WO2005058569A1 - Process for making a pellet - Google Patents

Process for making a pellet Download PDF

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Publication number
WO2005058569A1
WO2005058569A1 PCT/GB2004/005273 GB2004005273W WO2005058569A1 WO 2005058569 A1 WO2005058569 A1 WO 2005058569A1 GB 2004005273 W GB2004005273 W GB 2004005273W WO 2005058569 A1 WO2005058569 A1 WO 2005058569A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
poly
plasticiser
temperature
pellets
Prior art date
Application number
PCT/GB2004/005273
Other languages
French (fr)
Inventor
Francesc Ayats
Diana Oehms
Pavlinka Roy
Jordi Salvador
Ralf Wiedemann
Original Assignee
Reckitt Benckiser N.V.
Reckitt Benckiser (Uk) Limited
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=30776162&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2005058569(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to AU2004299333A priority Critical patent/AU2004299333B2/en
Priority to US10/595,919 priority patent/US20070075453A1/en
Priority to PL04806087T priority patent/PL1694480T3/en
Priority to BRPI0416904-2A priority patent/BRPI0416904A/en
Priority to EP04806087.5A priority patent/EP1694480B1/en
Application filed by Reckitt Benckiser N.V., Reckitt Benckiser (Uk) Limited filed Critical Reckitt Benckiser N.V.
Priority to CA2549149A priority patent/CA2549149C/en
Publication of WO2005058569A1 publication Critical patent/WO2005058569A1/en
Priority to ZA2006/04239A priority patent/ZA200604239B/en
Priority to AU2010212479A priority patent/AU2010212479B2/en
Priority to US12/949,302 priority patent/US9327425B2/en
Priority to US15/139,577 priority patent/US20160279830A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
    • B29B13/022—Melting the material to be shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/86—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the nozzle zone
    • B29C48/865—Heating
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • 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
    • C08J3/12—Powdering or granulating
    • 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
    • C08J3/18—Plasticising 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
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
    • B29K2029/04—PVOH, i.e. polyvinyl alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/0062—Degradable water-soluble
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7128—Bags, sacks, sachets
    • 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
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to a process for making pellets of a thermoplastic extrudable polymer.
  • pellets of thermoplastic extrudable polymer are well known in the plastic industry. Typically the pellets are cylindrical and approximately 3mm in diameter and 3mm in length. The pellets are used in a wide range of plastic article manufacturing processes.
  • the pellet manufacturing process generally includes a plas- tification step.
  • the formulation to be pellet- ised is melted and fed into a twin screw extruder. This has been seen to be beneficial as the pellets produced have been found to comprise of a homogeneous blend of the pellet components due to effective mixing of all molten components in the extruder.
  • EP-A-0 415 357 describes the making of pellets comprising polyvinylalcohol (PVOH) by melt extrusion with the extrusion being carried out in the temperature range of 150-195°C.
  • PVOH polyvinylalcohol
  • Pelletising processes having a plastification . step have sev- eral disadvantages associated therewith.
  • the principle disadvantage is the requirement for heating, which means that the energy consumption of these processes is very high.
  • these 'hot' processes are not suitable for poly- mers which are heat sensitive (such as PVOH) due to heat induced decomposition. Also these 'hot' processes give a heat history to the polymer which has been found to negatively influence properties of the polymer. In the case of PVOH this has been found to detrimentally affect the PVOH water solubility .
  • WO-A-98/26911 describes a low temperature process for the manufacture of PVOH pellets.
  • the pellets components in this case a mixture of powdered PVOH and various additives such as plasticisers is fed between two rollers and compressed into pellets.
  • the PVOH component in the pellet blend is not melted in the process and so the issue of heat degradation is avoided.
  • GB-937 057 describes such a low temperature compression process. This follows initial mixing of the plasticiser and PVOH at an elevated temperature.
  • pellets wherein the thermoplastic polymer component of the pellets is PVOH
  • the pouches are commonly used to contain a detergent composition for use in an automatic washing machine (laundry / dishwasher) .
  • laundry / dishwasher automatic washing machine
  • thermoplastic extrudable resin composition comprising a thermoplastic polymer, plasticiser and optionally further additives, the plasticiser comprising a component which is solid at room temperature, wherein the process is run at a temperature above the melting point of the plasticiser and below the melting / plasti- fication temperature of the thermoplastic polymer.
  • the shaping process may comprise pressing, extrusion, calendering and / or compaction. Most preferably the shaping process comprises extrusion.
