ES2450137T5 - Láminas fibrosas recubiertas o impregnadas con polímeros o mezclas poliméricas biodegradables - Google Patents
Láminas fibrosas recubiertas o impregnadas con polímeros o mezclas poliméricas biodegradables Download PDFInfo
- Publication number
- ES2450137T5 ES2450137T5 ES04743833.8T ES04743833T ES2450137T5 ES 2450137 T5 ES2450137 T5 ES 2450137T5 ES 04743833 T ES04743833 T ES 04743833T ES 2450137 T5 ES2450137 T5 ES 2450137T5
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- polymers
- polymer
- weight
- biodegradable polymers
- polymer blends
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Landscapes
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Description
B. Polímeros biodegradables
Los polímeros biodegradables que se pueden utilizar dentro del alcance de la presente invención para recubrir o impregnar láminas fibrosas incluyen los que se degradan mediante la acción de organismos vivos, la luz, el aire, el
5 agua y sus combinaciones. Dichos polímeros incluyen una serie de polímeros sintéticos, tales como poliésteres, poliesteramidas, policarbonatos y similares. También se pueden utilizar poliésteres semisintéticos de origen natural (por ejemplo, procedentes de la fermentación). Las reacciones de biodegradación normalmente están catalizadas por enzimas y en general se producen en presencia de humedad. Las macromoléculas naturales que contienen uniones hidrolizables, tales como proteínas, celulosa y almidón, en general son susceptibles a la biodegradación por parte de las enzimas hidrolíticas de microorganismos. No obstante, unos pocos polímeros fabricados por el hombre también son biodegradables. El carácter hidrófilo/hidrófobo de los polímeros afecta enormemente a su biodegradabilidad, siendo los polímeros más polares, como norma general, los más fácilmente biodegradables. Otras características que afectan a la biodegradabilidad del polímero incluyen la cristalinidad, la flexibilidad de la cadena y la longitud de la cadena.
15 Aparte de poderse biodegradar, con frecuencia es importante que un polímero o una mezcla polimérica presente ciertas propiedades físicas, tales como rigidez, flexibilidad, resistencia al agua, resistencia a aceites, resistencia a disolventes, resistencia, elongación, estabilidad a la temperatura, transmisión de la humedad del vapor, permeabilidad a gases, y/o pliegue muerto. La aplicación prevista de una mezcla polimérica particular con frecuencia dictará qué propiedades son necesarias con el fin de que un polímero, una mezcla polimérica particular, o una lámina tratada a partir de ellos, presente los criterios de comportamiento deseados. Cuando se utilicen para formar láminas tratadas adecuadas para su uso como materiales de envasado, los criterios de comportamiento deseados pueden incluir la elongación, pliegue muerto, resistencia, aptitud para su impresión, impermeabilidad a líquidos, transpirabilidad, estabilidad a la temperatura, y similares.
25 Debido al número limitado de polímeros biodegradables con frecuencia es difícil, o incluso imposible, identificar un único polímero o copolímero que cumpla con todos o incluso la mayoría de los criterios de comportamiento deseados para una aplicación dada. Esto es particularmente cierto en el área de los materiales de envasado. Los polímeros que tienen una elevada temperatura de transición vítrea (Tg) son con frecuencia difíciles, sino imposibles, de conformar mediante soplado o fundido en películas a gran escala. Por otra parte, los polímeros que tienen una temperatura de transición vítrea muy baja normalmente también tienen unos puntos de ablandamiento y/o fusión relativamente bajos, lo que hace que la producción en masa de láminas o películas sin la tendencia al bloqueo, o auto-adhesión sea muy difícil. Además, dichas láminas o películas pueden carecer de las suficientes propiedades de resistencia, propiedades de barrera al vapor de agua, alta estabilidad a la temperatura y/o módulo para que sean
35 adecuadas en ciertas aplicaciones, tales como la fabricación de envoltorios o recubrimientos laminados.
