SI9200092A - Process for preparing a foam sheet of thermoplastic polyurethane and product obtained therefrom - Google Patents
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- 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
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Abstract
Description
Postopek za izdelavo penaste folije iz termoplastičnega poliuretana kot tudi produkt, ki se ga da dobiti z njimProcess for the production of thermoplastic polyurethane foam as well as the product obtainable therefrom
Izum se nanaša na postopek za izdelavo penaste folije iz termoplastičnega poliuretana kot tudi na produkt, ki se ga da dobiti z njim.The invention relates to a process for making a foam film of thermoplastic polyurethane as well as to a product obtainable therefrom.
Poliuretani nastanejo iz poliadicijske reakcije izocianatov z najmanj dvema skupinama NCO in diolov oz. poliolov ob tvorbi uretanske grupacije (RCNH-CO-O-R2). Medtem ko uporabljajo kot izocianatne komponente v glavnem nižjemolekulske diizocianate, kot TDI (izomerna zmes iz 2,4- in 2,6toluilendiizocianata), so kot dioli oz. polioli pomembni pretežno poliester- in polieter-polioli, t.j. spojine z daljšimi verigami, tudi razvejene, s terminalnimi hidroksilnimi skupinami. V posebnih primerih uporabljajo - ob tvorbi derivatov sečnine-, za podaljšanje verige tudi nižjemolekulske diamine.Polyurethanes are formed from the polyaddition reaction of isocyanates with at least two groups of NCOs and diols or. polyols upon formation of the urethane group (RCNH-CO-OR 2 ). While used as isocyanate components, they are mainly lower molecular weight diisocyanates, such as TDI (isomeric mixture of 2,4- and 2,6-toluylenediisocyanate), they are like diols or. polyols important predominantly polyester and polyether polyols, i.e., longer chain compounds, also branched, with terminal hydroxyl groups. In special cases, when urea derivatives are formed, lower molecular weight diamines are used to extend the chain.
Za izdelavo poliuretanskih pen uporabljajo danes različne postopke:Today different processes are used to make polyurethane foams:
a) z reakcijo izocianata z vodo se tvori CO, ki fungira kot penilni plin (prednostno pri izdelavi mehke pene);a) by reaction of isocyanate with water, CO is formed which functions as a foam gas (preferably in the manufacture of soft foam);
b) z dodatkom tekočin z nizkim vreliščem spenijo ob uparjenju penila zmes, ki reagira eksotermično (prednostno pri izdelavi trde pene); inb) by the addition of low boiling liquids, the foam is reacted exothermically (preferably in the manufacture of hard foam) by evaporation of the foam. and
c) z vpihavanjem ali vtepanjem zraka tvorijo med reakcijo peno (prednostno pri izdelavi penjenih premazov).c) by blowing or boiling in air, they form a foam during the reaction (preferably in the production of foam coatings).
Pri tem je treba reakcijo penjenja in reakcijo premreženja s specialno katalizo drugo z drugo uskladiti tako, da nobena ne prehiteva druge.In doing so, the foaming reaction and the crosslinking reaction with special catalysis must be coordinated with each other so that none overtakes the other.
Čeprav je že od 5O-tih let znana izdelava termoplastičnih poliuretanskih elastomerov, ki se odlikujejo z veliko natezno trdnostjo in pretržnim raztezkom, veliko fleksibilnostjo tudi pri nizkih temperaturah, visoko temperaturo trajne uporabe, majhno trajno deformacijo pri statični dinamični obremenitvi, visoko obstojnostjo pri drgnjenju in obrabi, visoko trgalno trdnostjo, visoko dušilnostjo, visoko obstojnostjo proti oljem, maščobam in mnogim topilom in energetsko bogatemu ter UV-sevanju in ki so brez mehčal, se doslej še ni posrečilo dobiti penastih folij iz tovrstnega materiala. Zato so bili na področjih, na katerih uporabljajo penaste folije v velikem obsegu, kot v avtomobilski industriji, navezani na uporabo produktov iz mehkega PVC, ki so z ekoloških vidikov vprašljivi. Termoplastičen poiiuretan, ki bi tu lahko nadomestil PVC, v stanju tehnike ni znan.Although the manufacture of thermoplastic polyurethane elastomers has been known since the 5Os, with high tensile strength and tear strength, high flexibility even at low temperatures, high durability, low durable deformation under static dynamic loading, high abrasion resistance, and wear, high tear strength, high damping, high resistance to oils, fats and many solvents and energy-rich and UV-free, and which have no softeners, have not yet been fortunate enough to obtain foam foils of this kind. Therefore, in areas where foam films are used on a large scale, such as in the automotive industry, they have been linked to the use of soft PVC products, which are questionable from an ecological point of view. Thermoplastic polyurethane, which could replace PVC here, is unknown in the art.
