CA2549149C

CA2549149C - Process for making a pellet

Info

Publication number: CA2549149C
Application number: CA2549149A
Authority: CA
Inventors: Francesc Ayats; Diana Oehms; Pavlinka Roy; Jordi Salvador; Ralf Wiedemann
Original assignee: Reckitt Benckiser NV
Current assignee: Reckitt Benckiser Finish BV
Priority date: 2003-12-19
Filing date: 2004-12-16
Publication date: 2015-08-25
Anticipated expiration: 2024-12-16
Also published as: EP1694480B1; US20070075453A1; BRPI0416904A; EP2202040A2; US20110062620A1; US9327425B2; AU2004299333A1; WO2005058569A1; CN1894080A; CA2549149A1; EP2202040A3; ES2536277T3; PL2202040T3; AU2010212479A1; GB2409204A; EP2202040B1; AU2010212479B2; TR201900584T4; PL1694480T3; GB0329529D0

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 pel-lets 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 diame-ter 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 com-ponents 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 dis-advantage 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 in-duced decomposition. Also these 'hot' processes give a heat

2 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 dis-advantages of the 'hot' 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 is-sue 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 proc-ess) 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

3 size of the pellets is difficult and so the size of the pel-lets can vary significantly.
Furthermore significant dust formation is typical for this kind of process. Additionally the pellets are commonly fri-able having poor integrity and easily form dust from fric-tion rubbing against each other, thus worsening the dust is-sue. 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 associ-ated 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 manufac-ture of water soluble PVOH pouches in extrusion / injection moulding processes. The pouches, as an example, are com-monly 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 homoge-neity to ensure that the pouches produced have good integ-rity to be stable in storage and have the expected water dissolution properties.

4 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/plastification temperature of the thermoplastic polymer.
According to one aspect of the present application, there is provided an extrusion process of making water-soluble pellets in an extruder of a thermoplastic extrudable resin composition comprising a thermoplastic polymer and a plasticiser, wherein:
the thermoplastic polymer is a water-soluble polyvinyl alcohol (PVOH) or a derivative thereof, and is the only thermoplastic polymer in the composition; and the plasticiser consists of a component which is solid at room temperature and a further auxiliary component selected from the group consisting of glycerine, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethanol amine, diethanol amine, methyldiethyl amine and mixtures thereof; the process comprising the step of extruding said composition in an extruder, wherein: the maximum temperature at which the 4a extruder is run is above the melting point of said solid component of the plasticiser and below the melting or plastification temperature of the thermoplastic polymer; and the temperature of the composition within the extruder does not exceed a temperature which is 45 C below the melting or plastification temperature of the thermoplastic polymer at any time.
According to another aspect of the present invention, there is provided a shaping process for making water-soluble pellets of a thermoplastic extrudable resin composition comprising a thermoplastic polymer and a plasticiser, wherein: the thermoplastic polymer is a water-soluble polyvinyl alcohol (PVOH) or a derivative thereof, and is the only thermoplastic polymer in the composition; the plasticiser consists of a component which is solid at room temperature, or the plasticiser consists of a component which is solid at room temperature and one or more further auxiliary components selected from the group consisting of glycerine, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethanol amine, diethanol amine, and methyldiethyl amine; the process is run at a temperature above the melting point of said solid component of the plasticiser and below the melting or plastification temperature of the thermoplastic polymer; and the process comprises pressing, calendering and/or compaction.
The shaping process may comprise pressing, extrusion, calendering and/or compaction. Most preferably the shaping process comprises extrusion.

