Peelable sealant containing thermoplastic composite blends for packaging applications.
Abstract
Un sistema de empaquetadura tiene una sección de sello desprendible la cual incluye una primera capa de sellado y una segunda capa de sellado tal que la primera capa de sellado haga contacto con la segunda capa de sellado para formar un sello desprendible. La primera capa de sellado incluye polímero termoplástico o una mezcla física de polímeros termoplásticos, una organoarcilla dispersa dentro del polímero termoplástico, y un componente de aditivo inorgánico adicional, tal como carbonato de calcio, disperso dentro del polímero termoplástico. El sello desprendible ha logrado efecto de sinergia y ofrece alta conductividad térmica, mayor capacidad de calafateo y es consistente con un rango amplio de temperaturas de sellado sin pérdida de la funcionalidad de sello desprendible deseada conforme el sello envejece.

Term
5.3 yearsleft in the term
Expires 3 January 2032.
- Priority
- Filed
- Granted
- Today
- Expires
37 claims: 7 independent, 30 dependent
- 1REIVINDICACIONES I μ ρ a χ. ¿Vjí -~ tNmWTO MEXIOMíO DE LA ÍSOFiBOaD industrial 1. Un sistema de empaquetadura, carac±©f®eek^”porqtie'tfehe una sección de sello desprendible, la sección de sello desprendióle incluyendo una primera capa de sellado y una segunda capa de sellado tal que la primera capa de sellado haga contacto con la segunda capa de sellado para formar un sello desprendible, la primera capa de sellado Incluye:un polímero termoplástico que Incluye etllvinllacetato y polietileno lineal de baja densidad;una organoarcilla dispersa dentro del polímero termoplástico, la organoarcilla Incluye una pluralidad de partículas que tiene por lo menos una dimensión espacial menor que 200 nm;y carbonato de calcio disperso dentro del polímero termoplástico, el carbonato de calcio Incluye una pluralidad de partículas que tiene un diámetro promedio de 0.5 mieras a 20 mieras, la organoarcilla estando presente en una cantidad de 5% en peso a 20% en peso del peso combinado del polímero termoplástico y la organoarcilla y el carbonato de calcio, y el carbonato de calcio estando presente en una cantidad de 6% en peso a 25% en peso del peso combinado del polímero termoplástico y la organoarcilla y el carbonato de calcio, el sello desprendible tiene una fuerza de desprendimiento de entre 0.5 Ibs y 5 Ibs por pulgada (0.056490.5649 N/m) de anchura de sellado.
- 2El sistema de empaquetadura de la reivindicación 1, caracterizado además porque el carbonato de calcio es tratado con un agente de tratamiento de superficie.
- 3El sistema de empaquetadura de la reivindicación 1, caracterizado además porque el sello desprendible tiene una pendiente de calafateo que es menor de aproximadamente 0.0032. U'tC · á ·. 'j ¿ X.» Λ ζ .ί»ΛΙ »*ΛΙ’V . - . LA PROíiSDAD ’ INDUSTRIAL -a-.:
- 4El sistema de empaquetadura de la reivindicación 1, caracterizado además porque el sello desprendible tiene una pendiente de calafateo de aproximadamente 0.0026 a aproximadamente 0.0032.
- 5El sistema de empaquetadura de la reivindicación 1, caracterizado además porque el sello desprendible tiene un grosor de sello perfecto final de entre 5 a 300 mieras.
- 6El sistema de empaquetadura de la reivindicación 1, caracterizado además porque una superficie de sello es deformable dentro del sello desprendible a todas las temperaturas dentro de un intervalo de temperatura de sello desprendible, el intervalo de temperatura de sello desprendible estando desde una temperatura de inicio de sello a una temperatura que está por lo menos 100°F (55.56°C) por arriba de la temperatura de inicio de sello.
- 7El sistema de empaquetadura de la reivindicación 6, caracterizado además porque la temperatura de inicio de sello es de aproximadamente 170°F a aproximadamente 420°F (76.67-215.56°C).
- 8El sistema de empaquetadura de la reivindicación 1, caracterizado además porque la organoarcilla comprende plaquetas teniendo una separación promedio de por lo menos 20 angstroms y una relación de aspectos promedio de aproximadamente 50 a aproximadamente 1,000.
- 9El sistema de empaquetadura de la reivindicación 1, caracterizado además porque la organoarcilla comprende una arcilla seleccionada del grupo que consiste de arcillas bentonita, caolinita, montmorilonita-esmectita, hectorita, fluorohectorita, saponita, beidelita, nontronita, ilita y combinaciones de las mismas. -63 J X \ '- ·· .^'S’
- 10El sistema de empaquetadura de lá^'TeííÍÍ^S^óht;caracterizado además porque el polímero termoplástico comprende además un componente seleccionado del grupo que consiste de nilones, poliolefinas, pollestlrenos, poliésteres, policarbonatos, copolímeros de etileno, copolímeros de propileno y mezclas de los mismos.
- 11El sistema de empaquetadura de la reivindicación 1, caracterizado además porque el polímero termoplástico comprende además un componente seleccionado del grupo que consiste de polietileno, polipropileno, etileno ácido acrílico, etileno acrllato de etilo, ¡onómeros de etileno y combinaciones de los mismos.
- 12El sistema de empaquetadura de la reivindicación 1, caracterizado además porque la combinación de organoarcilla y carbonato de calcio requiere menos organoarcilla para producir el sello desprendióle que organoarcilla sin carbonato de calcio.
- 13El sistema de empaquetadura de la reivindicación 1, caracterizado además porque la relación de carbonato de calcio a organoarcilla es de 0.4 a 2.5.
- 14El sistema de empaquetadura de la reivindicación 1, caracterizado además porque la primera capa de sellado comprende además talco.
- 15El sistema de empaquetadura de la reivindicación 1, caracterizado además porque la primera capa de sellado tiene una conductividad térmica que es mayor que 0.60 w/m*K y menos de 10 w/m*K a temperaturas de 30°C a 160°C.
- 16El sistema de empaquetadura de la reivindicación 1, caracterizado además porque la primera capa de sellado tiene una pendiente -64 ζτ τι ν *· ? 1 A A · msrfniTO mexicano CI LA riOFIEDAD de calafateo que es menor a aproximadamente 0.003 y un gro^f 1 ?^ seTTadcT' final mayor que aproximadamente 5 mieras.
- 17El sistema de empaquetadura de la reivindicación 1, caracterizado además porque la primera capa de sellado tiene una pendiente de calafateo que es aproximadamente 0.0025 a aproximadamente 0.003.
- 18El sistema de empaquetadura de la reivindicación 1, caracterizado además porque la primera capa de sellado tiene un grosor de sellado final de 260 mieras a 400 mieras.
- 19Un sistema de empaquetadura, caracterizado porque comprende:una sección de recipiente;y una sección de sello desprendible unida a la sección de recipiente, la sección de sello desprendible incluyendo una primera capa de sellado y una segunda capa de sellado tal que la primera capa de sellado haga contacto con la segunda capa de sellado para formar un sello desprendible, la primera capa de sellado incluyendo: un polímero termoplástico que incluye etilvinilacetato y polietileno lineal de baja densidad;una organoarcilla dispersa dentro del polímero termoplástico;y un componente de aditivo inorgánico que comprende carbonato de calcio disperso dentro del polímero termoplástico, el carbonato de calcio incluye una pluralidad de partículas que tienen un diámetro promedio de 0.5 mieras a 20 mieras, la organoarcilla estando presente en una cantidad de 5% en peso a 20% en peso del peso combinado del polímero termoplástico y la organoarcilla y el carbonato de calcio, y el carbonato de calcio estando presente en una cantidad de 6% en peso al 20% en peso del peso combinado del polímero termoplástico y la organoarcilla y el carbonato de calcio, la primera capa de sellado incluyendo una superficie de sellado, el sello desprendible tiene una - 65 INSTITUTOMEXICANO OF IA PROPIEDAD -J ’ INDUSTRIAL -¾ fuerza de desprendimiento de entre 0.5 Ibs y 5 Ibs por pulgada (0.056 0.5649 N/m) de anchura de sellado.
- 20El sistema de empaquetadura de la reivindicación 19, caracterizado además porque el carbonato de calcio es tratado con un agente de tratamiento de superficie.
- 21El sistema de empaquetadura de la reivindicación 19, caracterizado además porque el sello desprendible tiene una pendiente de calafateo que es menor a aproximadamente 0.003 y un grosor de sellado final mayor que aproximadamente 5 mieras.
- 22El sistema de empaquetadura de la reivindicación 19, caracterizado además porque la organoarcilla comprende una pluralidad de partículas que tienen por lo menos una dimensión espacial de menos de 200 nm.
- 23El sistema de empaquetadura de la reivindicación 19, caracterizado además porque la organoarcilla comprende una arcilla seleciconada del grupo que consiste de caolinita, montmorilonita-esmectita, betonita, ilita y combinaciones de las mismas.
- 24El sistema de empaquetadura de la reivindicación 19, caracterizado además porque el polímero termoplástico comprende además un componente seleccionado del grupo que consiste de nilons, poliolefinas, poliestirenos, poliésteres, policarbonatos, copolímeros de etileno, copolímeros de propileno y mezclas de los mismos.
- 25El sistema de empaquetadura de la reivindicación 19, caracterizado además porque comprende adicionalmente un producto alimenticio contenido en el mismo. DE LA VRLVnpAD
- 26El sistema de empaquetadura de la reivíffáícacíón *T9,” caracterizado además porque comprende un componerrte™ronteniido‘ en eí mismo, el componente se selecciona del grupo que consiste de objetos esterilizados, componentes electrónicos y productos de higiene personal.
- 27El sistema de empaquetadura de la reivindicación 19, caracterizado además porque la sección de recipiente tiene una forma seleccionada del grupo que consiste de ampollas, charolas, bolsas, bolsillos, y combinaciones de los mismos.