Izum temelji zato na nalogi ustvariti novovrstno penasto folijo na osnovi poliuretanov, ki lahko nadomesti doslej znane penaste folije iz mehkega PVC.The invention is therefore based on the task of creating a new type of foam based on polyurethane, which can replace the previously known soft foam of PVC.
V smislu izuma rešimo to nalogo pri splošnem postopku tako, da poiiuretan zmešamo s penilom in v primerni pripravi kontinuirno ali diskontinuirno izoblikujemo z učinkovanjem toplote.According to the invention, this task is accomplished in the general process by mixing polyurethane with foam and in a suitable preparation continuously or discontinuously shaped by heat.
Posebno s pridom uporabimo kot termoplastičen poiiuretan alifatski ah aromatski poiiuretan na osnovi polietrov, poliestrov, polialkanov, polialkenov ali polialkinov ali njihove zmesi.Particularly advantageously used as thermoplastic polyurethane aliphatic ahromatic polyurethane based on polyethers, polyesters, polyalkanes, polyalkenes or polyalkines or mixtures thereof.
V smislu izuma predlagamo, da uporabimo kot penilo termično razkrojljive, anorganske hidrogenkarbonate.According to the invention, it is proposed to use as foaming thermally degradable, inorganic hydrogen carbonates.
Alternativno lahko uporabimo kot penilo termično razkrojljive soli organskih mono-, di- ali polifunkcionalnih kislin.Alternatively, the thermally degradable salts of organic mono-, di- or polyfunctional acids can be used as a foam.
Pri tem je posebno prednostno uporabiti kot soli hidrogenske soli.It is particularly advantageous to use the hydrogen salts as salts.
Pri tem je posebno ugodno, če dodamo kot pomožno penilo anorganske in/ali organske kisline.Particularly advantageous is the addition of inorganic and / or organic acids as an auxiliary foam.
Nadalje predlagamo, da uporabimo kot penilo diamid diazendikarboksilne kisline.It is further proposed to use diazendicarboxylic acid diamide as a foam.
Posebno prednostno je pri tem dodati katalizatorje za razkroj diamidov diazendikarboksilnih kislin.It is particularly advantageous to add catalysts for the decomposition of diazendicarboxylic acid diamides.
Nadalje predlagamo, da uporabimo kot penilo sulfohidrazide.We further propose to use sulfohydrazides as a foaming agent.
Alternativno lahko uporabimo kot penilo sulfonilsemikarbazide.Alternatively, it can be used as a foaming sulfonylsemicarbazide.
V smislu izuma končno predlagamo, da uporabimo kot penilo tetrazole.According to the invention, it is finally proposed to use tetrazoles as foam.
Prednostno je predvideno, da se vrši izoblikovanje penaste folije preko ekstrudeija.Preferably, foaming of the foil is performed via extrusion.
S pridom lahko uporabimo poliuretan v obliki granulata in/ali prahu.Polyurethane in the form of granulate and / or powder can be advantageously used.
Nadalje predlagamo, da penasto folijo po izoblikovanju termično poobdelujemo 15 do 20 ur pri 80 do 120 °C, da bi dosegli optimalni nivo njenih lastnosti. Pri tem pride do naknadne kemične reakcije komponent. Termična poobdelava je posebno važna za obnašanje pri vračanju v prvotno obliko.It is further suggested that foam foil is thermally wetted after formation for 15 to 20 hours at 80 to 120 ° C to achieve the optimum level of its properties. This results in a subsequent chemical reaction of the components. Thermal empowerment is especially important for the return behavior to its original form.
Izum se poleg tega nanaša na penasto folijo, ki jo lahko dobimo po postopku v smislu izuma.The invention further relates to a foam which can be obtained by the process of the invention.