En un aspecto de la invención, se ha descubierto que se pueden obtener composiciones adecuadas para el recubrimiento o la impregnación de láminas fibrosas al mezclar uno o más polímeros "rígidos", o de alta temperatura de transición vítrea, con uno o más polímeros "blandos", o de baja temperatura de transición vítrea. En otro aspecto de la invención, los polímeros o mezclas poliméricas se pueden rellenar con agentes de relleno particulados, y/o las láminas o películas tratadas fabricadas a partir de ellos se pueden texturizar, con el fin de producir láminas que tengan unas propiedades de pliegue muerto mejoradas.
A pesar de los beneficios que se pueden obtener de la utilización de una mezcla de polímeros rígidos y blandos, en
45 particular cuando se extruden o se soplan películas o láminas utilizadas para recubrir láminas fibrosas, se apreciará que hay métodos de recubrimiento que no requieren la formación de una lámina o película extrudida o soplada, tales como la extensión utilizando una rasqueta o el recubrimiento por pulverización. En esos casos, puede no ser necesario utilizar una mezcla polimérica. No obstante puede ser deseable utilizar agua, un disolvente o un plastificante para incrementar el MFI con el fin de facilitar el proceso de recubrimiento o impregnación. Puede ser deseable incorporar una cantidad significativa de un agente de relleno inorgánico (por ejemplo, sílice o piedra caliza) con el fin de incrementar la estabilidad térmica de la lámina tratada resultante. En el caso de un envoltorio alimentario, el incremento de la estabilidad térmica aumenta la capacidad de la lámina tratada para soportar microondas.
55 1. Polímeros rígidos
Aunque la utilización de términos tales como polímeros "rígidos" y "blandos" puede ser algo arbitraria, dicha clasificación es útil a la hora de determinar qué polímeros se mezclan con el fin de obtener una mezcla polimérica que tenga los criterios de comportamiento deseados. En general, los polímeros que se pueden caracterizar como relativamente "rígidos", o menos flexibles, normalmente incluyen polímeros que tienen una temperatura de transición vítrea de al menos 10 °C aproximadamente. Los polímeros rígidos preferentemente tendrán una temperatura de transición vítrea de al menos 15 °C aproximadamente, más preferentemente de al menos 25 °C aproximadamente, y lo más preferentemente de al menos 35 °C aproximadamente. Las temperaturas anteriores tratan de tener en cuenta que la "temperatura de transición vítrea" no siempre es una temperatura discreta sino, con frecuencia, un intervalo
65 de temperaturas dentro del cual el polímero pasa de ser un material vidrioso y más frágil a ser un material más blando y más flexible.
8
pueden utilizar fibras inorgánicas hechas de vidrio, grafito, sílice, cerámica, lana de roca, o materiales metálicos. Las fibras preferidas incluyen algodón, fibras de madera (tanto fibras de madera dura como de madera blanda, ejemplos de las cuales incluyen fibras de madera sureña y pino sureño), lino, abacá, sisal, ramio, cáñamo y bagazo, ya que se descomponen fácilmente en condiciones normales. En muchos casos incluso se pueden utilizar fibras de papel
5 reciclado, y son muy baratas y abundantes.
Las fibras utilizadas en la fabricación de las láminas y otros artículos de la presente invención preferentemente tienen una elevada relación de longitud a anchura (o "relación de aspecto") ya que las fibras más largas y más estrechas pueden conferir una mayor resistencia a la mezcla polimérica al tiempo que añaden mucha menos masa y
10 volumen a la matriz que las fibras más espesas. Las fibras tendrán una relación de aspecto de al menos 10:1 aproximadamente, preferentemente superior a 25:1 aproximadamente, más preferentemente superior a 50:1 aproximadamente, y lo más preferentemente superior a 100:1 aproximadamente.