- 28Un sistema de empaquetadura, caracterizado porque tiene una sección de sello desprendióle, la sección de sello desprendióle incluyendo:una estructura de sellado que tiene la fórmula 1: Li/.../L n /P (1) donde P es una primera capa de sellado, Li hasta L n son capas dentro de una base de soporte en la cual está dispuesta la capa de sellado, n es un entero que representa el número de capas en la base de soporte;un sustrato tal que la primera capa de sellado haga contacto con el sustrato para formar un sello desprendióle, la primera capa de sellado incluye: un polímero termoplástico que incluye etilvinilacetato y polietileno lineal de baja densidad;una organoarcilla dispersa dentro del polímero termoplástico;y un componente de aditivo inorgánico que comprende carbonato de calcio disperso dentro del polímero termoplástico, el carbonato de calcio incluye una pluralidad de partículas que tienen un diámetro promedio de 0.5 mieras a 20 mieras, la organoarcilla estando presente en una cantidad desde 5% en peso al 20% en peso del peso combinado del polímero termoplástico y la organoarcilla y el carbonato de calcio, y el carbonato de calcio estando presente en una cantidad desde 6% en peso al 20% en peso del peso combinado del polímero - 67 I Μ ρ 1Γ ¿ΜJlv Η K V''*’** ·, CNSTÍTVTO M'~-'T¿/ i-?O V' · *-?., N-¡Zg¡t Ϊ 0£ΐΑΓ'Κ0Η20ΑΠ \/ - .ζξίΓ^ fííDLbTSLAÍ. termoplástico y la organoarcilla y el carbonato de calcio, el sello desprendible tienen una fuerza de desprendimiento de entre 0.5 Ibs y 5 Ibs por**pulgá3á' (0.05649-0.5649 N/m) de anchura de sellado.
- 29El sistema de empaquetadura de la reivindicación 28, caracterizado además porque n es un entero desde 1 a 10.
- 30El sistema de empaquetadura de la reivindicación 28, caracterizado además porque el sello desprendible tiene una pendiente de calafateo de aproximadamente 0.0026 a aproximadamente 0.0032.
- 31El sistema de empaquetadura de la reivindicación 28, caracterizado además porque la organoarcilla comprende una pluralidad de partículas teniendo por lo menos una dimensión espacial menor que 200 nm.
- 32El sistema de empaquetadura de la reivindicación 28, caracterizado además porque la organoarcilla comprende plaquetas teniendo una separación promedio de por lo menos 20 angstroms y una relación de aspectos promedio de aproximadamente 50 a aproximadamente 1,000.
- 33El sistema de empaquetadura de la reivindicación 28, caracterizado además porque la organoarcilla comprende una arcilla seleccionada del grupo que consiste de caolinita, montmorilonita-esmectita, bentonita, ¡lita y combinaciones de las mismas.
- 34El sistema de empaquetadura de la reivindicación 28, caracterizado además porque el polímero termoplástico comprende además un componente seleccionado del grupo que consiste de nilones, poliolefinas, poliestirenos, poliésteres, policarbonatos, copolímeros de etileno, copolímeros de propileno, polietileno, polipropileno, etileno ácido acrílico, etileno acrilato de etilo, ionómeros de etileno y mezclas de los mismos.
- 35El sistema de empaquetadura de caracterizado además porque las capas L-|-L n termoplástico.
- 36El sistema de empaquetadura de la reivindicación 35, caracterizado además porque el polímero termoplástico comprende un componente seleccionado del grupo que consiste de nilones, poliolefinas, poliestirenos, poliésteres, policarbonatos, copolímeros de etileno, copolímeros de propileno, polietileno, polipropileno, etileno ácido acrílico, etileno acrilato de etilo, ionómeros de etileno y mezclas de los mismos.
- 37Un sistema de empaquetadura, caracterizado porque tiene una sección de sello desprendible, la sección de sello desprendible incluyendo una primera capa de sellado y una segunda capa de sellado tal que la primera capa de sellado haga contacto con la segunda capa de sellado para formar un sello desprendible, la primera capa de sellado incluyendo:un polímero termoplástico que incluye etilvinilacetato y polietileno lineal de baja densidad;una organoarcilla dispersa dentro del polímero termoplástico, la organoarcilla incluyendo una pluralidad de partículas teniendo por lo menos una dimensión espacial menor de 200 nm, la organoarcilla incluyendo aglomeraciones de apilamientos de organoarcilla;y carbonato de calcio disperso dentro del polímero termoplástico, el carbonato de calcio incluye una pluralidad de partículas que tienen un diámetro promedio de 0.5 mieras a 20 mieras, la organoarcilla estando presente en una cantidad desde 5% en peso a 20% en peso del peso combinado del polímero termoplástico y la organoarcilla y el carbonato de calcio, y el carbonato de calcio estando presente en una cantidad desde 6% en peso al 25% en peso del peso combinado del polímero termoplástico y la organoarcilla y el carbonato de calcio, el sello desprendible tienen una fuerza de desprendimiento de entre 0.5 Ibs y 5 Ibs por pulgada (0.05649-0.5649 N/m) de anchura de sellado.
Independent claims37
418 paragraphs in 52 sections, as filed
(54) Title: REMOVABLE SEALANT CONTAINING PHYSICAL MIXTURES OF THERMOPLASTIC COMPOUND FOR EMPAOUETADURA APPLICATIONS.
(54) Title: PEELABLE SEALANT CONTAINING THERMOPLASTIC COMPOSITE BLENDS FOR PACKAGING
APPLICATIONS.
(57) Summary
A packing system has a detachable seal section which includes a first seal layer and a second seal layer such that the first seal layer contacts the second seal layer to form a peel seal. The first sealing layer includes thermoplastic polymer or a physical mixture of thermoplastic polymers, an organoclay dispersed within the thermoplastic polymer, and an additional inorganic additive component, such as calcium carbonate, dispersed within the thermoplastic polymer. The release seal has achieved synergy effect and offers high thermal conductivity, higher caulking capacity and is consistent with a wide range of sealing temperatures without loss of the desired release seal functionality as the seal ages.
(57) Abstract
A packaging system has a peelable seal section which ineludes a first sealing layer and a second sealing layer such that the first sealing layer contacts the second sealing layer to form a peelable seal. The first sealing layer ineludes thermoplastic polymer or a blend of thermoplastic polymers, an organoclay dispersed within the thermoplastic polymer, and an additional inorganic additive component, such as calcium carbonate, dispersed within the thermoplastic polymer. The peelable seal has achieved synergistic effect and offers high thermal conductivity, great caulkability and is consistent over a broad range of sealing temperatures without loss of desired peelable seal functionality as the seáis age.
PATENT TITLE No. 355447
IMPI
C-<sup>;</sup> r <, μ
Headlines):
D micilio:
D nomination:
Classification:
INTERCONTINENTAL GREAT BRANDS LLC
100 Deforest Avenue, East Hanover, New Jersey, 07936, USA
REMOVABLE SEALANT CONTAINING PHYSICAL MIXTURES OF THERMOPLASTIC COMPOUND FOR PACKAGING APPLICATIONS.
CIP:
CPC:
B32B7 / Q & B2
B3 ^ 7toeM lnventor (s):
2 | / 0®; | 33ΐΒζ7Τ08; Β32Β27 / 20; B32B27 / 30; B32B27 / 32 ^^ 2B2T / (fez <O2B¿ | / ^; B65D75 / 5855; B65D77 / 2032;
: 264tl0; B32B2264 / 12; B32Éá »4 / 3ü4 (B32B2307 / 31; B32B2307 / 302;
<img file="MX355447B_D0001.tif" />
B32B2439 / 40; YING LÍANG; PANAGI% TI JOM ^ S; FRANGIS
AND*
Nummz
MX / a / 2013/0078 ^
Country:
<img file="MX355447B_D0002.tif" />
O t <sup>1</sup> *
Validity: Twenty years »Date of vMei ^ iient ^ 2032
ExiuÉlfctón sheet: ** with cover
In accordance with article Mñfe the Law<sup>; i</sup>8lt ^^ | dHndus1 ... from the date of presentation ^^ te ^^ Dlicidad ¡njS ^ acS iftahugset
Whoever subscribes to this title<sup>1 </sup>(Official Gazette of the Federation 25/01/2006, 06/05 / 2009,06 / 01/2010 Regulations of the Mexican Institute of articles 1, 3, 4, 5, section V, subsection a),
12/27/1999, amended on 10/10/2002, 07/29/20 '
Deputy Generals, Coordinator, Directors
The patent of reference
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<img file="MX355447B_D0004.tif" />
10Τ428 / 1352
CpeUNG; ALEXANDER D.
tamffcfonal:
Number:
W<sup>32</sup> ^ / §9pt »Cey déla! MMMÍe * óSa de veirffe ajá & toiprogrogables, counted at jMa fee pajjMUpntener yigentesla ^ rights.
the Industrial Property Law 1999, 01/26/2004, 06/16/2005, a), 4th and 12th sections I and III of 07/05/2004, 07/28/2004 and 09/07/2007 ); lexicon of Industrial Property (DOF. Agreement that delegates powers to the Divisional Subdirectors Directors, Coordinators (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004,
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Divisioi trial.
Departmental and other subordinates of the Instituto Mexicano de la róeRMatJnBBel 04/08/2004 and 13/09/2007).
^ Industrial.
This letter is signed with an advanced electronic signature (FIEL), based on articles 7 BIS 2 of the Industrial Property Law; 3 of its Regulations, and 1 section III, 2 section V, 26 BIS and 26 TER of the Agreement establishing the guidelines for the use of the Electronic Payment and Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.
THE DIVISIONAL DIRECTOR OF PATENTS
<img file="MX355447B_D0006.tif" />
NAHANNY CANAL REYES
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Arenal No 550 Piso 1, Pueblo Santa María Tepepan, Xochimilco, 16020. Mexico City, (55) 53340700 www.gob.mx/lmpl
<img file="MX355447B_D0007.tif" />
MX / 2018/32074
M7:
355 4^3
MEXICAN INSTITUTE
DELA PRC7ÍS0AO (. '> ·
INDUSTRIAL '<
REMOVABLE SEALANT CONTAINING MIXTURES
PHYSICS OF THERMOPLASTIC COMPOUND FOR
PACKAGING APPLICATIONS
Technical Field
The present invention relates to gasket systems that include a release seal and, in particular, the present invention relates to compositions and methods for forming such release stamps.
Background
Gasket is an important feature in protecting, selling, and marketing most products. The gasket has wide applications, for example, in food products, medical devices, electronic components, industrial products, personal hygiene products, pet products, collectibles, jewelry, and the like. The specific characteristics of such packaging require properties for the particular application. For example, medical products and food products may frequently require a hermetic seal in order to prevent contamination of the product contained within.