Ta se prednostno odlikuje s trdoto od 50 do 90 Shore A, pretržno silo v vzdolžni smeri od 300 do 600 N, pretržno silo v prečni smeri do 250 do 500 N, pretržnim raztezkom v vzdolžni smeri od 1300 do 1800 % in pretržnim raztezkom v prečni smeri od 800 do 1400 % pri debelini okoli 1,5 mm.This is preferably characterized by a hardness of 50 to 90 Shore A, a breaking force in the longitudinal direction from 300 to 600 N, a breaking force in the transverse direction up to 250 to 500 N, a breaking elongation in the longitudinal direction from 1300 to 1800%, and a breaking elongation in the transverse directions from 800 to 1400% at a thickness of about 1.5 mm.
Posebno prednostno ima trdoto od 65 do 75 Shore A, pretržno silo v vzdolžni smeri od 400 do 500 N, pretržno silo v prečni smeri od 300 do 450 N, pretržni raztezek v vzdolžni smeri od 1400 do 1600 % in pretržni raztezek v prečni smeri od 1100 do 1300 %.Particularly preferably, it has a hardness of 65 to 75 Shore A, a breaking force in the longitudinal direction from 400 to 500 N, a breaking force in the transverse direction from 300 to 450 N, a breaking elongation in the longitudinal direction from 1400 to 1600%, and a breaking elongation in the transverse direction from 1100 to 1300%.
Končno ima najbolj prednostno trdoto okoli 70 Shore A, pretržno silo v vzdolžni smeri okoli 460 N, pretržno silo v prečni smeri okoli 360 N, pretržni raztezek v vzdolžni smeri okoli 1550 % in pretržni raztezek v prečni smeri okoli 1200 %.Finally, the most preferred hardness is about 70 Shore A, a breaking force in the longitudinal direction of about 460 N, a breaking force in the transverse direction of about 360 N, a breaking elongation in the longitudinal direction of about 1550% and a breaking elongation in the transverse direction of about 1200%.
Pri tem je penasta folija v smislu izuma posebno prednostno izoblikovana z enostransko zaprto zunanjo površino, kar vpliva posebno pozitivno na njeno predelavnost glede na zgoraj navedene postopke nadaljnje predelave.In this case, the foam of the invention is particularly preferably formed with a single-sided closed outer surface, which has a particularly positive effect on its processability with respect to the above-mentioned further processing operations.
Kot je v nadaljevanju še podrobneje opisano, se je pokazalo, da tovrstna penasta folija na osnovi poliuretanov izpolnjuje vse zahteve, da jo lahko uporabimo kot (v mnogih primerih boljši) nadomestek za penaste folije iz mehkega PVC. Medtem ko dosežejo doslej uporabljane penaste folije iz mehkega PVC pri navedeni debelini trdoto okoli 60 Shore A, pretržno silo v vzdolžni smeri največ 200 N, pretržno silo v prečni smeri prav tako največ 200 N, pretržni raztezek v vzdolžni smeri največ 300 % in pretržni raztezek v prečni smeri prav tako največ 300 %, nova penasta folija na osnovi poliuretanov v smislu izuma vse te lastnosti daleč prekaša. Razen tega je novovrstna penasta folija odporna proti staranju, da se toplo oblikovati in z različnimi postopki (med drugim tudi z vtiskovalnim kalandrom) vtiskovati in kaširati. Tako predstavlja polnovreden nadomestek za penaste folije iz mehkega PVC, ki so jih doslej uporabljali v avtomobilski industriji, in le-te zlasti z ekološkega vidika daleč prekaša, ker se da pene na osnovi poliuretanov daljnosežno reciklirati, pri morebitnem gorenju ne sproščajo nobenih zdravju škodljivih produktov in mehčala jim niso potrebna.As further described below, it has been shown that this type of polyurethane-based foam meets all the requirements to be used as a (in many cases better) substitute for soft PVC foam. While soft PVC foams used hitherto have a hardness of about 60 Shore A, a breaking force in the longitudinal direction of not more than 200 N, a breaking force in the transverse direction also not exceeding 200 N, a breaking elongation in the longitudinal direction of not more than 300% and a breaking elongation up to 300% in the transverse direction, the new polyurethane-based foam of the invention surpasses all these properties. In addition, the new type of foam is resistant to aging, to be molded warmly and to be embossed and lined by various processes (including the embossing calender). Thus, it is a valuable substitute for soft PVC foam films used so far in the automotive industry, which are far superior in ecological terms, since polyurethane-based foams can be recycled far away, without any harmful products being burned and they do not need plasticizers.
