US20070075453A1 - Process for making a pellet - Google Patents

Process for making a pellet Download PDF

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Publication number
US20070075453A1
US20070075453A1 US10/595,919 US59591904A US2007075453A1 US 20070075453 A1 US20070075453 A1 US 20070075453A1 US 59591904 A US59591904 A US 59591904A US 2007075453 A1 US2007075453 A1 US 2007075453A1
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US
United States
Prior art keywords
temperature
process according
thermoplastic polymer
plasticiser
poly
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US10/595,919
Other languages
English (en)
Inventor
Francesc Ayats
Diana Oehms
Pavlinka Roy
Jordi Salvador
Ralf Wiedemann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reckitt Benckiser NV
Original Assignee
Reckitt Benckiser NV
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=US20070075453(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Reckitt Benckiser NV filed Critical Reckitt Benckiser NV
Assigned to RECKITT BENCKISER N.V. reassignment RECKITT BENCKISER N.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SALVADOR, JORDI, AYATS, FRANCESC, OEHMS, DIANA, ROY, PAVLINKA, WIEDEMANN, RALF
Assigned to RECKITT BENCKISER N.V. reassignment RECKITT BENCKISER N.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RECKITT BENCKISER N.V.
Publication of US20070075453A1 publication Critical patent/US20070075453A1/en
Priority to US12/949,302 priority Critical patent/US9327425B2/en
Priority to US15/139,577 priority patent/US20160279830A1/en
Abandoned legal-status Critical Current

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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 3 mm in diameter and 3 mm in length. The pellets are used in a wide range of plastic article manufacturing processes.
  • the pellet manufacturing process generally includes a plastification step.
  • the formulation to be pelletised 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 several 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 polymers 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.
  • 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). 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.
  • 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.
  • 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 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.
  • 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 polymer.
  • 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 O) 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, galactitol, dulcitol, xylitol, erythritol, isomaltutose and isomalt.
  • plasticiser systems include solid fatty acid alkoxylates, fatty alcohol alkoxylates or polyalkylene glycols (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 connections, 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, manageable 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 (0.3 MPa), preferably in excess of 5 bar (0.5 MPa), and more preferably is preferably in excess of 8 bar (0.8 MPa). More preferably still is preferably in excess of 12 bar (1.2 MPa). Most preferably it is in excess of 40 bar (4 MPa).
  • the extrusion pressure preferably does not exceed 100 bar (10 MPa), more preferably 60 bar (6 MPa).
  • the pellets are for use in injection moulding processes.
  • 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 cellulose), 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 was attached to a two-roll unit used as a cooling source and connected to a pellet cutter.
  • the pellets obtained were chilled to room temperature.
  • the formula yielded solid pellets having low friability.
  • 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: 5 m/s Motor: 30 kW Temperature: 98-102° C.

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  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US10/595,919 2003-12-19 2004-12-16 Process for making a pellet Abandoned US20070075453A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
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

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB0329529A GB2409204A (en) 2003-12-19 2003-12-19 Plasticized thermoplastic polymer
GB0329529.2 2003-12-19
PCT/GB2004/005273 WO2005058569A1 (en) 2003-12-19 2004-12-16 Process for making a pellet

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2004/005273 A-371-Of-International WO2005058569A1 (en) 2003-12-19 2004-12-16 Process for making a pellet

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/949,302 Continuation US9327425B2 (en) 2003-12-19 2010-11-18 Process for making a pellet

Publications (1)

Publication Number Publication Date
US20070075453A1 true US20070075453A1 (en) 2007-04-05

Family

ID=30776162

Family Applications (3)

Application Number Title Priority Date Filing Date
US10/595,919 Abandoned US20070075453A1 (en) 2003-12-19 2004-12-16 Process for making a pellet
US12/949,302 Expired - Fee Related US9327425B2 (en) 2003-12-19 2010-11-18 Process for making a pellet
US15/139,577 Abandoned US20160279830A1 (en) 2003-12-19 2016-04-27 Process for making a pellet

Family Applications After (2)

Application Number Title Priority Date Filing Date
US12/949,302 Expired - Fee Related US9327425B2 (en) 2003-12-19 2010-11-18 Process for making a pellet
US15/139,577 Abandoned US20160279830A1 (en) 2003-12-19 2016-04-27 Process for making a pellet

Country Status (12)

Country Link
US (3) US20070075453A1 (zh)
EP (2) EP2202040B1 (zh)
CN (1) CN1894080A (zh)
AU (2) AU2004299333B2 (zh)
BR (1) BRPI0416904A (zh)
CA (1) CA2549149C (zh)
ES (1) ES2536277T3 (zh)
GB (1) GB2409204A (zh)
PL (2) PL1694480T3 (zh)
TR (1) TR201900584T4 (zh)
WO (1) WO2005058569A1 (zh)
ZA (1) ZA200604239B (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8318230B2 (en) * 2005-05-02 2012-11-27 Henkel Ag & Co. Kgaa Use of debranched starch in extrusion-spheronization pharmaceutical pellets
US20150057398A1 (en) * 2013-08-26 2015-02-26 Ingenia Polymers, Inc. Compacted pelletized additive blends containing a polymer carrier
US20160311984A1 (en) * 2013-12-24 2016-10-27 The Nippon Synthetic Chemical Industry Co., Ltd. Saponified ethylene-vinyl ester copolymer pellet and method for producing saponified ethylene-vinyl ester copolymer pellet

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007026166A1 (de) 2007-06-04 2008-12-11 Kuraray Europe Gmbh Verfahren zur thermoplastischen Formgebung von Polyvinylalkohol und hiermit hergestellte Formkörper oder Granulate
ES2293859B1 (es) * 2007-09-28 2009-04-01 Plasticos Hidrosolubles, S.L. Procedimiento para la elaboracion de una granza de polietenol de alta fluidez.
US20110248423A1 (en) * 2010-04-07 2011-10-13 Steven Proper Synthetic Mulch and Method of Making Same
KR102388870B1 (ko) * 2016-05-13 2022-04-20 메르크 파텐트 게엠베하 가소제로서의 아미노 당의 용도
CN107802041A (zh) * 2017-11-28 2018-03-16 广东汇星新材料科技股份有限公司 一种可长期去除体味的内衣

Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607812A (en) * 1968-12-17 1971-09-21 Denki Kagaku Kogyo Kk Method of manufacturing polyvinyl alcohol films and product
US3997489A (en) * 1974-11-25 1976-12-14 E. I. Du Pont De Nemours And Company Melt extrudable polyvinyl alcohol compositions
US4119604A (en) * 1976-08-18 1978-10-10 E. I. Du Pont De Nemours And Company Polyvinyl alcohol compositions for use in the preparation of water-soluble films
US4150009A (en) * 1977-06-27 1979-04-17 Abtec Chemical Company ABS extrusion compositions
US4206101A (en) * 1974-01-03 1980-06-03 E. I. Du Pont De Nemours And Company Melt extrudable cold water-soluble films
US4323492A (en) * 1978-03-23 1982-04-06 Hoechst Aktiengesellschaft Plasticizer containing polyvinyl alcohol granules
US4469837A (en) * 1981-10-30 1984-09-04 Pietro Cattaneo Polyvinyl-alcohol-based thermoplastic composition
US4775720A (en) * 1987-10-29 1988-10-04 International Flavors & Fragrances Inc. Schiff base reaction products of aldehydes and alkyl anthranilates and organoleptic uses thereof
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