Food products, in particular, have fairly severe packaging requirements to preserve freshness and provide desired shelf life. Some
<img file="MX355447B_D0008.tif" />
Médicos Medical devices also demand strict packaging requirements to preserve the sterility of such devices. In such applications, the packing is typically vacuum packed or gas flushed and subsequently hermetically sealed. Although efficient product packaging is mandatory, several aesthetic properties of a product packaging are also important. For example, the appearance of the gasket is highly important to consumer appeal. In addition, functional properties of the gasket such as ability to reuse and ease of opening of a gasket are important considerations. In many of these applications, the ability to easily open a gasket will depend on the mechanical properties of the seal. Furthermore, the ability of the sealant substrate to transfer heat at a high rate (heat / thermal conductivity) results in a significant reduction in seal residence time, and allows for higher cycle speed and lower energy consumption of sealing with total material reduction (sustainability).
One such packing structure uses a release seal. When a gasket having a peelable seal is opened, a sealing layer can be peeled off of a substrate. It is desirable for such a peel to be achievable with a relatively constant low peel force. The elastic properties of the release seal
-3 ~ Γ ()
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and you
MEXICAN INSTITUTE OF PROPERTY
INDUSTRIAL
<img file="MX355447B_D0010.tif" />
ensure that seal failure does not occur from flexing and normal packing handling. In some state-of-the-art gaskets, removable seals are constructed from multilayer sheets. Examples of gasket systems having such seals include erect and regular bags, boxed bag, tray-type food gaskets, bottles or ampoule gaskets, top wrap and the like. Although some of these peel seal gaskets work reasonably well, it has been difficult to construct suitable gasket systems that will consistently form watertight seals that resist leakage even when wrinkles, folds, and gussets are present, and will still be easily opened by an end user. Furthermore, such prior peelable packing systems tend to operate over relatively narrow ranges, and in particular narrow temperature seal ranges. Narrow sealing temperature ranges tend to result in packing defects. For example, at the low end of the useful temperature range, leak seals may form (not hermetically sealed). At the upper end of the useful temperature range, non-release seals are formed which tear when opened.
Accordingly, there is a need for improved removable gasket systems that resist leakage by providing more caulking of the film seal channels, provide a watertight seal, and are easily opened and sealed.
V '·· ··
-4J.VA Jí INSTITUTO MEXICANO
PE INDUSTUAL PROPERTY consistently over a wide range of tempOTSCOTaS 'TCS<sup>-</sup> The seal is without loss of the desired release seal functionality as the seal ages.
Compendium
The present invention solves one or more prior art problems by providing at least one embodiment of a packing system having a removable seal section. The release seal section includes a first seal layer and a second seal layer such that the first seal layer contacts the second seal layer to form a release seal. The first seal layer includes a thermoplastic polymer, an organoclay dispersed within the thermoplastic polymer, and an additional additive component comprising inorganic filler, such as calcium carbonate dispersed within the thermoplastic polymer. The combined weight of the organoclay and the additional filler (e.g., calcium carbonate) is from about 10% by weight to about 35% by weight of the combined weight of the thermoplastic polymer and the organoclay and the additional filler (v .gr., calcium carbonate). The organoclay is present in an amount of 5% by weight to 20% by weight of the combined weight of the thermoplastic polymer and the organoclay and the additional filler (eg, calcium carbonate). The inorganic filler, such as calcium carbonate, is present in an amount of 6% by weight to 25% by weight of the combined weight of the thermoplastic polymer and the
<img file="MX355447B_D0011.tif" />
'πο organoclay and additional filler (v ... gr .________ rJaonaliQ ...... calcium). The first seal layer includes a sealing surface, the peelable seal having a peel force between 0.5 pounds and 5 pounds per inch (87.56-875.63 N / m) of seal width. In another embodiment of the present invention, a gasket system incorporating the release seal structures of the invention is provided. The packing system of the invention includes a container section and a removable sealing section attached to the container section. The release seal section includes a first seal layer and a second seal layer such that the first seal layer contacts the second seal layer to form a release seal. The first sealing layer includes a thermoplastic polymer, an organoclay dispersed within the thermoplastic polymer, and an additional additive component comprising inorganic filler, such as calcium carbonate dispersed within the thermoplastic polymer. The combined weight of the organoclay and the additional filler (e.g., calcium carbonate) is from about 10% by weight to about 35% by weight of the combined weight of the thermoplastic polymer and the organoclay and the additional filler (v .gr., calcium carbonate). The organoclay is present in an amount of 5% by weight to 20% by weight of the combined weight of the thermoplastic polymer and the organoclay and the additional filler (eg, calcium carbonate). Inorganic filler, such as
IMPIf? ···
MEXICAN INSTITUTE \ * ·
OF PROPERTY <· '· g IN DVSTWAl'. .1, · calcium carbonate is present in a can ti'da'd<sup>1</sup> %<sup>!</sup>”By weight at 25% by weight of the combined weight of the thermoplastic polymer and organoclay and calcium carbonate. The first seal layer includes a sealing surface, the peelable seal having a peel force of between 0.5 pounds and 5 pounds per inch of seal width (87.56-875.63 N / m).
In yet another embodiment of the present invention, a gasket system having a removable seal section is provided. The detachable seal section ~ ru includes a sealing structure having formula 1:
LJ ... / - LJV (1) where P is a first sealing layer, to L<sub>n</sub> they are layers within a support base on which the sealing layer is provided, and n is an integer representing the number of layers in the support base. The release seal section also includes a substrate such that the first seal layer contacts the substrate to form a release seal, the first seal layer includes a thermoplastic polymer, an organoclay dispersed within the thermoplastic polymer, and an additive component additional comprising inorganic filler, such as calcium carbonate, dispersed within the thermoplastic polymer. The combined weight of the organoclay and the additional filler (e.g., calcium carbonate) is from about 10% by weight to about 35% by weight of the combined weight of the thermoplastic polymer and the organoclay and the additional filler (v .gr.,
<img file="MX355447B_D0012.tif" />
^ ΤΟ calcium carbonate). The organoclay is fiféáéFif'é 'in an amount of 5% by weight to 20% by weight of the combined weight of the thermoplastic polymer and the organoclay and additional filler (eg, calcium carbonate). The inorganic filler, such as calcium carbonate, is present in an amount of 6% by weight to 25% by weight of the combined weight of the thermoplastic polymer and the organoclay and the calcium carbonate. The first seal layer includes a sealing surface, the peelable seal having a peel force between 0.5 pounds and 5 pounds per inch (87.56-875.63 N / m) of seal width.
In yet another embodiment, a packing system having a removable seal section is provided. The removable seal section includes a sealing structure having formula 2:
. ./L<sub>n</sub>/ P / L<sub>F</sub> (2) where P is a first sealing layer, L<sub>x</sub> to L<sub>n</sub> represent layers within a support base on which the sealing layer is disposed, L<sub>F</sub> it is an additional layer disposed on the first sealing layer, and n is an integer representing the number of layers in the support base. The sealing section also includes a substrate such that the first sealing layer contacts the substrate to form a release seal. The first sealing layer includes a thermoplastic polymer, an organoclay dispersed within the thermoplastic polymer, and an additional additive component comprising inorganic filler,
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OOTTTUTO MHXlCIAJ'-ίΟ '/ DI LA 7' ''
L <uj I such as calcium carbonate, dispersed 'Sént'ro “^ eT' '<sup>i</sup>'pbTimer thermoplastic. The combined weight of the organoclay and the additional filler (e.g., calcium carbonate) is from about 10% by weight to about 35% by weight of the combined weight of the thermoplastic polymer and the organoclay and the additional filler (see. gr., calcium carbonate). The organoclay is present in an amount of 5% by weight to 20% by weight of the combined weight of the thermoplastic polymer and the organoclay and the additional filler (eg, calcium carbonate). The inorganic filler, such as calcium carbonate, is present in an amount of 6% by weight to 25% by weight of the combined weight of the thermoplastic polymer and the organoclay and the calcium carbonate. The first seal layer includes a sealing surface, the peelable seal having a peel force between 0.5 pounds and 5 pounds per inch (87.56-875.63 N / m) of seal width.
In another embodiment of the present invention, a formulation to form a release sealant layer is provided. The formulation contains one master batch of organoclay and one master batch of calcium carbonate with thermoplastic polymers. Gasket sealant systems formed from such formulations have a synergistic effect and deliver peel ability over a wide range of sealing temperatures, with better thermal conductivity and improved caulking ability. Furthermore, such formulations (particularly easy release formulations) have *
<img file="MX355447B_D0014.tif" />
<img file="MX355447B_D0015.tif" />
-9 MEXICAN INSTITUTE OF THE PÍCIMEDaD
INDUSTRIAL 'ΎΟ
<img file="MX355447B_D0016.tif" />
Much better aging characteristics without significant loss of seal functionality as desired as the seals age, compared to polybutylene-based easy open systems.
Brief Description of Drawings
Figure IA is a schematic cross section of a single layer sealing structure containing organoclay and an inorganic filler, such as calcium carbonate additives;
Figure IB is a schematic cross section of a two layer structure with an additional layer of organoclay sealer / additive;
Figure 1C is a schematic cross section of a three layer structure with an additional layer of organoclay sealer / additive;
Figure ID is a schematic cross section of a five layer structure with an additional layer of organoclay sealer / additive;
Figure 1E is a schematic cross section of a three layer structure with an additional layer of organoclay sealer / additive;
Figure 2A is a schematic cross section of a bag-like packing system incorporating an embodiment of the sealing structure of the invention;
- 10IMP
MEXICAN INSTITUTE,. OF PROPERTY V? INDUSTRIAL FIG. 2B is a side view of the bag-like packing system of FIG. 2A;
Figure 2C is a side view of a bag-like packing system of Figure 1E;
Figure 3A is a schematic cross section of an improvement in which a sealing substrate includes a second sealing layer;
Figure 3B is a schematic cross section of an improvement in which a sealing substrate includes a second sealing layer with a detachable seal being formed between a first sealing layer and a second sealing layer;
Figure 4A is a schematic cross section of a cup-like packing system using the release seal structures of the invention;
Figure 4B is a schematic cross section of an ampoule packing system using the release seal structures of the invention and incorporating multiple cup-like containers;
Figure 5 is a diagram illustrating a method of processing and laminating sealant substrate layers of the invention and forming the gasket system;
Figure 6 provides traces of the peel resistance against seal temperature for seals made from a thermoplastic polymer / carbonate composition.