Nadaljnje lastnosti in prednosti penaste folije v smislu izuma kot tudi nadaljnje podrobnosti postopka v smislu izuma se nahajajo v sledečem opisu nekaterih izvedbenih primerov.Further features and advantages of the foam of the invention as well as further details of the process of the invention are provided in the following description of some embodiments.
PRIMER 1EXAMPLE 1
Kot izhodno spojino smo uporabili polieter-poliuretan firme Bayer AG, Leverkusen, z oznako Desmopan KA 8550. Po predhodnem sušenju smo granulat zmešali z 2 mas.% penila, ki sestoji iz natrijevega hidrogenkarbonata in citronske kisline, in ga v običajnem ekstruderju s šobo s široko režo ekstrudirali v penasto folijo z debelino okoli 1,5 mm, pri čemer smo izbrali temperaturne cone v ekstruderju naraščajoče od okoli 170 ° do okoli 220 °C. Ekstruzijski produkt je imel trdoto od 65 do 70 Shore A, pretržno silo v vzdolžni smeri okoli 380 N, pretržno silo v prečni smeri okoli 300 N, pretržni raztezek v vzdolžni smeri okoli 1400 % in pretržni raztezek v prečni smeri okoli 1150 %. Dodatno ocenjevanje folije je pokazalo daljnosežno pravilno porazdelitev mehurčkov pene pri nekoliko nepravilni velikosti mehurčkov. Predelavnost s šobo s široko režo je bila podana, čeprav ni bila optimalna.Polymer-polyurethane from Bayer AG, Leverkusen, under the designation Desmopan KA 8550 was used as the starting compound. After pre-drying, the granulate was mixed with 2 wt% of foam consisting of sodium hydrogen carbonate and citric acid and in a conventional nozzle extruder with the wide slit was extruded into foam film about 1.5 mm thick, selecting the temperature zones in the extruder increasing from about 170 ° to about 220 ° C. The extrusion product had a hardness of 65 to 70 Shore A, a breaking force in the longitudinal direction of about 380 N, a breaking force in the transverse direction of about 300 N, a breaking elongation in the longitudinal direction of about 1400%, and a breaking elongation in the transverse direction of about 1150%. Further evaluation of the foil revealed a far-reaching correct distribution of foam bubbles at a slightly irregular bubble size. Workability with a wide-slot nozzle was given, although it was not optimal.
PRIMER 2EXAMPLE 2
Kot izhodni produkt smo uporabili polieter-poliuretan firme Elastogran Polyurethan-Elastomere GmbH z oznako Elastolan VP 1175 AW. Predhodno posušenemu granulatu smo dodali okoli 1 mas.% kemičnega penila, ki ga prodaja firma Bohringer Ingelheim pod oznako Hydroceyrol BH 70 kot bel valjast granulat na PE-vosku kot nosilčnem materialu in z okoli 70 %-nim deležem kombinacije iz organskih kislin in karbonatov oz. njihovih derivatov.We used polyester-polyurethane from Elastogran Polyurethan-Elastomere GmbH under the label Elastolan VP 1175 AW as the starting product. About 1% by weight of the chemical foam sold by Bohringer Ingelheim under the Hydroceyrol BH 70 label was added to the previously dried granulate as a white cylindrical granulate on PE wax as a carrier material and with about 70% by weight of the combination of organic acids and carbonates or . their derivatives.
Predelava se je vršila z istim običajnim ekstrudeijem s šobo s široko režo pri približno istem temperaturnem profilu kot v primeru 1. Dobljena penasta folija je kazala zelo enakomerno porazdelitev mehurčkov pri prav tako zelo enakomerni velikosti mehurčkov. Predelavnost materiala z ekstrudeijem je bila zelo dobra. Preizkus trdote na sveže ekstrudirani penasti foliji je dal srednjo trdoto 71 Shore A. S temperiranjem oz. po okoli 6-tedenskem skladiščenju folije pri sobni temperaturi je prišlo do majhnega zvišanja do največ 73 Shore A.Processing was carried out with the same conventional extrusion with a wide-slot nozzle at approximately the same temperature profile as in Example 1. The foam obtained showed a very uniform bubble distribution at a very uniform bubble size. The workability of the extruded material was very good. The hardness test on freshly extruded foam film gave a mean hardness of 71 Shore A. after about 6 weeks of storage of the film at room temperature, a slight increase to a maximum of 73 Shore A occurred.