  • the process of the present invention has been found to overcome the disadvantages associated with the prior art. Firstly as the process is operated at a temperature below the melting / plastification temperature of the thermoplas- tic polymer the process has been found to be extremely energy efficient . Furthermore the heat degradation of heat sensitive materials in the resin blend is dramatically reduced by the lowered process temperatures .
  • the pellets have been found to have a very low friability. Thus the pellets have a much lower tendency to release dust upon friction rubbing.
  • pellets are produced at a temperature above the melting point of the plasticiser component the pellets have been found to have excellent homogeneity. More specifically both the overall composition of each pellet and the distribution of the individual components within the pellets have been found to have an high level of predictability and low variance. This is especially important when the pellets are used in a further processing step such as a second extrusion process (e.g. injection moulding) for the manufacture of an article comprising the thermoplastic poly- raer.
  • a second extrusion process e.g. injection moulding
  • the components are delivered to the shaping equipment used in the process in particulate form.
  • the particle size of the raw materials used to make the pellets should be small . This has been observed to ensure high homogeneity of the pellets.
  • the particle size of the raw materials used preferably is below 2000 ⁇ m, more preferably below 1200 ⁇ m, more preferably below 400 ⁇ m and most preferably about 200 ⁇ m.
  • the plasticiser is present in the composition with at least 5%, more preferably 10%, most preferably 15%.
  • the temperature of the material within the extruder does not exceed a temperature which is 10°C below the melting / plastification temperature of the thermoplastic polymer at any time. More preferably it does not exceed 15°C, more preferably 30°C and most preferably 45°C below the melting / plastification temperature of the thermoplastic polymer. However, it is desired that the temperature of the material exceeds the ambient air temperature .
  • the temperature of material within the extruder is at least 40°C, more preferably at least 45°C, and most preferably at least 50°C.
  • the plasticiser has to at least partially melt at the preferred operating temperature.
  • the melting point of the plasticiser component is preferably at least 15°C, preferably at least 30°C and most preferably at least 45°C below the melting / plastification temperature of the thermoplastic polymer.
  • the plasticiser comprises a carbohydrate.
  • Carbohydrates are usually represented by the generalised formula C x (H 2 0) y .
  • the term herein also includes materials which are similar in nature like gluconic acids or amino sugars which cannot be fully represented by this formula.
  • Other carbohydrate derivatives like sugar alcohols such as sorbitol, glucitol, mannitol, galactitol, dulcitol, xylitol, erythritol, isomaltutose and isomalt fall within this term.
  • Most preferred carbohydrates include the more thermally stable carbohydrates such as sorbitol, glucitol, mannitol, ga- lactitol, dulcitol, xylitol, erythritol, isomaltutose and isomalt .
  • Other preferred plasticiser systems include solid fatty acid alkoxylates, fatty alcohol alkoxylates or polyalkylene gly- cols (such as long chain polyethylene glycol) .
  • the plasticiser may comprise a further auxilliary component.
  • Preferred auxilliary components include glycerin, ethylene glycol, propylene glycol, diethylene glycol, diproylene glycol, triethanol amine, diethanol amine and methyldiethyl amine.
  • cooling may be assisted.
  • One way in which this may be done is by employing a cooled metal belt onto which the or each strand issues.
  • Another way in which this may be done is by using a cooled fluid, preferably cooled air, downstream of the extruder.
  • Another way is by blowing a fluid, preferably air, across the or each strand.
  • the or each strand is separated into pellets, during the manufacture.
  • the strands are separated into pellets preferably by cutting.
  • other separation methods for example twisting, are not ruled out.
  • a method may be envisaged whereby the strand is twisted at intervals when still plastic, to form "sausages", which can be separated by breaking the con- nections, once they have, become more brittle.
  • Partial cutting or pressing or nipping or perforating (all such methods collectively called “scoring” herein) to form frangible separation webs, may also be employed, to form tablet precursors. Separation of the precursors to produce pellets may be effected during manufacture or by the consumer, man- ageable lengths being provided from which the consumer breaks or twists off pellets as required.
  • a pellet precursor may be, for example, a straight row of pellets, to be broken off as needed.
  • the extrusion pressure may be whatever is required to carry out the process in an efficient manner. Suitably it is in excess of 3 bar (0.3MPa), preferably in excess of 5 bar (0.5MPa), and more preferably is preferably in excess of 8 bar (O. ⁇ MPa). More preferably still is preferably in excess of 12 bar (1.2MPa). Most preferably it is in excess of 40 bar (4MPa) .