<img file="MX355447B_D0017.tif" />
calcium and a thermoplastic / organoclay polymer;
Figure 7 provides traces of the peel resistance against sealing temperature for seals made from the compositions having varying amounts of organoclay and calcium carbonate;
Figure 8 provides traces of the peel strength against the sealing temperature for seals made from compositions having organoclay and high levels of calcium carbonate;
Figure 9 provides traces of the peel resistance against sealing temperature for seals made from compositions having organoclay and metallocene LLDPE;
Figure 10 provides an illustration of the caulking test method in which caulk slope and final seal thickness are calculated;
Figure 11 provides a trace of unsealed area against contaminant thickness used to determine caulking slope and final seal thickness in the caulking ability test method;
Figure 12A provides a series of unsealed area traces against contaminant thickness for various polymer / organoclay / calcium carbonate combinations;
Figure 12B provides the caulking slope.
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for various film compositions; ___ Figures 13A and 13B provide traces of G 'and G against frequency (a<sub>T</sub>o) for a number of compositions;
Figure 14A provides a caulking slope trace from G '/ a<sub>T</sub>or;
Figure 14B provides a trace of the final perfect seal thickness against G '/ a<sub>T</sub>or;
Figure 15 provides a plot of the ratio of
G '/ a<sub>T</sub>o and the caulking slope for various samples; and Figures 16A-16D provide traces of heat flux versus temperature for various film compositions.
Detailed description
Reference will now be made in detail to presently preferred compositions, embodiments, and methods of the present invention that constitute the best modes for practicing the invention currently known to the inventors. The figures are not necessarily to scale. However, it will be understood that the disclosed embodiments are merely explanatory of the invention that can be carried out in several and alternative ways. Therefore, specific details disclosed herein should not be construed as limiting, but merely as a representative basis for any aspect of the invention and / or as a representative basis for teaching a person skilled in the art how to variously employ the present invention.
-131J
INSTIT> 1
Except in the examples, or where ^ uie ^ ntr.a..specifically stated, all numerical amounts in this description indicating amounts of material or reaction conditions and / or use are to be understood as modified by the word around in describing the broader scope of the invention. Practice within the aforementioned numerical limits are generally preferred. Also, unless expressly mentioned otherwise, percentage (%), parts of, and ratio values are by weight; the term polymer includes oligomer, co-polymer, ter-polymer, and the like; The description of a group or class of materials as is suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; chemical constituent description refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily prevent chemical interactions between the constituents of a mixture once mixed; The first definition of an acronym or other abbreviation applies to all subsequent uses hereof of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation; and, unless expressly mentioned otherwise, measurement of a property is determined by the same technique as previously or subsequently referenced for the same property.
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INSTITUTE
OF THE PILIf ^ aD INDUS'íiUAL
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It should also be understood that this. invene44n-<sup>,</sup> It is not limited to the specific embodiments and methods described below, as specific components and / or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments of the present invention and is not intended to be limiting in any way.
It should also be noted that, as used in the specification and the appended claims, the singular forms one, one, the, and are comprised of plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components.
Through this application, where publications are referenced, the disclosures in these publications in their entireties are therefore incorporated by reference into this application in its entirety to more fully describe the state of matter to which this invention belongs.
The term organoclay as used herein means organically modified clay. Typically, such a modification makes a clay to be more compatible and therefore polymer-collapsible.
The terms clay layers, clay sheets, clay plates as used herein mean that
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MEXICAN INSTITUTE ϊ «· x /,<sub>;</sub>
OF PROPERTY C · ~ J? >
INDUSTRIAL 'individual layers of the layered material T— ^ 31 ^ 5 ^ 501 ^ - ^ 1 ^ 1113 smectite.
The term exfoliated organoclay used herein means that at least a portion of the organoclay includes a plurality of platelets in which the separation between platelets is greater than the separation of platelets in unmodified clay and that at least a portion of the placetas are not parallel. In typical unmodified clay, the adjacent platelets tend to be parallel. tu Typically, the average separation of an exfoliated organoclay will be greater than about 20 angstroms. Clays with average separations greater than about 100 nanometers are considered to be fully exfoliated. It should also be appreciated that the individual stacks of organoclay platelets may themselves be associated with other stacks to form a stack agglomeration. Such agglomerations are characterized by a maximum spatial dimension. From a point of view of morphology, scanning electron microscope (SEM), or light microscopy provide information on the size of the agglomerations in polymer matrix, the maximum spatial dimension is used to represent the distribution of organoclay in polymer and physical polymer blends. A large value of the maximum spatial dimension represents good dispersion of the organoclay. The maximum spatial dimension is 1 nanometer to 100 microns. In refining, the
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f average maximum spatial dimension is 1 ñrrTa 100 nm. In another refinement, the average maximum spatial dimension is from 1nm to 1,000nm. In another embodiment, the diameter is from 1 miera to 100 micras.
The term pure polymer or pure polymer physical blend as used herein means a thermoplastic polymer, or different types of physical thermoplastic polymer blends, that do not contain an inorganic filler.
The term release seal as used herein means a seal having a release force of between 0.5 pounds to 5 pounds per one inch (87.56875.63 N / m) of sample width and an open release force of the seal. Typically, the upper limit is less than or equal to 5 pounds per inch of (875.63 N / m) sample width. In other variations, the upper limit is less than or equal to 4 pounds per inch (700.51 N / m) of sample width or less than the tear resistance on the film substrate.
The term breakout force as used herein means a force to separate two layers as defined in ASTM F-88, which is incorporated by reference. For example, this is the force required to separate two one-inch (2.54 cm) width layers by pulling the two layers in opposite directions.
The term seal start temperature as used herein refers to the lowest temperature at which a
<img file="MX355447B_D0023.tif" />
MEXICAN INSTITUTE OF THE FROM AGE
INDUSTRIAL
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seal is formed with a peeling force of ..... υ '.' ΤΓ'ΊΙUfas per inch (87.56 N / m). Specifically, the seal start temperature is the temperature of a surface (typically metal) contacting a layer or layers that should not be sealed thereby promoting such a seal. In some variations, the surface contacts the layers with a residence time of about 0.1 to 2 seconds with a pressure of 5 psi to 1,200 psi (34.47-8273.71 kPa).
The term peel seal temperature range as used herein means the temperature range at which a seal between two materials is formed such that the peel force is between 0.5 pounds per one inch of sample to 5 pounds per one inch of sample width (87.56-875.63 N / m) with a force that tears the films as noted above.
The term scaling temperature as used herein means a temperature at which a seal is formed between two materials.
The terms caulk slope and final perfect seal thickness as used herein are defined as follows. A caulking test method introduces a gap with a flat cable to a certain thickness (i.e. thickness of contaminant) in the sealing region to simulate a contaminant inadvertently introduced near or in the sealing area during the sealing process heat (see figure 10). The / Τ
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unsealed area is measured using epi'gQ ^ -Uraa · -1-eetura · microscopy. Lower area of unsealed area represents better caulking ability and improved ability to provide a watertight seal. The unsealed area is plotted as a function of contaminant thickness. Data are fitted by linear regression (eg, least squares fit) with the caulking slope being the slope of the fitted line. The final perfect seal thickness is the thickness of contaminants in a non-seal area of zero. A higher final perfect seal thickness indicates high caulking ability.
In one embodiment of the present invention, a release seal structure is provided. The peelable seal structure provides an improvement over the structures outlined in patent application publication US 2008/0118688, the entire disclosure of which is incorporated herein by reference. The release seal section includes a first seal layer and a second seal layer such that the first seal layer contacts the second seal layer to form a release seal. The first sealing layer includes a thermoplastic polymer or physical blend of thermoplastic polymers, an organoclay dispersed within the thermoplastic polymer or physical blend of thermoplastic polymers, and an inorganic additive component such as calcium carbonate dispersed within the thermoplastic polymer or physical blend of thermoplastic polymers.
<img file="MX355447B_D0026.tif" />
INSTITUTO ME'DC 'di la raosvx INDUSí'3' T
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The combination of organoarcilte — and— © i — eaxfeojiatQ ... de. Calcium operate synergistically such that the first seal layer produces a release seal when the first and second seal layers are sealed together. Specifically, some embodiments of the present invention advantageously form release seals that peel open to the Type A Adhesive failure mechanism (see patent application publication US 2008/0118688, which is incorporated herein by reference). In a further development, the peel seals formed herein have a peel strength of 0.5 pound per inch of sample width to 5 pound per inch of sample width (87.56-875.63 N / m). In another improvement, the peel seals formed herein have a peel strength of 1.0 pound per one inch of sample width at 4.5 pounds per inch of sample width (175.13-788.07 N / m). In yet another refinement, the peel seals formed herein have a peel strength of 1.0 pound per one inch of sample width at 4.0 pounds per inch of sample width (175.13-700.51 N / m).
Peel seals formed herein are also characterized by seal strength as noted in ASTM F 88. Seal strength is tested and measured at the time a seal is formed. The preferred condition is to measure the seal resistance within one minute of the seal detached7> ITT T) 7 <·
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The releasable seals of the present embodiment are also characterized by the caulking slope and the final perfect sealing thickness (thickness of contaminants). In a refinement, the caulking slope is less than or equal to 0.0032. In a further refinement, the caulking slope is 0.001 to 0.0032. In another refinement, the caulking slope is 0.0026 to 0.0032. In yet another refinement, the caulking slope is 0.0025 to 0.003. In yet another refinement, the caulking slope is 0.0027 to 0.003. Typically, the final perfect seal thickness is greater than 5 microns. In a refinement, the final perfect seal thickness is 5 microns to 400 microns. In another refinement, the final perfect seal thickness is from microns to 300 microns.
As noted in patent application publication US 2008/0118688, organoclay is a contributing component in release sealant formulation. It should be noted that without organoclay, calcium carbonate does not produce a release seal. Furthermore, the combination of organoclay and calcium carbonate requires less organoclay to produce a
-21 . .0:
MEXICAN INSTITUTE OF PROPERTY
INDUSTRIAL 'ΤΟ
High quality removable V-seal. Since —l'a- ^ ggan'oa'geé-íla- is a relatively expensive component compared to calcium carbonate, the combination of organoclay and calcium carbonate offers considerable cost reduction. The combined weight of organoclay and calcium carbonate is from about 10% by weight to about 35% by weight of the combined weight of the thermoplastic polymer and organoclay and calcium carbonate. The organoclay is present in an amount of 5% by weight to 20% by weight of the combined weight of the thermoplastic polymer and the organoclay and calcium carbonate. Calcium carbonate is present in an amount of 6% by weight to 25% by weight of the combined weight of the thermoplastic polymer and the organoclay and the calcium carbonate. In some refinements, the ratio of calcium carbonate to organoclay varies from 0.4 to 2.5. The first seal layer includes a seal surface that contacts a surface of the second seal layer to form the release seal. The release seal is characterized by a release force between 0.5 lbs. And 5 lbs. Per inch (87.56-875.63 N / m) of sealing width.