Nateznih poskusov nismo - enako kot v primeru 1 - izvedli po DIN-normi 53517, temveč po tovarniški normi na 50 mm širokih trakovih pri natezni hitrosti pri 100 ml/m. Prosta dolžina je znašala 20 mm, celotna dolžina 140 m. Pri penasti foliji z debelino okoli 1,5 mm je pri tem znašala srednja pretržna sila v vzdolžni smeri okoliWe did not perform tensile tests - as in Example 1 - according to DIN standard 53517, but according to the factory standard on 50 mm wide strips at a tensile speed of 100 ml / m. Free length was 20 mm, overall length 140 m. In the case of foam foil about 1.5 mm thick, the mean breaking force in the longitudinal direction was
460 N, srednja pretržna sila v prečni smeri okoli 360 N, srednji pretržni raztezek v vzdolžni smeri okoli 1550 % in srednji pretržni raztezek v prečni smeri okoli 1200 %. Te vrednosti karakterizirajo izvrstno trdnost novovrstne penaste folije in daleč prekašajo višje zgoraj navedene primeijalne vrednosti folij iz mehkega PVC.460 N, mean transverse force in transverse direction of about 360 N, mean transverse elongation in longitudinal direction of about 1550%, and mean transverse elongation in transverse direction of about 1200%. These values characterize the excellent strength of the new foam foil and far surpass the higher priming values of the soft PVC foil.
PRIMERI 3 DO 11EXAMPLES 3 TO 11
Izhodni produkti in penila za te poskuse so zbrani v naslednji tabeli I. Predelava se je vršila v vseh primerih v istem običajnem ekstrudeiju s šobo s široko režo kot v primerih 1 in 2. Temperaturno območje je pri tem (v odvisnosti od izhodnega materiala) nihalo med 150 °C in 300 °C.The starting products and the foams for these experiments are summarized in the following Table I. The processing was performed in all cases in the same conventional wide-slot nozzle extrusion as in cases 1 and 2. The temperature range fluctuated (depending on the starting material). between 150 ° C and 300 ° C.
Vse dobljene penaste folije so kazale zelo enakomerno porazdelitev mehurčkov pri prav tako zelo enakomerni velikosti mehurčkov. Predelavnost materiala je bilo treba v vsakem primeru označiti kot dobro. Ustrezne navedbe o lastnostih materiala so prav tako razvidne iz tabele I.All foams obtained showed a very uniform bubble distribution with a very uniform bubble size. In any case, the workability of the material had to be characterized as good. Relevant indications of material properties are also shown in Table I.
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Primer poliuretan penilo trdota pretržna sila pretržna sila pretržni raztezek pretržni raztezek (delež) (Shore A) v vzdolžni v prečni v vzdolžni prečni smeri (%) •HExample polyurethane foam hardness breaking force breaking force breaking elongation breaking elongation (proportion) (Shore A) in longitudinal in transverse in longitudinal transverse direction (%) • H
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V nadaljevanju so podrobneje opisani poskusi, ki smo jih izvedli na novovrstnih, za primer izdelanih penastih folijah, da bi preverili njihovo predelavnost, zlasti glede njihove sposobnosti, da bi nadomestile penaste folije iz PVC, ki jih uporabljajo sedaj.The following describes in more detail the experiments we have carried out on new, for example, foamed foils to test their processability, in particular as regards their ability to replace the foamed PVC foils they are currently using.
Poskus 1Experiment 1
V tem poskusu smo najprej preverili sposobnost folij iz primera 1 in 2 za toplo oblikovanje. V ta namen smo vpeli vzorec folije 100 x 100 mm med dve okrogli aluminijasti plošči z okroglim izsekom s premerom 50 mm v sredini. Vpeto folijo smo najprej obremenili z zaobljenim trnom s premerom 10 mm s podajalno hitrostjo 10 mm/m. Po globini vleka 30 mm je kazal preizkuševalnik silo okoli 10 N. Po razbremenitvi so se vzorci spontano vrnili v prvotno obliko. To kaže, da kažejo novovrstne penaste folije na osnovi poliuretanov pri sobni temperaturi izvrstno elastičnost.In this experiment, we first checked the ability of the foils of Examples 1 and 2 for hot forming. For this purpose, a 100 x 100 mm foil sample was inserted between two round aluminum plates with a round section of 50 mm diameter in the center. The clamped foil was first loaded with a rounded 10 mm diameter mandrel with a feed rate of 10 mm / m. After a draw depth of 30 mm, the tester showed a force of about 10 N. After unloading, the samples spontaneously returned to their original shape. This indicates that the new grade polyurethane-based foams at room temperature exhibit excellent elasticity.
