EP1527122A1 - Film a base de polyurethanne thermoplastique a memoire de forme - Google Patents

Film a base de polyurethanne thermoplastique a memoire de forme

Info

Publication number
EP1527122A1
EP1527122A1 EP03766180A EP03766180A EP1527122A1 EP 1527122 A1 EP1527122 A1 EP 1527122A1 EP 03766180 A EP03766180 A EP 03766180A EP 03766180 A EP03766180 A EP 03766180A EP 1527122 A1 EP1527122 A1 EP 1527122A1
Authority
EP
European Patent Office
Prior art keywords
film
melting temperature
temperature
temporary
shape
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.)
Withdrawn
Application number
EP03766180A
Other languages
German (de)
English (en)
Inventor
Johann Diedrich Brand
Herbert MÖLLERING
Daniela Herkenhoff
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.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1527122A1 publication Critical patent/EP1527122A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2280/00—Compositions for creating shape memory
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters

Definitions

  • the invention relates to films based on thermoplastic polyurethane in a temporary form, the film in the permanent form having a thickness which is at least 10% greater than the thickness of the film in the temporary form.
  • the invention further relates to methods for packaging or coating materials, one of the films according to the invention based on thermoplastic polyurethane being brought into contact with the material to be packaged, preferably the material to be packaged, into the
  • shrink films based on known thermoplastic plastics are often used, which, by applying a vacuum in the space to be packaged, closely fit the object to be packaged
  • the object of the present invention was to develop a film, in particular packaging film, which has both excellent mechanical properties such as low abrasion and 30 high tear resistance and can also be used in the simplest possible process for packaging and preferably sealing objects.
  • Thermoplastic polyurethane hereinafter also referred to as TPU, is used as the material for the production of the film, which is generally known, widely described and commercially available. It is essential to the invention that the film can be transferred from a temporary state in which the film is in a stretched state with a small thickness to a permanent state, in particular by heating the film to a temperature greater than / equal to the switching temperature and a lower melting temperature of the hard phase ,
  • the object of the invention is the film in the temporary form, that is, in the elongated form. 45
  • the temporary shape is defined by the possibility of converting it to the permanent shape by heating the foil to a temperature greater than or equal to the switching temperature can.
  • the "permanent shape" of the film according to the invention is, in particular, the shape of the film which is present at a temperature in the range of greater than or equal to the switching temperature, ie in particular the melting temperature of the soft phase, and a low melting temperature of the hard phase.
  • the "temporary shape” of the film according to the invention is in particular the shape of the film which is below the switching temperature, ie the melting temperature of the soft phase, and by heating the film to a temperature in the range of greater than or equal to the melting temperature of the soft phase and a lower melting temperature of the hard phase the temporary form can be converted into the permanent form.
  • the transition from a temporary form to a permanent form by heating the TPU is described in the article "For - memory polymers" by A. Landlein and S. Kelch, Angewandte Chemie, 2002. 114, 2138-2162, WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, in which terms such as “temporary shape”, “permanent shape”, “switching temperature” or “Ttrans” and “Tperm” are also explained.
  • the switching temperature is defined in particular as the melting temperature of the soft phase of the polyurethane, which can be determined using generally known methods.
  • the melting temperature of the soft phase of the polyurethane is, in particular, the temperature at which the maximum of the melting peak of the soft phase is present in the DSC (differential scanning calorimetry) measurement.
  • Tperm is in particular the melting temperature of the hard phase of the TPU, i.e. the melting temperature of the entire TPU.
  • This melting temperature can also be determined by generally known methods, for example using the temperature at which the maximum of the melting peak of the hard phase is present in the DSC (differential scanning calometry) measurement.
  • the switching temperature is preferably in a range from 25 ° C. to 50 ° C.
  • This switching temperature can be determined in particular by the selection of suitable polyols (b), which will be presented later, in particular the butane-1,4-diol and / or hexane-1,6-diol adipates with a molecular weight of 2000 g / mol to 4000 g / mol, can be set in a targeted manner since the ratio of butane-1,4-diol to hexane-1,6-diol in the polyester can be controlled in a targeted manner while maintaining the molecular weight and crystallinity.