In a variation, the sealing surface can be formed into a peel seal at all temperatures within a peel seal temperature range, which is, from a seal start temperature to a temperature that is at least 50 ° F (27.78 ° C) above temperature ο
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start stamp. At a perfectionamiefttO / —- r ^ ngO - of., Peelable seal temperatures are from a seal start temperature to a temperature that is at least 75 ° F (41.67 ° C) above the seal start temperature . In yet another refinement, the peel seal temperature range is from a seal start temperature to a temperature that is at least 100 ° F (55.56 ° C) above the seal start temperature. Typically, for gasket applications, the seal onset temperature ranges from nu around 170 ° F to around 420 ° F (76.67-215.56 ° C). In a refinement, the seal start temperature varies from around 170 ° F to around 350 ° F (76.67-176.67 ° C). In another refinement for gasket applications, the seal start temperature ranges from around 170 ° F to around 270 ° F (76.67-132.22 ° C). All of the above temperature limits may vary with the heat resistance of the outer layers of lamination, co-extrusion, or cladding. For example, when the outer shell is HDPE, the upper seal temperature limit is around 270 ° F (132.22 ° C); When the outer layer is oriented polyester, the upper temperature limit is around 420 ° F (215.56 ° C).
In general, peel-off sealing structures are multi-layer structures that are useful for sealing applications. Such layered structures include a sealing layer including organoclay and an additional additive ▼ ν *. r
-23IMPIf
MEXICAN INSTITUTE
OF THE PROHSDAO «
INOUSTtUAL selected from the group consisting of calcium carbonate, magnesium carbonate, hydrated magnesium silicate (talc), titanium oxide, magnesium oxide, magnesium sulfate, barium sulfate, barium aluminates, barium borate, silicate barium and combinations thereof. A variation of the multi-layer sealing structure is described by formula 1:
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LJ ... / LJV (1) where P is the sealing layer that includes organoclay and organic filler, such as calcium carbonate and additional additive component, L<sub>x</sub> to L<sub>n</sub> represent layers within a support base on which the sealing layer is provided, and n is an integer representing the number of layers in the support base. The support base usually includes one or more polymer layers (rigid or flexible) as noted below. Typically, n is an integer from 1 to 10. Examples of such multilayer structures have the following structures L ^ P; L ^ Lj / P; L2 / L2 / L3 / P; 'L2 / L2 / L3 / L4 / L5 / P; L1 / L2 / L3 / L4 / L<sub>5</sub>/ L<sub>6</sub>/ P: and
L<sub>1</sub>/ L<sub>2</sub>/ L3 / L<sub>4</sub>/ L<sub>5</sub>/ L<sub>6</sub>/ L<sub>7</sub>/ P. Another variation of the multi-layer sealing structure is described by formula 2:
Li /. . . / L<sub>n</sub>/ P / L<sub>F</sub> (2) where P is the sealing layer including organoclay and organic filler, such as calcium carbonate and additional additive component, L<sub>7</sub> to L<sub>n</sub> represent layers within a support base on which the sealing layer is disposed, L<sub>F</sub> is a
-24IMP
INSTITUTE Μ '
OF THE <sup>p</sup> adrieirental non-release sealant polymeric layer — arranged<sup>; </sup>on the opposite side of P than L<sub>n</sub>, and n is an integer representing the number of layers in the support base. The support base usually includes one or more polymer layers as noted below. Typically, n is an integer from 1 to 10. Examples of such multilayer structures have the following structures L ^ P / Lf, · L<sub>1</sub>/<sub>L2</sub>/ P / L<sub>F</sub>; L<sub>1</sub>/<sub>L2</sub>/ L<sub>3</sub>/ P / L<sub>F</sub>; L<sub>1</sub>/<sub>L2</sub>/ L<sub>3</sub>/ L<sub>4</sub>/ P / L<sub>F</sub> ;
Li / l2 / L<sub>3</sub>/ L<sub>4</sub>/ L<sub>5</sub>/ P / L<sub>F</sub>; L<sub>1</sub>/<sub>L</sub>2 / L<sub>3</sub>/ L<sub>4</sub>/ L<sub>5</sub>/ Lg / P / L<sub>F</sub>; and í, -<sub>i</sub>/<sub>1¡2</sub>/ You<sub>3</sub>/ 1j<sub>i</sub>/ 1j<sub>5</sub>/ í¡<sub>6</sub>/ 1jj / P / 1j<sub>£</sub>. The present embodiment also encompasses variations in which the sealing structure includes a single P-layer.
In another embodiment, a peel seal using the peelable seal structures noted above is provided. In general, these removable seals are described by formula 3:
Li /. . ./L<sub>n</sub>/ P * S (3) where S is the substrate to which the sealing structure is sealed, P is the sealing layer, L<sub>x</sub> to L<sub>n</sub> they represent layers within a support base on which the sealing layer is disposed, and n is an integer representing the number of layers in the support base, and the substrate does not contain organoclay or calcium carbonate. The symbol * represents that P and S are sealed together (eg, bonded or adhered). In a more specific variation, the release seal is described by formula (4):
L, /. . ./L<sub>n</sub>/ P * P '/ L'<sub>n</sub>/. . ./L'j (4) where P and P 'are independently sealing layers that v- * ·', __-, f<sup>r</sup>
-25 MEXICAN PROPERTY INSTITUTE
INDUSTRIAL ιυ include an organoclay, an inorganic filler, such as calcium carbonate, and additional additive components, L<sub>T</sub> to L<sub>n</sub> represent layers within a substrate on which the sealing layer P is disposed, at L '<sub>n</sub> represent layers within a substrate on which the sealing layer P 'is disposed, n is an integer representing the number of layers at the base lying under P'. The symbol * represents that P and P 'are sealed together (eg, bound or adhered). Typically, nyn 'are each independently an integer from 1 to 10. The present embodiment also contemplates variations in which the sealing structure is a single layer where the seal is P * P. In a further development, the packing system includes a container section attached to the sealing section that includes the release seal. It should be appreciated that the present sealing sections are designed to separate at the P * P seal. In a refinement, such separation is by a delamination mechanism.
In another embodiment, a peelable seal using the peelable seal structures noted above is provided. In general, these removable seals are described by formula 5:
L, /. . ./L<sub>n</sub>/ P / L<sub>F</sub>* S (5) where S is the substrate to which the sealing structure is sealed, P is the sealing layer, Li to L<sub>n</sub> represent layers within a support base before which the sealing layer is
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disposes, L<sub>x</sub> it is an additional layer arranged on top of the sealing line, and n is an integer representing the number of layers in the support base. The symbol * represents that P and S are sealed together (eg, bound or adhered). Substrate S includes any material to which the Li /.../L multilayer structure<sub>n</sub>/ P / L<sub>F</sub> can adhere. Examples of suitable substrates include, but are not limited to, a multilayer structure (ie, of an analogous construction as provided by Formula 1 or of a different design), plastics, and metals. In another more specific variation, the seal detached is described by formula 6:
Li /. . . / -LjP / LfP '/ L' t / L 'J. . ./L where P and P 'are independently sealing layers including an organoclay, an inorganic filler, such as calcium carbonate, and additional additive component, 1 ^ a L<sub>n </sub>represent layers within a substrate on which the sealing layer P is disposed, L '<sub>x</sub> to L '<sub>n</sub> represent layers within a substrate on which the sealing layer P ', L is disposed<sub>F</sub> it is an additional layer arranged on top of the sealing layer P, L '<sub>F</sub> is an additional layer arranged on top of the sealing layer P ', n is an integer representing the number of layers at the base lying under P, and n' is an integer representing the number of layers at the base lying under P '. Typically, nyn 'are each independently an integer from 1 to 10. In one embodiment, the packing system includes a container section attached
<img file="MX355447B_D0031.tif" />
to the sealing section that includes the Selium, I detached bl ft ^, .-. £ symbol * represents that P and L '<sub>F</sub> they are sealed together. It should be appreciated that the present sealing sections are designed to separate at the P * P seal. In a refinement, such separation is by a delamination mechanism.
In a variation of the sealing structures described by formulas 1-6, the total thickness of the multilayer structure is from about 5 to about 78 microns. In a refinement, the total thickness of the multilayer structure is from about 15 to about 75 microns. In another refinement, the total thickness of the multilayer structure is from about 35 to about 75 microns. In another variation of the multi-layer structures outlined by Formulas 1-6, the sealing layer typically has a thickness of about 2.5 to about 130 microns. In a further development, the sealing layer is from about 5 to about 50 microns thick.
Referring to Figures IA, IB, 1C, ID, and 1E, illustrations of release seal structures used in the gasket systems of the present invention are provided. The multilayer structure can be constructed by co-extrusion blown film, cast film, adhesive lamination, extrusion lamination, extrusion coating, surface printing process or surface coating, or combinations thereof. In this embodiment, the
<img file="MX355447B_D0032.tif" />
Sealing structure peeled off is attached to the substrate to form a seal or sealing section peeled off. Figure IA is a schematic cross section of a single layer sealing structure. In this variation, the sealing structure detached 10<sup>1</sup> includes sealing layer 12. Figure IB is a schematic cross section of a two-layer sealing structure consistent with formula 1. The sealing structure detached 10<sup>2</sup> includes sealing layer 12 and additional layer 14. Figure IC is a schematic cross section of a three layer sealing structure consistent with formula 1. In this variation, the sealing structure detached 10<sup>3</sup> includes sealing layer 12 and additional layers 14, 16. Figure ID is a schematic cross section of a three layer sealing structure consistent with formula 1. In this variation, the sealing structure detached 10<sup>4</sup> includes seal layer 12 and additional layers 14, 16, 18, 19. Figure 1E is a schematic cross section of a three layer seal structure consistent with the seal structures of formula 2. In this variation, the structure sealing detached 10<sup>4</sup> includes sealing layer 12 disposed between additional layers 14, 17. Any layer 14 or 17 is a non-stripping sealant layer that is capable of sealing itself or sealing to a substrate. The sealing layer 12 allows opening delamination. Generalization to sealing structures with additional layers as noted in
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<img file="MX355447B_D0033.tif" />
formulas 1-6 is direct. It should be noted "" that "in" each of the variations of Figures IA, IB, 1C, ID, and 1E, the sealing layer 12 comprises a thermoplastic polymer, an organoclay dispersed within the thermoplastic film, and an additive comprising an additional additive (eg, calcium carbonate, magnesium carbonate, titanium oxide, talc, barium silicate) dispersed within the thermoplastic polymer. The sealing layer 12 is adapted to contact a substrate section of a container to form a release seal. Such containers can be of virtually any shape that is useful for packaging an object. Examples of such figures include, but are not limited to, ampoules, trays, bags, pockets, and combinations thereof.