La cantidad de fibras añadidas a las mezclas poliméricas variará dependiendo de las propiedades deseadas para el
15 artículo de fabricación acabado, con la resistencia a la tracción, la tenacidad, la flexibilidad y los costes que son los criterios principales para determinar la cantidad de fibra a añadir a cualquier diseño. Por consiguiente, la concentración de fibras dentro de las mezclas poliméricas de la presente invención puede estar incluida en un intervalo amplio del 0 % al 90 % en peso aproximadamente de la mezcla polimérica. Si llegan a incluirse, las fibras se incluirán preferentemente en una cantidad en el intervalo entre el 1 % aproximadamente y el 80 % en peso
20 aproximadamente de la mezcla polimérica, más preferentemente en el intervalo del 3 % aproximadamente al 50 % en peso aproximadamente, y lo más preferentemente en un intervalo entre el 5 % aproximadamente y el 30 % en peso aproximadamente de la mezcla polimérica.
c. Agentes de relleno orgánicos
25 Las mezclas poliméricas también pueden incluir una amplia variedad de agentes de relleno orgánicos. Dependiendo de los puntos de fusión de la mezcla polimérica y del agente de relleno orgánico a añadir, el agente de relleno orgánico puede permanecer en forma de partículas discretas y constituir una fase sólida separada de la fase termoplástica, o se puede fundir parcial o completamente y asociarse parcial o completamente con la fase
30 termoplástica.
Los agentes de relleno orgánicos pueden comprender una amplia variedad de agentes de relleno de origen natural tales como, por ejemplo, SEAgel, corcho, semillas, gelatinas, harina de madera, serrín, materiales poliméricos molidos, materiales a base de agar, gránulos de almidón nativo, almidón pregelatinizado y seco, partículas
35 expandibles y similares. Los agentes de relleno orgánicos también pueden incluir uno o más polímeros sintéticos de los que existe una variedad casi interminable. Debido a la naturaleza diversa de los agentes de relleno orgánicos, en general no habrá un intervalo de concentraciones preferido para el componente opcional de agente de relleno orgánico.
40 Los agentes de relleno orgánicos pueden ocupar parcial o completamente el lugar de los agentes de relleno inorgánicos. En algunos casos, los agentes de relleno orgánicos se pueden seleccionar para que confieran las mismas propiedades que los agentes de relleno inorgánicos, tales como el incremento del pliegue muerto, la sensación de volumen en mano, la transpirabilidad y la transmisión del vapor de agua. Si llega a incluirse, el componente del agente de relleno orgánico por lo general se incluirá en una cantidad de al menos el 5 % en peso
45 aproximadamente de la composición total, preferentemente de al menos el 10 % en peso aproximadamente, más preferentemente de al menos el 20 % en peso aproximadamente, y más preferentemente en particular de al menos el 30 % en peso aproximadamente, y lo más preferentemente de al menos el 35 % en peso aproximadamente de la composición total.
50 3. Polímeros naturales
Además del almidón o partículas de almidón termoplástico, otros polímeros naturales que se pueden utilizar en las mezclas poliméricas comprenden o son derivados de celulosa, otros polisacáridos, gomas de polisacárido y proteínas.
55 Los ejemplos de almidones y derivados de almidón incluyen, pero no están limitados a, almidones modificados, almidones catiónicos y aniónicos, y ésteres de almidón tales como acetato de almidón, almidón hidroxietil éter, alquil almidones, dextrinas, amino almidones, almidones fosfato, y dialdehído almidones.
60 Los ejemplos de derivados de celulosa incluyen, pero no están limitados a, ésteres celulósicos (por ejemplo, formato de celulosa, acetato de celulosa, diacetato de celulosa, propionato de celulosa, butirato de celulosa, valerato de celulosa, ésteres mixtos, y sus mezclas) y éteres celulósicos (por ejemplo, metilhidroxietilcelulosa, hidroximetiletilcelulosa, carboximetilcelulosa, metilcelulosa, etilcelulosa, hidroxietilcelulosa, hidroxietilpropilcelulosa, y sus mezclas).
65
17
Otros polímeros basados en polisacáridos que se pueden incorporar a las mezclas poliméricas de la invención incluyen ácido algínico, alginatos, ficocoloides, agar, goma arábiga, goma de guar, goma de acacia, goma de carragenano, goma de furcelaran, goma ghatti, goma de psyllium, goma de membrillo, goma de tamarindo, goma de algarroba, goma de karaya, goma de xantano, y goma de tragacanto, y sus mezclas o derivados.