  • the TPUs preferably have an at least partially crystalline soft phase, since the crystallinity of the soft phase determines the "width" of the switching temperature.
  • the temporary inventive form of the film according to the invention can be produced, for example, by cold stretching or rolling a generally customary and commercially available TPU film starting from the permanent form and in the stretched form at a temperature lower than the switching temperature. temperature until the film has taken on this temporary shape.
  • This form conversion from the permanent form to the temporary form takes place through the partial crystallization of the soft phase at temperatures lower than the melting temperature of the soft phase.
  • the film By cooling to a temperature lower than the switching temperature, the film is fixed in the stretched, temporary shape, which only changes back to the permanent shape when heated above or equal to the switching temperature.
  • Generally known machines or devices for stretching or rolling the film can be used, for example known gusset machines or rollers. Manual stretching is also possible.
  • the stretching can be one-dimensional or two-dimensional, that is to say in width and length.
  • the film is preferably stretched by 10% to 300%, particularly preferably by 10% to 100%, in particular 50% to 100%, ie the film covers an area in the temporary shape which 10% to 300%, particularly preferably 10% to 100%, in particular 50% to 100% larger than the area of the film in the permanent form.
  • the process for producing the film according to the invention can thus preferably be carried out by stretching or rolling the film from the permanent shape, the thickness of which is at least 10% greater than the thickness of the film in the temporary shape, in the range higher or equal melting temperature of the soft phase and lower melting temperature of the hard phase in the temporary form and in this temporary form cools to a temperature lower than the melting temperature of the soft phase.
  • the film in the temporary, ie stretched form usually has a thickness of 0.01 mm to 1.5 mm, preferably 0.02 mm to 0.2 mm, particularly preferably 0.02 mm to 0.1 mm, in particular 0, 02 mm to 0.06 mm.
  • the thickness of the film in the permanent form is at least 10%, preferably 15% to 500%, particularly preferably 20% to 100% greater than the thickness of the film in the plastic rare form.
  • the thickness of the film in the temporary or permanent form can be determined precisely using generally known methods.
  • Coating of materials especially sensitive devices, e.g. automobiles, machines, boats, electronic goods such as Computers, mobile telephones, printers, monitors, televisions, hi-fi devices as well as other sensitive goods such as books, storage media and lamps are caused by the shrinking of the film during the transition from the stretched, temporary form through an increase in temperature to the permanent form has a greater thickness, but correspondingly a smaller length and / or width.
  • the material to be packaged is preferably wrapped closely with the film in the temporary form in order to ensure that the film in the permanent form lies as closely as possible to the material and does not slip.
  • Thermoplastic polyurethanes and processes for their production are generally known and have been described in many different ways.
  • the TPUs according to the invention preferably have an at least partially crystalline soft phase.
  • TPU are characterized by good strength, abrasion, tear resistance and chemical resistance, among other things, and can be produced in almost any hardness by suitable raw material composition.
  • TPUs offer the advantage of cost-effective production, for example by the belt or reaction extruder process, which can be carried out continuously or batchwise, and the simple processing of thermoplastics.
  • the production of films from the thermoplastic polyurethane, for example by means of extrusion is generally known to the person skilled in the art.
  • the preparation is usually carried out by reacting (a) diisocyanates, in the present case preferably aliphatic diisocyanates, with (b) compounds which are reactive toward isocyanates and have a molecular weight of 500 g / mol to 8000 g / mol, if appropriate in the presence of (c) chain extension means with a molecular weight of 60 g / mol to 499 g / mol, (d) catalysts and / or (e) customary auxiliaries.
  • diisocyanates in the present case preferably aliphatic diisocyanates
  • the build-up components (b) and (c) can be varied in relatively wide molar ratios.
  • Molar ratios of component (b) to chain extenders (c) to be used in total from 1: 0.5 to 1: 8, in particular from 1: 1 to 1: 4, have proven useful, the hardness of the TPUs increasing with the content of (c) increases.