  • the extrusion pressure preferably does not exceed 100 bar (lOMPa) , more preferably 60 bar (6MPa) .
  • the pellets are for use in injection moulding pro- Devices.
  • the injection moulding process is preferably used for the manufacture of water soluble pouches intended to contain a detergent formulation for use in an automatic washing machine or in an automatic dishwasher.
  • the pellets preferably comprising a water-soluble / water- dispersible thermoplastic polymer
  • the advantageous properties of the pellets produced in accordance with the invention have been found to be particularly beneficial. It is believed that this property is most beneficial as the integrity of the injection moulded product relies upon such high homogeneity of the composition being injection moulded as otherwise the low homogeneity will be reflected in the injection moulded product.
  • the high homogeneity has been found to lead to predictable water solubility of injection moulded products.
  • the water-soluble / water-dispersible thermoplastic polymer comprises PVOH or a derivative thereof.
  • water-soluble / water-dispersible polymers may be used in the process either as an alternative or in addition to PVOH.
  • Preferred examples include poly (vinylpyrollidone) , poly (acrylic acid), poly(maleic acid), a cellulose derivative (such as a cellulose ether / hydroxypropyl methyl cel- lulose) , poly(glycolide) , poly (glycolic acid), poly (lactides) , poly (lactic acid) and copolymers thereof.
  • Processing aids may be present in the admixture which is processed.
  • Preferred processing aids include mono-, di-, tri-carboxylic acids / salts thereof, fatty acids such as stearic acid / salts thereof, mono-, di- or triglycerides / salts thereof, aerosil, inorganic and organic pigments.
  • the pelletising process was conducted on an extruder (twin screw, ICMA S. Giorgio, Milan (dedicated to processing of plastic blends and alloys) .
  • the extruder had the following characteristics.
  • Screw diameter 35 mm Screw length: 40 cm
  • the extruder was attached to a two-roll unit used as a cooling source and connected to a pellet cutter.
  • Example 2 The pellets obtained were chilled to room temperature. The formula yielded solid pellets having low friability.
  • Example 2 The pellets obtained were chilled to room temperature. The formula yielded solid pellets having low friability.
  • Example 2 Example 2 :
  • the pelletising process was conducted on a pellet press (model V3-75 from Universal Milling Technologies) .
  • the press had the following characteristics.

Abstract

The invention comprises a shaping process for making pellets of a thermoplastic extrudable resin composition. The resin composition comprises a thermoplastic polymer, plasticiser and optionally further additives. The plasticiser comprises a component which is solid at room temperature. The process is run at a temperature above the melting point of the plasticiser and below the melting / plastification temperature of the thermoplastic polymer.

Description

PROCESS FOR "MAKING A PELLET
The present invention relates to a process for making pellets of a thermoplastic extrudable polymer.
Processes for making pellets of thermoplastic extrudable polymer are well known in the plastic industry. Typically the pellets are cylindrical and approximately 3mm in diameter and 3mm in length. The pellets are used in a wide range of plastic article manufacturing processes.
The pellet manufacturing process generally includes a plas- tification step. In this step the formulation to be pellet- ised is melted and fed into a twin screw extruder. This has been seen to be beneficial as the pellets produced have been found to comprise of a homogeneous blend of the pellet components due to effective mixing of all molten components in the extruder.
EP-A-0 415 357 describes the making of pellets comprising polyvinylalcohol (PVOH) by melt extrusion with the extrusion being carried out in the temperature range of 150-195°C.
Pelletising processes having a plastification . step have sev- eral disadvantages associated therewith. The principle disadvantage is the requirement for heating, which means that the energy consumption of these processes is very high.
Furthermore these 'hot' processes are not suitable for poly- mers which are heat sensitive (such as PVOH) due to heat induced decomposition. Also these 'hot' processes give a heat history to the polymer which has been found to negatively influence properties of the polymer. In the case of PVOH this has been found to detrimentally affect the PVOH water solubility .
In other pelletising processes dry compaction of the pellet components is carried out at low temperature. Thus the disadvantages of the λhot' processes are avoided.
WO-A-98/26911 describes a low temperature process for the manufacture of PVOH pellets. In the process the pellets components, in this case a mixture of powdered PVOH and various additives such as plasticisers is fed between two rollers and compressed into pellets. The PVOH component in the pellet blend is not melted in the process and so the issue of heat degradation is avoided.
Also GB-937 057 describes such a low temperature compression process. This follows initial mixing of the plasticiser and PVOH at an elevated temperature.