4b According to another aspect of the present invention, there is provided a process for manufacturing a water soluble pouch for containing an automatic washing machine detergent composition or an automatic dishwasher detergent composition, said process comprising: a) extruding a thermoplastic extrudable resin composition in an extruder to form pellets, said composition comprising: i) a thermoplastic polymer which is a water-soluble polyvinyl alcohol (PVOH) or a derivative thereof; and ii) plasticiser consisting of a component which is solid at room temperature, or consisting of a component which is solid at room temperature and one or more further auxiliary components selected from the group consisting of glycerine, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethanol amine, diethanol amine, and methyldiethyl amine; wherein the maximum temperature at which the extruder is run is above the melting point of said solid component of the plasticiser and below the melting or plastification temperature of the thermoplastic polymer; and the temperature of the composition within the extruder does not exceed a temperature which is 45 C below the melting or plastification temperature of the thermoplastic polymer at any time; and b) injection moulding of said pellets to form said pouch; wherein said composition is in the form of a homogeneous blend in said pellets and said pouch.
According to another aspect of the present invention, there is provided a process for manufacturing a water soluble pouch for containing an automatic washing machine detergent composition or an automatic dishwasher detergent composition, said process comprising: a) shaping a thermoplastic extrudable resin 4c composition to form pellets using a shaping process comprising pressing, calendering and/or compaction, said composition comprising: i) a thermoplastic polymer which is a water-soluble polyvinyl alcohol (PVOH) or a derivative thereof; and ii) plasticiser consisting of a component which is solid at room temperature, or consisting of a component which is solid at room temperature and one or more further auxiliary components selected from the group consisting of glycerine, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethanol amine, diethanol amine, and methyldiethyl amine; wherein the maximum temperature at which the shaping process is run is above the melting point of said solid component of the plasticiser and below the melting or plastification temperature of the thermoplastic polymer; and the temperature of the composition during the shaping process does not exceed a temperature which is 45 C below the melting or plastification temperature of the thermoplastic polymer at any time; and b) injection moulding of said pellets to form said pouch; wherein said composition is in the form of a homogeneous blend in said pellets and said pouch.
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 thermoplastic 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.

4d 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.

5 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 predict-ability 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-mer.
Generally the components are delivered to the shaping equip-ment 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 ob-served to ensure high homogeneity of the pellets. The par-ticle 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.
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 ex-truder does not exceed a temperature which is 10 C below

6 the melting / plastification temperature of the thermoplas-tic 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 pre-ferred operating temperature.
The melting point of the plasticiser component is preferably at least 15 C, prefera-bly at least 30 C and most preferably at least 45 C below the melting / plastification temperature of the thermoplas-tic polymer.
Preferably the plasticiser comprises a carbohydrate.
Carbohydrates are usually represented by the generalised formula C.(H20)7.
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 sta-ble carbohydrates such as sorbitol, glucitol, mannitol, ga-lactitol, dulcitol, xylitol, erythritol, isomaltutose and isomalt.

7 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 gly-col, 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.
Alterna-tively 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 cut-ting. However, other separation methods, for example twist-ing, 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 cut-ting or pressing or nipping or perforating (all such methods

8 collectively called "scoring" herein) to form frangible separation webs, may also be employed, to form tablet pre-cursors. 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 precur-sor 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 (0.8MPa). 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 ex-ceed 100 bar (10MPa), 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 pro-duced 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

9 PCT/GB2004/005273 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 thermoplas-tic 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 deriva-tive (such as a cellulose ether / hydroxypropyl methyl cel-ls 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:
5 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 cool-ing source and connected to a pellet cutter.
. 20 The following formula was fed into the extruder in powder form.
Material PVOH resin 85.0 Sorbitol 11.0 Processing aids 4.0 Total 100.0 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.
Material Formula 1 Formula 2 Formula 3 PVOH resin 81.0 87.0 85.0 Sorbitol 15.0 11.0 11.0 Processing aids 4.0 2.0 4.0 Total 100.0 100.0 100.0 The pellets obtained were chilled to room temperature. Each formula yielded solid pellets having low friability.

Claims

CLAIMS:

1. An extrusion process of making water-soluble pellets in an extruder of a thermoplastic extrudable resin composition comprising a thermoplastic polymer and a plasticiser, wherein:
- the thermoplastic polymer is a water-soluble polyvinyl alcohol (PVOH) or a derivative thereof, and is the only thermoplastic polymer in the composition; and - the plasticiser consists of a component which is solid at room temperature and a further auxiliary component selected from the group consisting of glycerine, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethanol amine, diethanol amine, methyldiethyl amine and mixtures thereof;
the process comprising the step of extruding said composition in an extruder, wherein:
- the maximum temperature at which the extruder is run is above the melting point of said solid component of the plasticiser and below the melting or plastification temperature of the thermoplastic polymer; and - the temperature of the composition within the extruder does not exceed a temperature which is 45 C below the melting or plastification temperature of the thermoplastic polymer at any time.

