7 microns may produce a thermoplastic end product with a surface texture which is coarse to the touch with low gloss while the use of the same concentrate of carbonate filler with a mean diameter of about 0.7 to about 1.5 microns may produce a thermoplastic end product with a much "smoother" surface and a significantly higher gloss.
  • This control of surface texture and/or appearance may be used to provide different tactile qualities to the molded thermoplastics or to provide different levels of surface roughness for adherence of various substrates which may be applied at any later point in time.
  • a molded thermoplastic bottle may require having a coarse outer surface for adherence of a label.
  • the mean diameter of the particulate mineral may range from about 0.5 micron to about 7.0 microns and, preferably, from about 1.2 microns to about 5.0 microns.
  • the largest particle size (D L ) can range from about 10 microns to about 44 microns and, preferably, from about 15 to 23 microns with a smallest particle size (D s ) range from about 0.25 to about 1 micron and, preferably from about 0.3 to about 0.4 micron.
  • the largest particle size (D L ) can range from about 1 micron to about 9.9 microns and, preferably, from about 3.5 to about 4.3 microns with a smallest particle size (D s ) range from about 0.1 to about 0.5 micron and, preferably, from about 0.15 to about 0.25 micron.
  • the amount of loading of the calcium carbonate particles in the polymer can range from about 0% to about 30% by weight of the polymer and preferably about 20% by weight of the polymer.
  • the present loading of the carbonate filler in the polymer during manufacture affects the structural properties, such as stiffness or flexural modulus of the end product.
  • 0%, 10% 20% and 30% loading of the carbonate filler in the polymer can produce a flexural modulus of 696 mPa, 779 mPa, 841 mPa, and 901 mPa, respectively.
  • the weight percentage of the calcium carbonate particles in the thermoplastic granule may be about 82% to 95% by weight based on the weight of the granule and, preferably, greater than 85% by weight of the granule.
  • thermoplastic bottles were made in a blow molding process using high density polyethylene (HDPE) with a melt index of 0.3.
  • the first bottle was made without a calcium carbonate filler additive.
  • a second bottle was made with a 15% calcium carbonate loading where the calcium carbonate particles in the granules had a D L of 18 microns and a D s of 0.35 micron with a mean diameter of 5 microns and a 90% concentration.
  • the granules for this second bottle were blended with the HDPE resin.
  • a third bottle was made with a 15% calcium carbonate loading where the calcium carbonate particles in the granules had a D L of 3.8 microns and a D s of 0.2 micron with a mean diameter of 1.2 microns and a 90% concentration.
  • the granules for this third bottle were blended with the HDPE resin.
  • the granules blended with the HDPE resin were made similar to that discussed in Examples 1-4 above. Blending of the high solids granules with HDPE pellets is done mechanically by a number of means known to those skilled in the art, preferably just before the material is added to the machine which molds bottles.
  • the surfaces of these three bottles were characterized for their "smoothness” or “coarseness” using a modified Tallistep Profilometer, which is a "paperscape” profilometer, whereby a stylus is moved across the plastic surface.
  • the styles is attached to sensors which map the surface of the plastic in such a way that the surface can be represented graphically through the use of a computer based on software.
  • a three-dimensional representation for the inside and outside surfaces of the first bottle is shown in Figures 3 and 4, respectively; those for the inside and outside surfaces for the third bottle sample (present invention) are shown in Figures 5 and 6 respectively; and those for the inside and outside surfaces for the second bottle sample (present invention) are shown in Figures 7and 8, respectively.
  • An area of 5000 microns by 5000 microns for these samples are shown in these Figures 3-8 according to a root means square (RMS) taken by a Walsh
  • RMS refers to the standard deviation (Root Mean Square) of the surface from its mean plane. It is a direct measure of the surface's roughness. The higher the RMS number, the rougher the surface, i.e. an RMS value of 13 ( Figure 8, second bottle sample) indicates a rougher surface than that with a RMS value of 3.0 ( Figure 5, third bottle sample).
  • the third bottle sample had the smoothest surface on both the inside and outside ( Figures 5 and 6) .
  • the second bottle sample had the roughest surface with the outside being the roughest when compared to its inside surface and the surfaces of the other two bottle samples.
  • the inside surface showed considerable orientation of the roughness.
  • Smooth grooves could be seen that were due to melt fracture of the thermoplastic host material through the blow molding machine which creates grooves which are perpendicular to the machine direction.
  • the use of this additive modifies the rheology of the host resin, reducing melt fracture, but then influences the surface smoothness of the part by virtue of the characteristics of the mineral component.
  • This roughness of the surface of the resin for the bottles containing the granules is influenced by the to the coarseness of the particles in the granules and the percentage of granules used to manufacture the bottles
  • Table 1 shows the gloss and color values and the opacity for the three bottle samples.
  • L*, a*, b* color was measured according to ASTM E305 on a Macbeth Colorimeter.
  • L* generally is a number between 0 to 100, with 0 being completely black and 200 being completely white.
  • the a* value is the red/green value which is a positive number for red samples (the more positive, the redder) , and negative for green samples (the more negative, the greener) .
  • the b* value looks at blue/green values of the material. Positive values are yellow and negative values are blue.
  • an 85° gloss is the spectral gloss at an angle of 85° from the vertical (i.e.
  • a 60° gloss is the spectral gloss at an angle of 60° from the vertical
  • a 20° gloss is the spectral gloss at an angle of 20° from the vertical (i.e. high angle of observation).
  • “Degree gloss” is a useful measure of surface smoothness or roughness. At 85° gloss, the external surface of the first sample bottle was 12.0 (rough); that for the second bottle was 2.4 (smooth); and that for the third bottle was 12.2 (rough).
  • Gloss is a function of surface smoothness, so if the surface gets rougher, the gloss gets lower.
  • the small mean particle size distribution of the carbonate (ex. third bottle sample with a mean diameter of 1.2 microns) gives a high gloss (12.2 at 85° gloss) compared to the large mean particle size distribution of the carbonate (ex. second bottle sample - with a mean diameter of 5 microns) which has a gloss at 2.4 at an 85° gloss.
  • the above results are representative of the effects a particle size distribution of a carbonate filler can have on a thermoplastic end product.
  • Manipulation of the particle size distribution e.g., fine particles or coarse particles for the carbonate particles can be achieved through use of the particle packing equation in order to obtain the desired surface characteristics of a thermoplastic end product.
  • the carbonate particles discussed hereinabove may be a precipitated or a ground calcium carbonate or it may be any other inorganic mineral such as kaolin clay, or a silicate.
  • a first granule with a particle size distribution may be combined with a second granule having a particle size distribution differing from that of the first and/or granules with different percentage particle concentrations, i.e. from 85% to 92%, may be blended with the thermoplastic host material to obtain the desired "coarseness" or “smoothness" in the surface external texture and appearance of the end product.