However, although this process (the cold compression process) eliminates the problem of heat induced decomposition of the polymer, the pellets produced suffer from other disad- vantages.
Most of the disadvantages stem from the inherent nature of the compaction process, more specifically the rollers and the powder feed thereto. It has been found to be very dif- ficult to ensure that the powder feed is spread evenly across the rollers. This has the effect that control of the size of the pellets is difficult and so the size of the pellets can vary significantly.
Furthermore significant dust formation is typical for this kind of process. Additionally the pellets are commonly friable having poor integrity and easily form dust from friction rubbing against each other, thus worsening the dust issue. Both of these issues are attributed to the poor spreading and roller compression technique.
Furthermore significant variability of the composition of the pellets and poor homogeneity of the pellets has also been observed. The issues are also believed to be associated with the poor powder distribution over the rollers. The problem of the variability of the pellet composition and the poor homogeneity of the pellets is exacerbated when the pellets are taken and used in a further processing step.
These kinds of pellets, wherein the thermoplastic polymer component of the pellets is PVOH, are used in the manufacture of water soluble PVOH pouches in extrusion / injection moulding processes. The pouches, as an example, are commonly used to contain a detergent composition for use in an automatic washing machine (laundry / dishwasher) . In these applications is it vital that the pellets have high homogeneity to ensure that the pouches produced have good integrity to be stable in storage and have the expected water dissolution properties. Pellets produced in a cold compaction process, as described above, often fail to meet the level of homogeneity required for the processing into the pouch format.
It is an object of the present invention to obviate / mitigate the problems outlined above.
According to the present invention there is provided a shaping process for making pellets of a thermoplastic extrudable resin composition comprising a thermoplastic polymer, plasticiser and optionally further additives, the plasticiser comprising a component which is solid at room temperature, wherein the process is run at a temperature above the melting point of the plasticiser and below the melting / plasti- fication temperature of the thermoplastic polymer.
The shaping process may comprise pressing, extrusion, calendering and / or compaction. Most preferably the shaping process comprises extrusion.
The process of the present invention has been found to overcome the disadvantages associated with the prior art. Firstly as the process is operated at a temperature below the melting / plastification temperature of the thermoplas- tic polymer the process has been found to be extremely energy efficient . Furthermore the heat degradation of heat sensitive materials in the resin blend is dramatically reduced by the lowered process temperatures .
Additionally as the process operates above the melting point of the plasticiser (which is then allowed to cool to form the solid pellet) the pellets have been found to have a very low friability. Thus the pellets have a much lower tendency to release dust upon friction rubbing.
Furthermore as the pellets are produced at a temperature above the melting point of the plasticiser component the pellets have been found to have excellent homogeneity. More specifically both the overall composition of each pellet and the distribution of the individual components within the pellets have been found to have an high level of predictability and low variance. This is especially important when the pellets are used in a further processing step such as a second extrusion process (e.g. injection moulding) for the manufacture of an article comprising the thermoplastic poly- raer.
Generally the components are delivered to the shaping equipment used in the process in particulate form.
It has been found that he particle size of the raw materials used to make the pellets should be small . This has been observed to ensure high homogeneity of the pellets. The particle size of the raw materials used preferably is below 2000μm, more preferably below 1200μm, more preferably below 400μm and most preferably about 200μm.
Preferably the plasticiser is present in the composition with at least 5%, more preferably 10%, most preferably 15%.
Preferably the temperature of the material within the extruder does not exceed a temperature which is 10°C below the melting / plastification temperature of the thermoplastic polymer at any time. More preferably it does not exceed 15°C, more preferably 30°C and most preferably 45°C below the melting / plastification temperature of the thermoplastic polymer. However, it is desired that the temperature of the material exceeds the ambient air temperature . Preferably the temperature of material within the extruder is at least 40°C, more preferably at least 45°C, and most preferably at least 50°C.
The plasticiser has to at least partially melt at the preferred operating temperature. The melting point of the plasticiser component is preferably at least 15°C, preferably at least 30°C and most preferably at least 45°C below the melting / plastification temperature of the thermoplastic polymer.
Preferably the plasticiser comprises a carbohydrate.
Carbohydrates are usually represented by the generalised formula Cx(H20)y. The term herein also includes materials which are similar in nature like gluconic acids or amino sugars which cannot be fully represented by this formula. Other carbohydrate derivatives like sugar alcohols such as sorbitol, glucitol, mannitol, galactitol, dulcitol, xylitol, erythritol, isomaltutose and isomalt fall within this term.