Seal layers formed from the composition noted above have improved and uniform release performance when incorporated into a seal as more fully described below. Interfaces sealed using the removable sealing structure 10<sup>1</sup>, ΙΟ<sup>2</sup>, 10<sup>3</sup>, 10<sup>4</sup>, and 10<sup>5</sup> (collectively, peel-off seal structures 10) come off in a consistent pattern. Airtight seal integrity is not compromised even when film specimens include wrinkle, crease, and gusset configurations in various bag / pocket gasket styles, through forming, filling, and vertical seal (VFFS), forming, filling and horizontal seal (HFFS), and wrap
-30IV
<img file="MX355447B_D0034.tif" />
OF THE ··,: ·> v
IN? ... u 'flow. The unprepossessing sealing structure<sup>44</sup>Ίϋ * '* e xhibé * a release behavior consisting of the following combinations: 1) the sealing layer 12 making contact with another sealing layer of an analogous composition or the same; 2) the sealing layer 12 contacting a structure formed from pure sealant (e.g., organoclay-calcium carbonate / polyethylene layer and / or ethylene copolymer versus pure polyester layer, organo-clay layer -calcium carbonate / polyethylene against a layer of pure polyethylene). Processing aids such as anti-blocking agents, antioxidants, slip additives, heat stabilizers, plasticizers, UV absorbers, anti-static agents, colorants, pigments, processing aids, release agents and the like are optionally included in the sealing layers and do not affect the peeling pattern of the sealing structure 10.
Additional layers 14, 16, 18, 19, 20, 21, 22 and 23 (i.e.L layers<sub>1</sub>-L<sub>10</sub> and L<sub>F</sub>) are used to provide a number of features useful to the present embodiment. For example, additional layers 14, 16, and 18 can provide structural support, heat resistance, barrier properties, and improved appearance to gasket systems that incorporate release seal sections. It should also be appreciated that the present embodiment encompasses, in addition to single-layer peel-off sealing structures, structural
-31 .vi,<sup>1</sup>'.' i V
INSTITUTE λίΓΛ'ΟΛ ¿Or v · -, ·· ...
OF THE? Ε <<< ··· .Υ.Γϊ ~<sup>h</sup>
Multi-layered flush bearing nnalqnifir ηύτη ^ κς of additional shims in the form including lamination, co-extrusion or coated structure. In each variation of the present embodiment, multilayer sealing structures include release seals having the compositions described herein.
With reference to Figures 2A, 2B, and 2C, packing systems incorporating the loose seal structures outlined in Formulas 1-6 are described. Figure 2A is a cross section of a bag-like packing system incorporating one embodiment of the release release seal structure of the invention. FIG. 2B is a side view of a bag-like packing system incorporating one embodiment of the release release seal structure of the invention. Packing system 20 includes container section 22 and release seal section 24. Detachable seal section 24 is attached to container section 22. Figure 2A illustrates an example in which the peelable seal section 24 and the container section 22 are continuous, each being formed from the same multilayer structure (ie, sheet). Container section 22 can have virtually any shape that is useful for packaging an object in a bag, such as a pillow flow wrap, four-side seal, or gusseted bag. The sealing section 24 includes a structure
<img file="MX355447B_D0035.tif" />
-32Λ, l · ..? i); <· - ··> .'- <· Jt JL JL
INSTITUT -? - ?: 3
DE U f. ', 7.
seal detached him 10. In the var iacióñ ''<sup>1</sup> íTusTfa'd'áén 'Ta figure 2A, the detachable sealing structure 10 includes the sealing layer 12 arranged on the additional layer 14. As noted above in connection with the descriptions of Figures IA, IB, and IC, the layer Sealing 12 comprises a thermoplastic polymer with organoclay and calcium carbonate as additives dispersed within the thermoplastic polymer.
Even with reference to Figures 2A and 2B, the packing system 20 further includes a second 'D 10' sealing structure contacting the detached sealing structure to form the detachable seal 30. The seal 30 seals an opening in the side Top 32 of the gasket system 20. Similar release seals are optionally placed on the bottom side 34, left side 36, and right side 38. The detachable sealing structure 10 'also includes the sealing layer 12 arranged on additional layers 14. Specifically, a first portion of the combination of the sealing layer 12 arranged on the additional layers 14 forms the sealing structure 10 while a second portion of the sealing layer combination 12 arranged on additional layer 44 forms the sealing structure 10 '. The sealing structures 10, 10 'are continuous with container section 22. In a variation of the present embodiment, a third portion of the sealing layer combination 12 arranged on additional layers 14 at least partially forms the container section
<img file="MX355447B_D0036.tif" />
22. Advantageously, the emp a qu e ta duT3 system<sup>r</sup> '2Ü'SST is adapted to contain 40 objects (ie it may be one or more objects). Examples of objects 40 that can be packaged include, but are not limited to, food products and sterilized objects (e.g., medical devices and non-food products, such as personal hygiene products, diaper liners, pet products, etc. .).
Referring to Figure 2C, a gasket system incorporating the release seal structure of Formulas 5 and 6 is provided. Figure 2C is a cross section of such a packing system. The packing system 20 includes the container section 22 and the release seal section 24. The release seal section 24 is attached to the container section 22. Figure 2C illustrates an example in which the peelable seal section 24 and container section 22 are continuous, each being formed from the same multilayer structure (ie, sheets). Container section 22 can have virtually any shape that is useful for packaging an object in a bag, such as pillow flow wrap, four-side seal, or gusseted bag. The sealing section 24 includes the peelable sealing structure 10 in which the sealing layer 12 is interposed between the layers 17 and 44.
Referring to Figures 3A and 3B, variations of the peelable seal section 23 as used in
<img file="MX355447B_D0037.tif" />
Bag-like gaskets are illustrated — La ^ Xifflira ^ 3Aes, a schematic cross section of an improvement in which the sealing layer 12 is substantially confined to the vicinity of the peelable sealing section 24. This variation is achieved by either confining the incorporation of organoclay or by depositing a different layer in the vicinity of the sealing structure 24. This variation further includes the inner layer 42 and one or more additional polymer layers 14. Figure 3B is a schematic cross section of an improvement in which the gasket system 20 includes the second seal layer 46 with the release seal 30 being formed between first seal layers 12 and second seal layer 46. In this further refinement, the seal layer 12 extends minimally, if at all, towards container section 22. Furthermore, in this refinement, the container section 22 optionally includes the liner layer 42 which is different from the first seal layer 12. In a further refinement of this variation, the seal section 24 further includes one or more layers. of additional polymer 14 disposed on the first sealing layer 12 and / or the second sealing layer 46. In a particularly useful example of this refinement, one or more additional polymer layers 14 at least partially form the container section 22.
Referring to Figures 4A and 4B, variations of gasket systems using sealing structures
<img file="MX355447B_D0038.tif" />
MEXICAN INSTITUTE OF PROPERTY
INDUirnUAL
<img file="MX355447B_D0039.tif" />
Tear-outs of the invention with rigid container sections are illustrated. Figure 4A provides a schematic section of a cup-like gasket system using the peelable sealing structures of the invention. The packing system 50 includes the peelable sealing structure 10 and the sealing opening 52 of the container section 54. A peripheral portion of the peelable seal structure 10 is disposed on and contacts the substrate section 56 of the container section 54. Figure 4B provides a schematic cross section of a blister packing system incorporating multiple containers similar to Cup. The blister packing system 60 includes the peelable seal structure 12 and the container section seal openings 62, 64 66, 68. A removable seal structure portion 12 is disposed on and contacts substrate sections 70, 72 of container sections 66, 68.
The peelable seal layer 12 of the various embodiments of the invention includes an inorganic additive such as calcium carbonate. Calcium carbonate comprises a plurality of particles. In a refinement, the particles have an average diameter of 0.5 micras to 20 micras. In another refinement, the particles have an average diameter of 0.7 microns to 10 microns. In yet another refinement, the particles have an average diameter of 0.7 microns to 3 microns. Calcium carbonate can be natural calcium carbonate, ~ τυ
<img file="MX355447B_D0040.tif" />
λ χ · WO IIIU IV »Uii '*** · *' - ··
-JO- OWNED V jINDUSTSUL activated calcium carbonate with a surface treatment (eg, a stearic acid coating), or a precipitated calcium carbonate.
The release liner 12 of the various embodiments of the invention includes an organoclay. Organoclay is based on clay with organic surface modification. Examples of useful clays are natural or synthetic layered oxides which include, but are not limited to, bentonite, kaolinite, montmorillonite-smectite, hectorite, fluorohectorite, saponite, beidelite, nontronite, illite clays, and combinations thereof. Organoclay is generally modified on its surface with organic onium ion or phosphonium ion. The onium ion can be protonated primary, secondary, tertiary, or quaternary ammonium ion (R4N)<sup>+</sup>.
US Patents 5,780,376, 5,739,087, 6,034,163, and 5,747,560 provide specific examples of organoclays that are useful in practicing the present invention. The entire disclosure of each of these patents is incorporated herein by reference. In a further development of the present invention, the organoclay is present in an amount of from 1% by weight to 20% by weight of the combined weight of the thermoplastic polymer, the organoclay, and the additional inorganic additive. In another refinement of the present embodiment, the organoclay is present in an amount of from 2% by weight to 10% by weight of the combined weight of the thermoplastic polymer, the
<img file="MX355447B_D0041.tif" />
OF THE PROPERTY
INDUSTRIAL ''
-37organoclay, and the inorganic additive
The organoclay typically comprises a plurality of particles. These discrete particles can be derived from larger masses through a number of processes, most preferably through a well-known process called ion exchange that transforms clay from hydrophilic to hydrophobic organoclay and separates individual layers, resulting in particles that they remain separate through further processing. An organoclay from this process is then introduced to polymer and further separated into exfoliated clay. In one variation, the organoclay comprises a plurality of particles having at least one spatial dimension less than 200nm. In another variation, the organoclay comprises a plurality of particles having at least one spatial dimension less than 100nm. In another variation, the organoclay comprises a plurality of particles having at least one spatial dimension less than 50nm. In yet another variation, the organoclay comprises a plurality of particles having spatial dimensions greater than or equal to 1 nm. In yet another variation, the organoclay comprises a plurality of particles having spatial dimensions greater than or equal to 5 nm. In another variation, the organoclay comprises
<td></td><td>platelets</td><td>having</td><td>a</td>
<td></td><td>angstroms.</td><td>In even</td><td>other</td>
<td> 25</td><td>platelets</td><td>having</td><td>a</td>
<img file="MX355447B_D0042.tif" />
<img file="MX355447B_D0043.tif" />
ΡΙ: i '. Ti'UTO MEXICANO, Έ INDUSTRIAL PROPERTY
-38angstroms. In yet another variation, the organoclay comprises platelets having an average separation of at least 40 angstroms. Typically, before combining with the thermoplastic polymer, the organoclay comprises platelets having an average separation between 20 and 45 angstroms. Advantageously, when combined with the thermoplastic polymer, the organoclay remains in a fully or partially exfoliated state such that the average separation is maintained, decreased, or increased. In a variation of the present embodiment, the tool that the organoclay has a surface area greater than 100 m<sup>2</sup>/ gram and an aspect ratio greater than 10. In a refinement, organoclay platelets have an average aspect ratio of about 50 to about 1,000.