  • the Implementation for the production of the TPU can take place with a key figure of 0.8 to 1.2: 1, preferably with a key figure of 0.9 to 1: 1.
  • the characteristic number is defined by the ratio of the total isocyanate groups of component (a) used in the reaction to those which are reactive towards isocyanates
  • thermoplastic polyurethanes are usually produced in a one-shot or prepolymer process on the belt system or on the reaction extruder.
  • the components (a), (b) and (c) and, if appropriate, chain terminators which come to the reaction are combined together or in a specific order and brought to reaction.
  • the build-up components (a) to (c) and, if appropriate, chain terminators, (d) and / or (e) are introduced into the extruder individually or as a mixture, e.g. reacted at temperatures of 100 to 250 ° C, preferably 140 to 220 ° C, the TPU obtained is extruded, cooled and granulated.
  • the TPU film can be produced by generally known methods.
  • Aliphatic, cycloaliphatic, araliphatic and / or aromatic diisocyanates can be used as isocyanates, usually diisocyanates.
  • aromatic isocyanates may be mentioned by way of example: 2,4-tolylene diisocyanate, mixtures of 2,4- and 2,6-tolylene diisocyanate, 4,4'-, 2,4'- and / or 2,2 '-Diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'- and / or 2, 4-diphenylmethane diisocyanates, 4, 4' - Diisocyanatodiphenylethane (1,2) and 1,5-naphthylene diisocyanate.
  • aliphatic diisocyanates customary aliphatic and / or cycloaliphatic diisocyanates are used, for example tri, tetra, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methyl-pentamethylene-diisocyanate-1, 5, 2-ethylbutylene diisocyanate-1,4,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis ( isocyanatomethyl) - cyclohexane (HXDI), 1, 4-cyclohexane diisocyanate, l-methyl-2, 4- and / or -2, 6-cyclohexane diisocyanate, 4,4'-, 2,4'- and / or 2,2'-dicyclohexylme
  • Hexamethylene-1,6-diisocyanate (hexamethylene diisocyanate, HDI) is preferred and / or 4,4'-, 2,4'- and / or 2,2'-diphenylmethane diisocyanate (MDI) is used as isocyanate (a).
  • HDI hexamethylene diisocyanate
  • MDI 2,2'-diphenylmethane diisocyanate
  • isocyanate-reactive compounds generally known polyhydroxyl compounds with molecular weights of 500 g / mol to 8000 g / mol, preferably 800 g / mol to 6000 g / mol, in particular 2000 g / mol to 4000 g / mol, and preferably an average functionality of 1.8 to 2.6, preferably 1.9 to 2.2, in particular 2, for example generally known polyesterols, polyetherols and / or polycarbonate diols.
  • Ratio of butane-1,4-diol and hexane-1,6-diol can be selected depending on the desired melting point of the soft phase and the desired crystallinity of the soft phase.
  • chain extenders for example diamines and / or alkanediols having 2 to 10 carbon atoms in the alkylene radical, in particular ethylene glycol and / or 1,4-butanediol, and / or hexanediol and / or di - and / or tri-oxyalkylene glycols with 3 to 8 carbon atoms in the oxyalkylene radical, preferably corresponding oligo-polyoxypropylene glycols, it also being possible to use mixtures of the chain extenders.
  • diamines and / or alkanediols having 2 to 10 carbon atoms in the alkylene radical in particular ethylene glycol and / or 1,4-butanediol, and / or hexanediol and / or di - and / or tri-oxyalkylene glycols with 3 to 8 carbon atoms in the oxyalkylene radical, preferably corresponding oligo-polyoxypropylene
  • Suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the structural components (b) and (c), are the tertiary amines known and customary in the prior art, such as, for example, triethylamine , Dimethylcyclohexylamine, N-methylmorpholine, N, N '-Dirnethylpiperazin, 2- (Dirnethylaminoethoxy) -ethanol, Diazabicyclo- (2,2,2) -octane and similar as well as in particular organic metal compounds such as titanium esters, iron compounds such as iron ( III) - acetylacetonate, tin compounds, for example tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dil
  • customary auxiliaries can also be added to the structural components (a) to (d).
  • examples include surface-active substances, glass fibers, flame retardants, nucleating agents, lubricants and mold release agents, dyes and pigments, inhibitors, stabilizers against hydrolysis, light, heat, oxidation or discoloration, protective agents against microbial degradation, inorganic and / or organic fillers, reinforcing agents and plasticizers.
  • additives which, in this invention in particular, lead to an improvement in the adhesion between TPU and wood, particle board or wood substitutes.
  • adhesion promoters can e.g. Additives containing isocyanate.
  • TPU directly during synthesis or only during thermoplastic processing in bulk or incorporated in a carrier, e.g. TPU, can be added as so-called masterbatches.
  • chain terminators with a molecular weight of 46 to 499 can also be used.
  • chain terminators are compounds that have only one isocyanate-reactive functional group, such as Mono alcohols. The flow behavior can be specifically adjusted by means of such chain terminators.