Most preferred carbohydrates include the more thermally stable carbohydrates such as sorbitol, glucitol, mannitol, ga- lactitol, dulcitol, xylitol, erythritol, isomaltutose and isomalt . Other preferred plasticiser systems include solid fatty acid alkoxylates, fatty alcohol alkoxylates or polyalkylene gly- cols (such as long chain polyethylene glycol) .
The plasticiser may comprise a further auxilliary component. Preferred auxilliary components include glycerin, ethylene glycol, propylene glycol, diethylene glycol, diproylene glycol, triethanol amine, diethanol amine and methyldiethyl amine.
Once the or each strand has issued from the extruder it may be permitted to cool under ambient conditions. Alternatively cooling may be assisted. One way in which this may be done is by employing a cooled metal belt onto which the or each strand issues. Another way in which this may be done is by using a cooled fluid, preferably cooled air, downstream of the extruder. Another way is by blowing a fluid, preferably air, across the or each strand. One or more of these methods may be used.
Preferably the or each strand is separated into pellets, during the manufacture.
The strands are separated into pellets preferably by cutting. However, other separation methods, for example twisting, are not ruled out. A method may be envisaged whereby the strand is twisted at intervals when still plastic, to form "sausages", which can be separated by breaking the con- nections, once they have, become more brittle. Partial cutting or pressing or nipping or perforating (all such methods collectively called "scoring" herein) to form frangible separation webs, may also be employed, to form tablet precursors. Separation of the precursors to produce pellets may be effected during manufacture or by the consumer, man- ageable lengths being provided from which the consumer breaks or twists off pellets as required. A pellet precursor may be, for example, a straight row of pellets, to be broken off as needed.
The extrusion pressure may be whatever is required to carry out the process in an efficient manner. Suitably it is in excess of 3 bar (0.3MPa), preferably in excess of 5 bar (0.5MPa), and more preferably is preferably in excess of 8 bar (O.δMPa). More preferably still is preferably in excess of 12 bar (1.2MPa). Most preferably it is in excess of 40 bar (4MPa) . The extrusion pressure preferably does not exceed 100 bar (lOMPa) , more preferably 60 bar (6MPa) .
Generally the pellets are for use in injection moulding pro- cesses. The injection moulding process is preferably used for the manufacture of water soluble pouches intended to contain a detergent formulation for use in an automatic washing machine or in an automatic dishwasher. Thus the pellets preferably comprising a water-soluble / water- dispersible thermoplastic polymer
In this use the advantageous properties of the pellets produced in accordance with the invention, especially the high homogeneity have been found to be particularly beneficial. It is believed that this property is most beneficial as the integrity of the injection moulded product relies upon such high homogeneity of the composition being injection moulded as otherwise the low homogeneity will be reflected in the injection moulded product. The high homogeneity has been found to lead to predictable water solubility of injection moulded products.
Preferably the water-soluble / water-dispersible thermoplastic polymer comprises PVOH or a derivative thereof.
Other water-soluble / water-dispersible polymers may be used in the process either as an alternative or in addition to PVOH. Preferred examples include poly (vinylpyrollidone) , poly (acrylic acid), poly(maleic acid), a cellulose derivative (such as a cellulose ether / hydroxypropyl methyl cel- lulose) , poly(glycolide) , poly (glycolic acid), poly (lactides) , poly (lactic acid) and copolymers thereof.
Processing aids may be present in the admixture which is processed. Preferred processing aids include mono-, di-, tri-carboxylic acids / salts thereof, fatty acids such as stearic acid / salts thereof, mono-, di- or triglycerides / salts thereof, aerosil, inorganic and organic pigments.
The invention will now be illustrated with reference to the following non-limiting Examples. Examples ;
Example 1;
The pelletising process was conducted on an extruder (twin screw, ICMA S. Giorgio, Milan (dedicated to processing of plastic blends and alloys) .
The extruder had the following characteristics.
Screw diameter: 35 mm Screw length: 40 cm
Working pressure: 30 bar Output: 5 kg/h. Temperature zones: 6 (T1=50°C, T2=60°C, T3=T4=90°C, T5=105°C and T6 (the die) =105°C.)
The extruder was attached to a two-roll unit used as a cooling source and connected to a pellet cutter.
The following formula was fed into the extruder in powder form.
Figure imgf000011_0001
The pellets obtained were chilled to room temperature. The formula yielded solid pellets having low friability. Example 2 :
The pelletising process was conducted on a pellet press (model V3-75 from Universal Milling Technologies) .