As noted above, the release liner 15 15 also includes a thermoplastic polymer.
Suitable thermoplastic polymers include, but are not limited to, nylons, polyolefins, polystyrenes, polyesters, polycarbonates, and mixtures thereof. In one variation, the thermoplastic polymer comprises a component selected from the group consisting of polyethylene, polypropylene, ethylene vinyl acetate, ethylene acrylic acid, ethylene ethyl acrylate, ethylene ionomers (e.g., the Surlyn line of resins Available from I.. I. du Pont de Nemours and Company), and combinations thereof. Polyolefins are thermoplastic polymers particularly useful in the practice of the invention. In a variation, the
<img file="MX355447B_D0044.tif" />
MEXICAN PROPERTY INSTITUTE
INDUSTSIAL polyolefin is selected from the group "qüeCSYiSiste" "ctt homo-polymers and co-polymers of ethylene, propylene, vinyl acetate, and combinations thereof. Ethylene vinyl acetate (EVA) and physical mixtures of polyolefins with ethylene vinyl acetate (EVA) copolymer are found to be particularly useful in forming release seals especially when the additive is an organoclay. EVA is a co-polymer of ethylene and vinyl acetate. The amount of vinyl acetate in EVA varies from 3 to 40% by weight. Exemplary examples of the amount of vinyl acetate are 4%, 5.5%, 6%, 18%, and 33%. It should be appreciated that the additional layers (eg, L layers<sub>x</sub>-L<sub>n</sub>, L ^ -L ',,, L<sub>F</sub> noted above in connection with formulas 1-6) can be formed from the same pure thermoplastic polymers that are included in the seal layer.
The container sections of the various embodiments of the invention are formed from virtually any material used for packaging. Such materials include, but are not limited to, paper or card stock, metal foil, polymeric foil, metallized or otherwise coated polymeric foil, and combinations thereof. More specific examples include, oriented or non-oriented polyester, oriented or non-oriented polypropylene, oriented or non-oriented nylon, and combinations thereof, made from the adhesive lamination, extrusion lamination, co-extrusion or coating process. Each one of these
-40ΪΡΒ INSTITUTO MEXICO DE LA PROPIEDAD INDUSTRIAL ιυ materials may be coated or not re Examples of coatings include, but are not limited to, varnishes, lacquers, adhesives, inks, and barrier materials (ie, PVDC). Useful materials for packaging medical devices include high-density polyolefins, Tyvek (a synthetic material made of high-density polyethylene fibers commercially available from Dupont, Inc.) is an example of such a material used to package medical devices.
In a variation of the packing systems noted above, the packing systems are observed to have an advantageously high thermal conductivity to allow for improved processing efficiency. Generally, packing systems have a thermal conductivity of about 0.40 w / m * K to about 10 w / m * K. In one refinement, the packing systems have a thermal conductivity greater than about 0.40 w / m * K. In another refinement, the packing systems have a thermal conductivity that is greater than 0.60 w / m * K. In yet another refinement, the packing systems have a thermal conductivity that is greater than about 0.80 w / m * K. Typically, packing systems have a thermal conductivity that is less than about 10 w / m * K.
In yet another embodiment of the present invention, a method for forming the packing system noted above is provided. With reference to figure 5,
<img file="MX355447B_D0045.tif" />
-41 ιυ
MEXICAN INSTITUTE OF PROPERTY
INDUSTRIAL
<img file="MX355447B_D0046.tif" />
A diagram illustrating the method of this embodiment is provided. A thermoplastic polymer (TP) combines with an organoclay (OC) and an inorganic calcium carbonate (CC) additive to form an organoclay / calcium carbonate polymer compound (OC / CCB) in a step a). In a variation, this process occurs on extruder 80. The sealing layer 12 is then extruded from the die 82 in step b) from the organo-clay / calcium carbonate polymer compound. In a variation, additional layers are formed by providing material from additional extruders (such as extruder 90) to die 82. In a refinement of the present embodiment, the thermoplastic polymer and organoclay / calcium carbonate are premixed in a mixer 84 and then introduced into extruder 80. Typically, the seal layer 12 will be formed together as a cone or on one or more additional layers 14, 16, 18, 19 (as shown in Figures 1A-E). The open packing system 20 is then formed in step c). This process may include steps in which the sides are sealed to produce the bag structures of Figures 2-4. In a variation, the formation of the open packing system 20 occurs during step b).
In a variation of the present embodiment, a thermoplastic polymer is combined with an organoclay and an inorganic additive, such as calcium carbonate by mixing
MEXICAN INSTRUMENT
DE LA FR.OFIIDA »
INDUSTRIAL
-42Ο
<img file="MX355447B_D0047.tif" />
an organoclay master batch and a calcium carbonate master batch with a pure polymer. In one variation, the calcium carbonate masterbatch comprises calcium carbonate and a portion of the thermoplastic polymer. In an improvement, the calcium carbonate master batch typically includes 10 to 80% by weight of calcium carbonate. In another variation, the organoclay master batch comprises the organoclay and at least a portion of the thermoplastic polymer. In a refinement, the master batch typically includes 10 to 80% by weight of organoclay.
Calcium carbonate is well known for its thermal conductivity (Roussel, et al. The use of calciuia carbonate in polyolefins offers significant improvement in productivity, TAPPI 2005). Thermal conductivity of calcium carbonate is 2.7 W / (m * K) and for pure polyolefin it is usually less than 0.5 W / (m * K). Introducing calcium carbonate into the sealant formulation provides the ability to quickly heat and melt the polymer resin. On the other hand, clay has high heat storage capacity. It tends to keep warm longer. The combination of organoclay and calcium carbonate offers a synergistic effect and facilitates rapid melting of the sealant with slow cooling, allowing time for the physical polymer mixture to flow and caulk the channels, and provide improved caulking ability.
The step of forming the sealing layer 12 is accomplished by
-X
<img file="MX355447B_D0048.tif" />
Mexican INSTITUTE v DE LA. PROPERTY
INDUSTRIAL
-43 ~ ru any method capable of producing layers or ppj ί πηla.%. A..part from thermoplastic compositions. Examples of such methods include, but are not limited to, extrusion, co-extrusion, extrusion coating, blow molding, casting, extrusion blow molding, and film blowing.
Still referring to FIG. 5, the method of the present embodiment optionally further comprises placing objects 40 within the open packing system 20 (step d). Typically, objects 40 reside within container section 22. After objects 40 are placed within container section 22, sealing layer 12 is contacted with a sealing substrate (i.e., the sealing structure 10 ') during step c) to form a seal. Sealing can be accomplished by any number of sealing methods known in the art. Examples include, but are not limited to, conduction heat seal, ultrasonic seal, impulse heat seal, and induction seal.
The following examples illustrate the various embodiments of the present invention. Those skilled in the art will recognize that many variations are within the spirit of the present invention and the scope of the claims. Example 1
Comparison of Sealant Containing Organoclay and Carbonate
Calcium
A five layer film was prepared to contain
<img file="MX355447B_D0049.tif" />
INDUSTPJAL
BISrmrro MEXICANO \ DE LA PROPERTY;
<img file="MX355447B_D0050.tif" />
44 Layers HDPE / LLDPE / LLDPE / Union / Sealant. The sealant contained 10.4% by weight of calcium carbonate and without organoclay, in a physical mixture of polyethylene (Exact 3131 by ExxonMobil) and EVA (Ateva 1811 by Celanese Corporation with 18% vinyl acetate). The CaCO master batch<sub>3</sub> (CDMB) was a proprietary formulation containing around 80% by weight of CaCO<sub>3</sub>. CCMB was made at Heritage Plastics under the brand name of HM10 MAX (melt flow index of 1.40 g / 10 min, density 1.92 g / cm<sup>3</sup>). This film was compared to a second film (Film 1) having an organoclay sealant layer and no calcium carbonate. This film was discussed as 5% clay in US Patent 2008/0118688 Al, Figure 7A. Organoclay Master Batch (OCMB) was a proprietary formulation containing about 60% by weight of organoclay, manufactured by PolyOne under the trademark EXP MB 231-615. Breakout strength was tested on Lako SL-10. Films were sealed on a flat fin to fin seal bar, with pressure at 35 psi (241.32 kPa), a residence time of 0.33 seconds, and a cool down time of 20 seconds. Figure 6 provided a trace of the peel force against temperature for a seal formed from these two films. The film-containing calcium carbonate sealant was removable when sealed at 190 ° F (87.78 ° C) with a peel force of 6.3 lb / inch (1,103.30 N / m). As the seal temperature increased to 250 ° F (121.11 ° C), the seal was welded at the
<img file="MX355447B_D0051.tif" />
seal and was not able to be detached; some of the films were broken at the seal edge during peeling. Since the film was not peelable, the mean force was not accurately representing the peel force. For tracing purposes, a peel force of 3000 g / inch (6.8 pound / inch) was recorded. In the case of sealant composition containing organoclay / calcium carbonate, the seal was removable over a wide seal temperature range of 190 ° F to 260 ° F (87.78-126.67 ° C) as shown in Figure 6.