Nato smo okoli preizkusnega vzorca potisnili pečico z obtokom zraka in vključili gretje. Po okoli 20 minutah sta znašali tako temperatura v prostoru kot tudi temperatura krožečega zraka okoli 120 °C. Tlačna sila je sedaj padla na 3 N. Preizkusne vzorce smo ohladili bodisi počasi na zraku ali spontano z mrzlo vodo. Oba načina hlajenja sta dala stabilno klobukasto deformacijo, ki je imela gumielastičen značaj. Pri vnovičnem segretju deformirane folije na 81 °C in temu sledeči ohladitvi je folija obdržala svojo obliko.We then pushed an air-circulating oven around the test sample and turned on the heating. After about 20 minutes, both the room temperature and the circulating air temperature were around 120 ° C. The compressive force has now dropped to 3 N. The test specimens were cooled either slowly in air or spontaneously with cold water. Both cooling modes gave a stable hat deformation that had a rubbery character. Upon reheating the deformed film to 81 ° C and subsequent cooling, the film retained its shape.
Poskus 2Experiment 2
S kosi penaste folije, izdelane v primeru 1 in v primeru 2, smo izvedli v nadaljevanju podrobneje opisane vtiskovalne poskuse.The foam sheets made in Example 1 and Example 2 were followed by the embossing experiments described below.
Pri tem smo kos folije z dimenzijami 140 x 200 x 1,5 mm najprej segreli na gladki grelni ploskvi in vtisnili z mrzlim vtiskovalnim valjem. Vtisnjeno stran penaste folije smo vsakokrat položili za 15 sekund na predhodno segreto grelno ploskev, ki je bila preslojena s Teflonom. Temperatura folije je znašala za prvi poskus 220 °C. Za naslednje poskuse smo jo zviševali v stopnjah za vsakič po 10 °C.The piece of foil with dimensions of 140 x 200 x 1.5 mm was first heated on a smooth heating surface and stamped with a cold embossing cylinder. Each time, the foam side of the foil was placed for 15 seconds on a pre-heated Teflon coated heating surface. The foil temperature was 220 ° C for the first experiment. For the following experiments, it was increased in steps of 10 ° C each time.
Nato smo folijo vzeli z grelne ploskve in jo z bolj vročo stranjo navzgor položili v vtiskovalnik in porinili pod mrzli vtiskovalni valj. Vtiskovalni čas je znašal 30 sekund, kar ustreza vtiskovalni hitrosti okoli 2,5 m/min. Pri večkratni ponovitvi vtiskovalnih poskusov smo vedno dosegli enakomerno površino. Da bi preizkusili, kako toplotno obstojna je oblika vtiska, smo kose vtisnjene folije izpostavili za 5 ur temperaturi 140 °C. Ugotoviti nismo mogli nobene spremembe kvalitete vtiska. Tudi pri segretju folije na 160 °C je ostala kvaliteta vtiska enaka.We then removed the foil from the heating surface and placed it upwards with the hot side in the embosser and pushed it under the cold embossing cylinder. The embossing time was 30 seconds, which corresponds to an embossing speed of about 2.5 m / min. Repeated stamping experiments always resulted in a uniform surface. To test how heat-resistant the impression form is, the pieces of the impression film were exposed for 140 hours at 140 ° C. We couldn't detect any change in impression quality. Even when the film was heated to 160 ° C, the impression quality remained the same.