Abstract

L'invention concerne des films à base de polyuréthanne thermoplastique ayant une forme temporaire. Le film a, dans sa forme permanente, une épaisseur qui est supérieure d'au moins 10 % à l'épaisseur du film dans sa forme temporaire.
EP03766180A 2002-07-25 2003-07-16 Film a base de polyurethanne thermoplastique a memoire de forme Withdrawn EP1527122A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE2002134007 DE10234007A1 (de) 2002-07-25 2002-07-25 Folie auf der Basis von thermoplastischem Polyurethan
DE10234007 2002-07-25
PCT/EP2003/007684 WO2004013210A1 (fr) 2002-07-25 2003-07-16 Film a base de polyurethanne thermoplastique a memoire de forme

Publications (1)

Publication Number Publication Date
EP1527122A1 true EP1527122A1 (fr) 2005-05-04

Family

ID=30010382

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03766180A Withdrawn EP1527122A1 (fr) 2002-07-25 2003-07-16 Film a base de polyurethanne thermoplastique a memoire de forme

Country Status (4)

Country Link
EP (1) EP1527122A1 (fr)
AU (1) AU2003250071A1 (fr)
DE (1) DE10234007A1 (fr)
WO (1) WO2004013210A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007011239A1 (de) 2007-03-08 2008-11-06 Bayer Materialscience Ag Verfahren zur Herstellung von Formgedächtnisformkörpern mit einem breiten Einsatzbereich
WO2012146676A1 (fr) 2011-04-27 2012-11-01 Basf Se Profilés extrudés en matière plastique, contenant des éléments isolants introduits en continu
US9492957B2 (en) 2011-04-27 2016-11-15 Basf Se Extruded plastics profiles comprising continuously introduced insulation elements
WO2015144435A1 (fr) * 2014-03-27 2015-10-01 Basf Se Matériau thermoplastique à mémoire de forme

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4816094A (en) * 1984-05-01 1989-03-28 Kimberly-Clark Corporation Method of producing a heat shrinkable elastomer and articles utilizing the elastomer
US5189110A (en) * 1988-12-23 1993-02-23 Asahi Kasei Kogyo Kabushiki Kaisha Shape memory polymer resin, composition and the shape memorizing molded product thereof
JP3732404B2 (ja) * 1998-02-23 2006-01-05 ニーモサイエンス ゲーエムベーハー 形状記憶ポリマー組成物、形状記憶製品を形成する方法、および形状を記憶する組成物を形成する方法
JP4078411B2 (ja) * 2000-08-29 2008-04-23 ニチアス株式会社 自動車エンジン用防音カバー及び前記防音カバー用フォーム材の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004013210A1 *

Also Published As

Publication number Publication date
DE10234007A1 (de) 2004-02-05
WO2004013210A1 (fr) 2004-02-12
AU2003250071A1 (en) 2004-02-23

Similar Documents

Publication Publication Date Title
EP1338614B1 (fr) Procédé de production des elastomères de polyuréthane thermoplastiques, mous, facilement démoulables et à retrait minime
EP2139934B1 (fr) Procédé de réaction de polyuréthanes thermoplastiques avec des composés présentant des groupes isocyanate
EP1967537A1 (fr) Procédé de fabrication de corps de moulage à mémoire de forme dotés d'une grande zone d'utilisation
EP3122795B1 (fr) Tuyau flexible pneumatique en tpu
WO2006134138A1 (fr) Polyurethanne thermoplastique contenant de l'isocyanate
DE102005039933A1 (de) Verfahren zur Herstellung von thermoplastisch verarbeitbaren Polyurethanen
DE3321516A1 (de) Antistatische und/oder elektrisch leitfaehige, thermoplastische polyurethane, verfahren zu deren herstellung und deren verwendung
DE2248382C2 (de) Polyurethan-Elastomere, deren Herstellung und Verwendung
EP3394138B1 (fr) Materiau retractable en tpu
EP2760902B1 (fr) Articles homogènes extrudés à partir de polyuréthanes thermoplastiques à base de polyester diols de l'acide succinique et de 1,3-propanediol
DE3323520A1 (de) Weiche, gummielastische, thermoplastische polyurethane, verfahren zu deren herstellung und deren verwendung
EP3420009B1 (fr) Procede de fabrication d'un copolymere dibloc
EP2582757A1 (fr) Procédé de préparation de mélanges de polylactides (pla) et de polyuréthanes thermoplastiques (tpu)
EP1204688A1 (fr) Polyurethannes thermoplastiques
EP3645597B1 (fr) Polyuréthane thermoplastique
WO2010149636A2 (fr) Polyuréthane à base de polyuréthane thermoplastique souple
DE10022848A1 (de) Formkörper aus thermoplastischen Polyurethanen mit reduziertem Fogging
DE19757569A1 (de) Aliphatische, emissionsarme, sinterfähige thermoplastische Polyurethanformmassen
EP2569359A2 (fr) Polyuréthane thermoplastique contenant de la glycérine estérifiée avec au moins un acide carboxylique aliphatique, comme plastifiant
WO2004013210A1 (fr) Film a base de polyurethanne thermoplastique a memoire de forme
DE19816525A1 (de) Verfahren zur Herstellung von thermoplastischen Polyurethanen
WO2004012926A1 (fr) Corps moule cylindrique creux a base de polyurethanne thermoplastique
DE10037622A1 (de) Verfahren zur Herstellung von Folien auf der Basis von thermoplastischen Polyurethanen
DE102005021366A1 (de) Formgedächtnispolymer
DE10109302A1 (de) Thermoplastische Polyurethane auf der Basis aliphatischer Isocyanate

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050225

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20070201