5 Los polímeros adecuados basados en proteínas incluyen, por ejemplo, Zein® (una prolamina derivada del maíz), colágeno (extraído de tejido conjuntivo y huesos de animales) y sus derivados tales como gelatina y cola, caseína (la proteína principal en la leche de vaca), proteína de girasol, proteína de huevo, proteína de soja, gelatinas vegetales, gluten y sus mezclas o derivados.
4. Polímeros no biodegradables
Aunque las mezclas poliméricas preferentemente incluyen polímeros biodegradables, sin duda entra dentro del alcance de la invención incluir uno o más polímeros que no sean biodegradables. Si el polímero no biodegradable en
15 general comprende una fase dispersa en lugar de la fase continua dominante, las mezclas poliméricas que incluyen un polímero no biodegradable serán biodegradables a pesar de todo, al menos en parte. Cuando se degrada, la mezcla polimérica puede dejar tras de sí un residuo no biodegradable que sin embargo es superior al residuo que queda tras las láminas y películas que están fabricadas en su totalidad de polímeros no biodegradables.
Los ejemplos de polímeros no biodegradables habituales adecuados para la formación de láminas y películas incluyen, pero no están limitados a, polietileno, polipropileno, polibutileno, PET, PETG, PETE, cloruro de polivinilo, PVDC, poliestireno, poliamidas, nailon, policarbonatos, polisulfuros, polisulfonas, copolímeros que incluyen uno o más de los anteriores, y similares.
25 D. Mezclas poliméricas
1. Intervalos de concentración de polímeros biodegradables
Las concentraciones de los diversos componentes dentro de las mezclas poliméricas utilizadas para tratar láminas fibrosas dependerá de una serie de factores, incluyendo las propiedades físicas y mecánicas deseadas de la lámina tratada, los criterios de comportamiento de los artículos a fabricar a partir de una lámina tratada, el equipo de procesamiento utilizado en la fabricación y conversión de las mezclas y las láminas tratadas en el artículo de fabricación deseado, y los componentes particulares dentro de las mezclas. El experto en la materia será capaz, a la luz de los ejemplos específicos y otras enseñanzas desveladas en el presente documento, de seleccionar y
35 optimizar las concentraciones de los diversos componentes mediante ensayos rutinarios.
En vista de la amplia variedad de mezclas poliméricas dentro del alcance de la invención, así como de la amplia variedad de diferentes propiedades que se pueden diseñar en las mezclas, se pueden incluir polímeros duros y blandos dentro de intervalos de concentraciones muy variables. En aquellos casos en los que la mezcla o composición polimérica incluya una mezcla de polímeros biodegradables rígidos y blandos, el uno o más polímeros rígidos biodegradables en las mezclas de la invención puede tener una concentración en un intervalo del 20 % aproximadamente al 99 % en peso aproximadamente de los polímeros biodegradables excluyendo la lámina fibrosa y cualquier agente de relleno, preferentemente una concentración de al menos el 30 % en peso aproximadamente de la mezcla polimérica, más preferentemente de al menos el 40 % en peso aproximadamente de la mezcla
45 polimérica, más preferentemente en particular superior a, pero que no incluye, el 50 % en peso de la mezcla polimérica, y lo más preferentemente de al menos el 55 % en peso aproximadamente de la mezcla polimérica.
De forma similar, cuando se emplea una mezcla de polímeros rígidos y blandos, los polímeros blandos pueden tener una concentración en un intervalo entre el 1 % aproximadamente y el 80 % en peso aproximadamente, de los polímeros biodegradables excluyendo la lámina fibrosa y cualquier agente de relleno, preferentemente una concentración de hasta el 70 % en peso aproximadamente de la mezcla polimérica, más preferentemente hasta el 60 % en peso aproximadamente de la mezcla polimérica, más preferentemente en particular inferior a, pero que no incluye, el 50 % en peso de la mezcla polimérica, y lo más preferentemente de hasta el 45 % en peso de la mezcla polimérica.