Poskus 3Experiment 3
Poskusi vročega kaširanja oz. zlepljenja penaste folije z nepenjeno prekrivno folijo so dali prav tako dobre vrednosti trdnosti pri vročem kaširanju nad 170 °C oz. uporabi posebnih lepil na osnovi poliuretanov. Tako izdelane kompozitne folije smo v temu sledečih poskusih, ki so v svoji izvedbi ustrezali poskusu 1 in 2, preizkusili glede sposobnosti za vtiskovanje in toplo oblikovanje. Pokazalo se je, da je bila tudi kompozitna folija brez problemov sposobna za vtiskovanje in oblikovno obstojno preoblikovanje. S kaširanjem ustvarjeni, usnju podobni površinski strukturi predelava ni škodovala.Attempts to hot lash the adhesion of the foam film to the non-foamed coating film also gave good values of hot lining strength above 170 ° C or. use of special adhesives based on polyurethanes. The composite films made in this way were tested in the following experiments, which in their implementation correspond to Experiments 1 and 2, with respect to their ability for embossing and hot forming. It was also shown that the composite film was also capable of embossing and design-resistant transformation without problems. The lining-created, leather-like surface structure did not harm the processing.
Penaste folije v smislu izuma na osnovi poliuretanov so sprva v veliki meri brezbarvne in prozorne. Vendar se je pokazalo, da se da z dodatkom običajnih barvnih koncentratov, izdelanih kot veziva za poliuretanske izhodne produkte, doseči dobro kritnost barve, ki ji ne škodujejo niti ekstruzija niti morebitne sledeče stopnje nadaljnje obdelave.The foams of this invention based on polyurethanes are initially largely colorless and transparent. However, it has been shown that by adding conventional color concentrates made as binders to polyurethane starting products, good color coverage can be obtained which is not adversely affected by extrusion or any subsequent further processing step.
V zgornjem opisu kot tudi v zahtevkih in risbah opisane značilnosti izuma so lahko tako posamič kot tudi v poljubni kombinaciji bistvene za uresničenje izuma v njegovih različnih izvedbenih oblikah.The above description, as well as the claims and drawings described in the features of the invention, both individually and in any combination, may be essential for the realization of the invention in its various embodiments.
Claims (19)
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DE19914117649 DE4117649C1 (en) | 1991-05-29 | 1991-05-29 |
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SI9200092A SI9200092A (en) | 1991-05-29 | 1992-05-27 | Process for preparing a foam sheet of thermoplastic polyurethane and product obtained therefrom |
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EP (1) | EP0516024A1 (en) |
CN (1) | CN1067005A (en) |
DE (1) | DE4117649C1 (en) |
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CA2676108C (en) | 1999-01-26 | 2011-11-22 | Huntsman International Llc | Foamed thermoplastic polyurethanes |
AU2003236849A1 (en) * | 2002-05-27 | 2003-12-12 | Huntsman International Llc | Foamed supramolecular polymers |
EP1979401B1 (en) * | 2006-01-18 | 2010-09-29 | Basf Se | Foams based on thermoplastic polyurethanes |
CN101352145B (en) * | 2007-07-23 | 2012-07-25 | 中国林业科学研究院林业研究所 | Seedling cultivation method in tissue culture container and special container thereof |
CN101831036B (en) * | 2009-03-13 | 2011-12-21 | 黄汉平 | Manufacturing method of modified unsaturated polyester resin |
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US3933548A (en) * | 1974-08-19 | 1976-01-20 | Beatrice Foods Co. | Production of urethane foams and laminates thereof |
GB1512034A (en) * | 1975-06-04 | 1978-05-24 | Ici Ltd | Microcellular polyurethane elastomers |
CH598301A5 (en) * | 1975-07-10 | 1978-04-28 | Ciba Geigy Ag | |
JPH0737543B2 (en) * | 1987-04-24 | 1995-04-26 | 本田技研工業株式会社 | Vibration control sheet for automobiles |
JPH01230616A (en) * | 1988-03-11 | 1989-09-14 | Kao Corp | Thermoplastic polyurethane resin composition for foam molding |
DE3810595A1 (en) * | 1988-03-29 | 1989-10-12 | Wolff Walsrode Ag | Thermoplastic films |
DE3916874A1 (en) * | 1989-05-24 | 1990-11-29 | Basf Ag | SOFT, ELASTIC POLYURETHANE FILMS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
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1991
- 1991-05-29 DE DE19914117649 patent/DE4117649C1/de not_active Expired - Fee Related
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1992
- 1992-05-25 WO PCT/DE1992/000436 patent/WO1992021716A1/en unknown
- 1992-05-25 EP EP92108804A patent/EP0516024A1/en not_active Withdrawn
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DE4117649C1 (en) | 1993-01-07 |
CN1067005A (en) | 1992-12-16 |
EP0516024A1 (en) | 1992-12-02 |
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