The press had the following characteristics.
Die diameter: 350 mm Holes diameter: 2 mm
Hole length: 3 mm
Infeed cone: 45°
Space between die / rollers: 1.5 mm
Die speed: 5m/s Motor: 30 kW
Temperature: 98-102°C
The following formulae were fed into the extruder in powder form.
Figure imgf000012_0001
The pellets obtained were chilled to room temperature. Each formula yielded solid pellets having low friability.

Claims

1. A shaping process for making pellets of a thermoplastic extrudable resin composition comprising a thermoplastic polymer, plasticiser and optionally further additives, the plasticiser comprising a component which is solid at room temperature, wherein the process is run at a temperature above the melting point of the plasticiser and below the
"melting /" pϊastification temperature of the thermoplastic polymer.
2. A process according to claim 1, wherein the process comprises pressing, extrusion, calendering and / or compaction.
3. A process according to claim 1 or 2, wherein the plasticiser is present in the composition in at least 5%, more preferably 10%, most preferably 15%.
4. A process according to claim 2 or 3 , wherein the shaping process comprises extrusion.
5. A process according to claim 4, wherein the temperature of the material within the extruder does not exceed a temperature which is 10°C, more preferably 15°C, more prefera- bly 30°C and most preferably 45°C below the melting / plastification temperature of the thermoplastic polymer at any time.
6. A process according to claim 4 or 5, wherein the tempera- ture of material within the extruder is at least 40 °C, more preferably at least 45°C, and most preferably at least 50 °C.
7. A process according to any one of the proceeding claims, wherein the particle size of the raw materials used is below 2000μm/ more preferably below 1200μm, more preferably below 400μm and most preferably about 200μm.
8. A process according to according to any one of claims 1 to 7, wherein the plasticiser comprises a carbohydrate.
9. A process according to claim 8, wherein the carbohydrate is selected from the group comprising gluconic acids, amino sugars, sugar alcohols such as sorbitol, glucitol, mannitol, galactitol, dulcitol, xylitol, erythritol, isomaltutose and isomalt .
10. A process according to claim 8, wherein the carbohydrate is selected from the group comprising sorbitol, glucitol, mannitol, galactitol, dulcitol, xylitol, erythritol, isomaltutose and isomalt.
11. A process according to any one of claims 1 to 10, wherein the thermoplastic polymer is water-soluble / water dispersible.
12. A process according to claims 11, wherein the thermoplastic polymer comprises PVOH or a derivative thereof.
13. A process according to any one of claims 1 to 12, wherein the thermoplastic polymer comprises poly (vinylpyrollidone) , poly(acrylic acid), poly(maleic acid) , a cellulose derivative (such as a cellulose ether / hydroxypropyl methyl cellulose), poly (glycolide) , poly(glycolic acid), poly (lactides) , poly (lactic acid) and copolymers thereof.
14. A process according to claim 12 or 13, wherein the pellets are for use in injection moulding processes.
15. A process according to any one of claims 12 to 14, wherein the'^injection" moulding" process is used for the-manu- facture of water soluble pouches intended to contain a detergent formulation for use in an automatic washing machine or in an automatic dishwasher.
PCT/GB2004/005273 2003-12-19 2004-12-16 Process for making a pellet WO2005058569A1 (en)

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CA2549149A CA2549149C (en) 2003-12-19 2004-12-16 Process for making a pellet
US10/595,919 US20070075453A1 (en) 2003-12-19 2004-12-16 Process for making a pellet
PL04806087T PL1694480T3 (en) 2003-12-19 2004-12-16 Process for making a pellet
BRPI0416904-2A BRPI0416904A (en) 2003-12-19 2004-12-16 process to make a pallet
EP04806087.5A EP1694480B1 (en) 2003-12-19 2004-12-16 Process for making a pellet
AU2004299333A AU2004299333B2 (en) 2003-12-19 2004-12-16 Process for making a pellet
ZA2006/04239A ZA200604239B (en) 2003-12-19 2006-05-25 Process for making a pallet
AU2010212479A AU2010212479B2 (en) 2003-12-19 2010-08-20 Process for making a pellet
US12/949,302 US9327425B2 (en) 2003-12-19 2010-11-18 Process for making a pellet
US15/139,577 US20160279830A1 (en) 2003-12-19 2016-04-27 Process for making a pellet

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GB0329529A GB2409204A (en) 2003-12-19 2003-12-19 Plasticized thermoplastic polymer
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