2. A process according to claim 1, wherein the plasticiser comprises at least 5% by weight of the composition.

3. A process according to claim 1, wherein the plasticiser comprises at least 10% by weight of the composition.

4. A process according to claim 1, wherein the plasticiser comprises at least 15% by weight of the composition.

5. A process according to any one of claims 1 to 4, wherein the temperature of the extrudable resin composition within the extruder is at least 40°C.

6. A process according to any one of claims 1 to 5, wherein the thermoplastic polymer and the plasticiser are in particulated form having a particle size below 2000 µm.

7. A process according to any one of claims 1 to 6, wherein the further auxiliary component comprises the propylene glycol.

8. A process according to any one of claims 1 to 7, wherein the pellets are suitable for use in an injection moulding process.

9. A process according to claim 8, wherein the injection moulding process is for manufacture of a water soluble pouch for containing an automatic washing machine detergent composition or an automatic dishwasher detergent composition.

10. A shaping process for making water-soluble pellets of a thermoplastic extrudable resin composition comprising a thermoplastic polymer and a plasticiser, wherein:

- the thermoplastic polymer is a water-soluble polyvinyl alcohol (PVOH) or a derivative thereof, and is the only thermoplastic polymer in the composition;
- the plasticiser consists of a component which is solid at room temperature, or the plasticiser consists of a component which is solid at room temperature and one or more further auxiliary components selected from the group consisting of glycerine, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethanol amine, diethanol amine, and methyldiethyl amine;
- the process is run at a temperature above the melting point of said solid component of the plasticiser and below the melting or plastification temperature of the thermoplastic polymer; and - the process comprises pressing, calendering and/or compaction.

11. A
process for manufacturing a water soluble pouch for containing an automatic washing machine detergent composition or an automatic dishwasher detergent composition, said process comprising:
a) extruding a thermoplastic extrudable resin composition in an extruder to form pellets, said composition comprising: i) a thermoplastic polymer which is a water-soluble polyvinyl alcohol (PVOH) or a derivative thereof; and ii) plasticiser consisting of a component which is solid at room temperature, or consisting of a component which is solid at room temperature and one or more further auxiliary components selected from the group consisting of glycerine, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethanol amine, diethanol amine, and methyldiethyl amine;
wherein the maximum temperature at which the extruder is run is above the melting point of said solid component of the plasticiser and below the melting or plastification temperature of the thermoplastic polymer; and the temperature of the composition within the extruder does not exceed a temperature which is 45°C below the melting or plastification temperature of the thermoplastic polymer at any time; and b) injection moulding of said pellets to form said pouch;
wherein said composition is in the form of a homogeneous blend in said pellets and said pouch.

12. A
process for manufacturing a water soluble pouch for containing an automatic washing machine detergent composition or an automatic dishwasher detergent composition, said process comprising:
a) shaping a thermoplastic extrudable resin composition to form pellets using a shaping process comprising pressing, calendering and/or compaction, said composition comprising: i) a thermoplastic polymer which is a water-soluble polyvinyl alcohol (PVOH) or a derivative thereof; and ii) plasticiser consisting of a component which is solid at room temperature, or consisting of a component which is solid at room temperature and one or more further auxiliary components selected from the group consisting of glycerine, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethanol amine, diethanol amine, and methyldiethyl amine;
wherein the maximum temperature at which the shaping process is run is above the melting point of said solid component of the plasticiser and below the melting or plastification temperature of the thermoplastic polymer; and the temperature of the composition during the shaping process does not exceed a temperature which is 45°C below the melting or plastification temperature of the thermoplastic polymer at any time; and b) injection moulding of said pellets to form said pouch;
wherein said composition is in the form of a homogeneous blend in said pellets and said pouch.