55 Las concentraciones anteriores se miden en términos de la mezcla de polímeros duros y blandos excluyendo cualquiera de los componentes opcionales que se pueden añadir, como se ha descrito y se ha identificado anteriormente.
2. Propiedades de las mezclas poliméricas y las láminas tratadas
Las mezclas poliméricas se pueden diseñar para que tengan varias propiedades deseadas como se describe en este documento. Las propiedades de la lámina fibrosa tratada final dependerán de una serie de factores, que incluyen el diseño de mezcla de la mezcla polimérica, las condiciones de procesamiento, el procesamiento después 65 de su formación, el tamaño del producto, el espesor particular, y similares. En el caso de láminas tratadas destinadas a su utilización como "envoltorios", tales como envoltorios utilizados para encerrar carnes, otros artículos
18
- 15
- 30 % 0 % 25 % 0 % 11,55 % 20,3 % 3,15 % 10 %
- 16
- 50 % 0 % 25 % 0 % 8,25 % 14,5 % 2,25 % 0 %
- 17
- 50 % 0 % 10 % 0 % 13,2 % 23,2 % 3,6 % 0 %
- 18
- 50 % 0 % 5 % 0 % 11,55 % 20,3 % 3,15 % 10 %
- 19
- 50 % 0 % 0 % 0 % 16,5 % 29,0 % 4,5 % 0 %
- 20
- 50 % 0 % 0 % 0 % 132 % 23,2 % 3,6 % 10 %
- 21
- 50 % 0 % 0 % 0 % 11,55 % 20,3 % 3,2 % 15 %
- 22
- 50 % 0 % 0 % 0 % 9,9 % 17,4 % 2,7 % 20 %
- 23
- 50 % 0 % 0 % 0 % 8,25 % 14,5 % 2,25 % 25 %
- 24
- 27 % 0 % 64 % 0 % 2,97 % 5,22 % 0,81 % 0 %
- 25
- 25 % 0 % 58 % 0 % 5,61 % 9,86 % 1,53 % 0 %
- 26
- 23 % 0 % 54 % 0 % 7,59 % 13,3 % 2,07 % 0 %
- 27
- 30 % 0 % 40 % 0 % 0 % 0,0 % 0,0 % 30 %
- 28
- 15 % 0 % 60 % 0 % 0 % 0,0 % 0,0 % 25 %
- 29
- 25 % 0 % 25 % 0 % 16,5 % 29,0 % 4,5 % 0 %
- 30
- 20 % 0 % 20 % 0 % 19,8 % 34,8 % 5,4 % 0 %
- 31
- 35 % 0 % 5 % 0 % 19,8 % 34,8 % 5,4 % 0 %
- 32
- 40 % 0 % 10 % 0 % 16,5 % 29,0 % 4,5 % 0 %
- 33
- 50 % 0 % 0 % 0 % 16,5 % 29,0 % 4,5 % 0 %
- 34
- 20 % 0 % 0 % 20 % 19,8 % 34,8 % 5,4 % 0 %
- 35
- 27 % 0 % 36 % 0 % 3,3 % 5,8 % 0,9 % 27 %
- 36
- 21 % 0 % 28 % 0 % 9,9 % 17,4 % 2,7 % 21 %
- 37
- 28,5 % 0 % 38 % 5 % 0 % 0 % 0 % 28,5 %
- 38
- 40 % 0 % 0 % 7 % 16,5 % 29,0 % 4,5 % 3 %
- 39
- 40 % 0 % 7 % 0 % 16,5 % 29,0 % 4,5 % 3 %
- 40
- 50 % 0 % 0 % 0 % 16,5 % 29,0 % 4,5 % 0 %
- 41
- 20 % 0 % 0 % 20 % 19,8 % 34,8 % 5,4 % 0 %
- 42
- 30 % 0 % 0 % 14 % 16,5 % 29,0 % 4,5 % 6 %
- 43
- 40 % 0 % 0 % 14 % 13,2 % 23,2 % 3,6 % 6 %
- 44
- 0 % 40 % 0 % 14 % 13,2 % 23,2 % 3,6 % 6 %
- 45
- 0 % 50 % 0 % 0 % 16,5 % 29,0 % 4,5 % 0 %
- 46
- 0 % 45 % 0 % 0 % 18,15 % 31,9 % 4,95 % 0 %
- 47