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Abstract

L'invention concerne un procédé de réglage des caractéristiques de la surface d'un produit moulé par l'utilisation d'un granulé thermoplastique présentant une distribution granulométrie variée et un diamètre moyen particulaire varié. Pour une surface 'grossière', le diamètre moyen peut être compris entre 5 et 7 microns, la particule DL la plus grande peut être comprise entre 10 et 44 microns et la particule la plus petite Ds est de l'ordre de 0,25 et 1 micron. Pour une surface 'lisse', le diamètre moyen de la particule minérale peut être comprise entre 0,7 et 1,5 microns, la particule DL la plus grande peut aller de 1 à 9,9 microns et la particule la plus petite Ds peut être de l'ordre de 0,1 à 0,5 micron. La concentration de la particule minérale en granulé peut être comprise entre 85 et 92 % en poids du granulé.
PCT/US1998/027464 1997-12-29 1998-12-23 Procede permettant de regler les caracteristiques de surface de thermoplastiques et produit associe WO1999033909A1 (fr)

Priority Applications (1)

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AU19460/99A AU1946099A (en) 1997-12-29 1998-12-23 A method for controlling surface characteristics of thermoplastics and an associated product

Applications Claiming Priority (6)

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US6899297P 1997-12-29 1997-12-29
US60/068,992 1997-12-29
US7080898P 1998-01-08 1998-01-08
US60/070,808 1998-01-08
US5421398A 1998-04-02 1998-04-02
US09/054,213 1998-04-02

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1110991A1 (fr) * 1999-12-06 2001-06-27 Electrolux Zanussi S.p.A. Composition polymérique appropriée pour le moulage par soufflage
US20220275168A1 (en) * 2019-08-28 2022-09-01 Tbm Co., Ltd. Resin composition and molded product

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4803231A (en) * 1985-05-21 1989-02-07 Pluess Staufer A. G. Thermoplastic compositions with very high content of pulverulent mineral materials for incorporation into polymers
CA2016447A1 (fr) * 1989-05-11 1990-11-11 Hans-Peter Schlumpf Agglomerats dopes redispersables

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4803231A (en) * 1985-05-21 1989-02-07 Pluess Staufer A. G. Thermoplastic compositions with very high content of pulverulent mineral materials for incorporation into polymers
CA2016447A1 (fr) * 1989-05-11 1990-11-11 Hans-Peter Schlumpf Agglomerats dopes redispersables

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1110991A1 (fr) * 1999-12-06 2001-06-27 Electrolux Zanussi S.p.A. Composition polymérique appropriée pour le moulage par soufflage
US20220275168A1 (en) * 2019-08-28 2022-09-01 Tbm Co., Ltd. Resin composition and molded product

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