- 0 % 40 % 0 % 0 % 19,8 % 34,8 % 5,4 % 0 %
- 48
- 0 % 40 % 0 % 0 % 19,8 % 34,8 % 5,4 % 0 %
- 49
- 40 % 0 % 14 % 0 % 13,2 % 23,2 % 3,6 % 6 %
- 50
- 0 % 30 % 0 % 7 % 19,8 % 34,8 % 5,4 % 3 %
- 51
- 0 % 35 % 0 % 7 % 18,15 % 31,9 % 4,95 % 3 %
- 52
- 0 % 38 % 0 % 1,4 % 19,8 % 34,8 % 5,4 % 0,6 %
- 53
- 0 % 35 % 0 % 3,5 % 19,8 % 34,8 % 5,4 % 1,5 %
- 54
- 40 % 0 % 0 % 14 % 13,2 % 23,2 % 3,6 % 6 %
- 55
- 40 % 0 % 0 % 0 % 26,7 % 22,7 % 3,5 % 7,1 %
- 56
- 40 % 0 % 0 % 13,8 % 12,9 % 22,7 % 3,5 % 7,1 %
- 57
- 40 % 0 % 0 % 26,7 % 0 % 22,7 % 3,5 % 7,1 %
- 58
- 40 % 0 % 0 % 13,8 % 12,9 % 22,7 % 3,5 % 7,1 %
- 59
- 40 % 0 % 0 % 0 % 26,7 % 22,7 % 3,5 % 7,1 %
- 60
- 40 % 0 % 0 % 14 % 13,2 % 23,2 % 3,6 % 6 %
- 61
- 0 % 50 % 0 % 0 % 16,5 % 29,0 % 4,5 % 0 %
26
Claims (1)
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- 2004-06-02 EP EP04743833.8A patent/EP1660323B2/en not_active Expired - Lifetime
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- 2004-06-02 PT PT47438338T patent/PT1660323E/pt unknown
- 2004-06-02 AU AU2004243688A patent/AU2004243688B2/en not_active Ceased
- 2004-06-02 ES ES04743833.8T patent/ES2450137T5/es not_active Expired - Lifetime
- 2004-06-02 WO PCT/IB2004/002164 patent/WO2004106630A2/en active Application Filing
- 2004-06-02 EP EP20100185081 patent/EP2353862A3/en not_active Withdrawn
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2006
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2009
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Also Published As
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JP5290873B2 (ja) | 2013-09-18 |
US7344784B2 (en) | 2008-03-18 |
CN1826222A (zh) | 2006-08-30 |
JP4809215B2 (ja) | 2011-11-09 |
EP1660323B1 (en) | 2014-01-08 |
EP1660323A2 (en) | 2006-05-31 |
CA2526457C (en) | 2010-03-30 |
CA2526457A1 (en) | 2004-12-09 |
US7172814B2 (en) | 2007-02-06 |
WO2004106630A2 (en) | 2004-12-09 |
EP1660323B2 (en) | 2017-03-29 |
US20040248486A1 (en) | 2004-12-09 |
US20060240726A1 (en) | 2006-10-26 |
WO2004106630A3 (en) | 2006-04-06 |
ES2450137T3 (es) | 2014-03-24 |
PT1660323E (pt) | 2014-03-10 |
CY1115281T1 (el) | 2017-01-04 |
JP2009234266A (ja) | 2009-10-15 |
AU2004243688A1 (en) | 2004-12-09 |
JP2006526713A (ja) | 2006-11-24 |
DK1660323T4 (en) | 2017-07-03 |
EP2353862A2 (en) | 2011-08-10 |
AU2004243688B2 (en) | 2010-05-20 |
DK1660323T3 (en) | 2014-03-03 |
EP2353862A3 (en) | 2014-07-30 |
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