Example 2
Sealant Contains Physical Mix of Organoclay with Carbonate of
Calcium
Film samples 2, 3, 4, 5 and 6 were prepared for testing. They were five layer films containing HDPE / LLDPE / LLDPE / bond / sealant layers. Physical sealant mixtures of those films were formulated to contain different ratios of organoclay and calcium carbonate. Physical sealant mixtures of these films were formulated to contain different ratios of organoclay and calcium carbonate. Film 2 contains 78% by weight of EVA (18% vinyl acetate, Ateva 1811, Celanese Corporation), 10% by weight of metallocene LLDPE (Exact 3131), 6% by weight of OCMB and 6% by weight of CCMB. OCMB contains about 60% by weight of organoclay, and is purchased from PolyOne under the brand name EXP MB 231-615. The
<img file="MX355447B_D0052.tif" />
V JS JA. ¿,. , institute me; uca? ío and- '·<sup>:</sup> '·'. * * Dfi THE QUESTION V? ' V INE'úSTiiLtL '.τ'. · ** '*
CCMB is from Heritage Plastics under the brand name HM-10 MAX (melt flow rate 1.40 g / 10 min, density 1.92 g / cm<sup>3</sup>).
Film 3 sealant formulation contains 6% by weight OCMB and 13% by weight CCMB, 71% by weight EVA (18% vinyl acetate, Ateva 1811, Celanese Corporation), 10% by weight LLDPE metallocene (Exact 3131). In the sealant formulation for film 4, OCMB loading was increased by 10% by weight and CCMB loading was discharged to 6% by weight along with 74% by weight of EVA (18% vinyl acetate, Ateva 1811, Celanese tu Corporation) and 10% by weight of metallocene LLDPE (Exact 3131).
For film 5, OCMB loading in the sealant formulation was further increased to 13% by weight and the CCMB loading was not changed by 6% by weight along with 71% by weight EVA (18% vinyl acetate, Ateva 1811, Celanese Corporation) and 10% by weight of metallocene LLDPE (Exact 3131). The physical sealant mix for Film 6 consisted of high OC and CC loading, with 13% by weight OCMB, 12% by weight CCMB, 65% by weight EV (18% vinyl acetate, Ateva 1811, Celanese Corporation) and 10% by weight of metallocene LLDPE (Exact 3131).
Figure 7 provides traces of peel strength against seal temperature for seals made from these compositions having different ratios of organoclay (OC) to calcium carbonate (CC). At 6 wt% OCMB, Films 2 and 3 had narrow drop-out windows and gradually became non-release.
-47IMPI
INSTITUTO KFXtCAKO LIE LA ΙΆΟ'.ΊΕΟΑΟ industrial
<img file="MX355447B_D0053.tif" />
As the sealing temperature increased. When the OCMB load was increased to 10% by weight (film 4), the peel range was extended, and the film peeled below 265 ° F (129.44 ° C). When the OCMB wt% was further increased to 13% or higher, Films 5 and 6 provide peel ability over the entire seal range of 190 ° F to 265 ° F (87.78-129.44 ° C). Furthermore, Figure 7 clearly illustrates that some organoclay / calcium carbonate combinations produce peel seals over a wide range of sealing temperatures while others do not.
Example 3
Increased CCMB Load in Physical Sealant Mix Containing OC and CC
Additional test films were prepared with more variables in combination of organoclay and calcium carbonate for release sealant formulations. Films were built as a five-layer structure containing
HDPE / Union / Nylon / Union / Sealant. Table 1 lists the detailed sealant layer formulations, and Figure 8 plots the seal force over seal temperature.
institute mkxjc.v :. '»
DE LA PiíC?.? '/. ·.'>
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<img file="MX355447B_D0054.tif" />
-48 Table 1
<td>Movie #</td><td>EVE</td><td>OCMB</td><td>CCMB</td><td>LLDPE</td>
<td> 7</td><td> 65%</td><td> 13%</td><td> 12%</td><td> 10%</td>
<td> 8</td><td> 68%</td><td> 10%</td><td> 12%</td><td> 10%</td>
<td> 9</td><td> 65%</td><td> 10%</td><td> 15%</td><td> 10%</td>
<td> 10</td><td> 58%</td><td> 12%</td><td> 20%</td><td> 10%</td>
All films in this series have a peel force within an easy opening range of 1 to 5 lb / in (175.13-875.63 N / m). Film 8, with 10% OCMB and 12% CCMB in the physical sealant mix, had a breakout force range of from about 3lb / inch to 4.5lb / inch (525.38-788.07 N / m). The physical sealant mix for film 9 had the same OCMB load as for film 8, but with CCMB load increased to 15% by weight. Breakout force was reduced from 3 to 4.5 lb / inch (525.38-788.07 N / m) for film 8 to a range of about 1.5 to 3 lb / inch (262.69-525.38 N / m) for film 9. While OCMB is maintained at 10% by weight, CCMB increased to 15% by weight (Film 9), release force falls well within the release range. Film 10 contains 12% OCMB and 20% CCMB. As noted in Figure 9, the peel curve for film 10 was observed to be nearly flat from a seal temperature of 190 ° F to 265 ° F (° C).
Example 4
Higher Load of mLLDPE in Physical Sealant Mix Containing OC
-49ΙΜ
MRXICAKO INSTITUTE OF PROPERTY
INDUSTRIAL
<img file="MX355447B_D0055.tif" />
~ ιυ and CC
Five layer HDPE / bond / nylon / bond / sealant films were prepared. Details for these films are set forth in Table 2. Sample 11 was prepared for comparison to Sample 8. Samples 13 and 12 provide additional results demonstrating the effect of higher% by weight mLLDPE and its influence on peel strength. . Higher mLLDPE loading (34% vs. 10% for films 11 and 8; and 24% vs. 10% for films 13 and 12) resulted in a reduction in seal strength at lower temperature ranges, and made it impossible to achieve a seal of quality. Such a high mLLDPE load requires the Seal Start Temperature (SIT) to be increased to 220 ° F (104.44 ° C), which is not favored. Figure 9 shows the peeling force against the seal temperature.
Table 2
<td>Movie #</td><td>EVE</td><td>OCMB</td><td>CCMB</td><td>LLDPE</td>
<td> 8</td><td> 68%</td><td> 10%</td><td> 12%</td><td> 10%</td>
<td> 11</td><td> 44%</td><td> 10%</td><td> 12%</td><td> 34%</td>
<td> 12</td><td> 74%</td><td> 13%</td><td> 3%</td><td> 10%</td>
<td> 13</td><td> 60%</td><td> 13%</td><td> 3%</td><td> 24%</td>
Example 5
Age Effect of Sealant Containing OC and CC
The existing polybutylene-based sealant (PB-1) is well known for its ability to form a seal that opens easily. The aging effect of the sealant based on
<img file="MX355447B_D0056.tif" />
PB-1 has been described (Charles Hwo, Polybiil ^ J ^ O £ íJ & J¿SJ3ds, ... as. Eas. And Open Seal Coats for Flexible Packaging and Lidding, EFFECT J PLASTIC FILM AND SHEETING, 1987 V3, 245). During aging, PB-1 passes through a phase transformation from molten stable Form II crystals to Forma crystals.
I within 2-3 days at room temperature and pressure. During phase transformation, the crystallinity gradually increases and results in a higher breakout force.
In order to examine the effect of age of OC and CC containing sealants, the film was sealed and tested after aging. On the same day of testing on an aged sample, a set of films was sealed fresh and the peel strength was tested as a control. The film was cut into one inch strips and sealed, sealant to sealant, in a flat jaw with temperatures above 220 ° F (104.44 ° C), and a residence time of 0.3 seconds. The peel strength test was done on an Instron Tension Tester using a 100 pound (45.36 kg) load cell with a transverse speed of 12 inches / min (30.48 cm / min). Table 3 summarizes the breakout force results for this test.
<img file="MX355447B_D0057.tif" />
-*--*-* <sup>J ν</sup> * 'VINSTÍTUTO MEXICANO </ DE LA PROPÍWAD 1NÜÜSTOAÍ.
'S<sup>;</sup> . ·/ · ••.and
Table 3 Breakout Force After 1 — Aging Week
<td></td><td></td><td>g / inch</td><td>g / inch</td><td>% change</td>
<td>Movie 1</td><td>OC only</td><td> 743</td><td> 696</td><td> -6.3%</td>
<td>Movie 7</td><td>OC / CC</td><td> 1104</td><td> 1068</td><td> -3.3%</td>
As a polybutylene based sealant it has
Incrementaο Increased release upon aging, OC and OC / CC based sealants showed no increase in release strength. After 1 week of aging, the peel strength for OC and OC / CC is slightly decreased, which is similar to fresh sealed samples since the difference here is within experimental error. Example 6
Caulking Capacity and Rheology Test
One of the most important functions of a sealant is to maintain the complete integrity of a gasket. Functional sealants must have good heat seal resistance, low starting temperature, and be able to completely seal through the folds, contaminants, and wrinkles that occur in a current gasket environment. Testing of the integrity of flexible gaskets allows better prediction of performance in real life. One way to characterize such sealant behavior is the caulking ability of a sealant resin.
Generally, materials exhibiting good caulking ability are capable of preventing backflow of any flow
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INuvSTν, χι ιΧ · πυ plug during the sealing process. Rheologically, this behavior has been exhibited for materials having a solid-like character (tendency to store energy elastically) at lower experimental frequencies (longer experimental times). EVA / LLDPE / OC / CC sealant compositions are found to exhibit such characteristics.
One of the caulking ability test methods is illustrated in Figure 10 and Figure 11. Single-layer films of the sealant, or multi-layer gasket films bearing an outer layer of sealant, are formed into a square envelope of 3x3 (7.62x7.62 cm) with three sealed sides and one unsealed side. A 0.25 (0.635 cm) wide rectangular obstacle is inserted in the middle of the open side (not sealed) and a flat heat seal line is forced through the obstacle (the study is carried out for multiple envelopes of the same sealant with obstacles that increase in height from 0.25 mils to 35 mils (6.35 to 889 microns); all seals are made under the same conditions with an industrially relevant sealant, e.g., impulse sealer, flat plate sealer, etc.). For purposes of this work, rigid rectangular obstacles, such as kapton tape or copper tape, varying in height from 0.25 mil to 35 mil (6.35 to 889 microns), will be used, simulating rigid obstacles in practice, such as food particles , zippers, wrinkles and folds formed on the
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reinforcements, such as food particles, zippers, etc. More preferably, rectangular polyethylene-based obstacles were used with a height ranging from 0.25 mil to 35 mil (6.35 to 889 microns), simulating packing material obstacles in practice, such as wrinkles, folds, reinforcements, etc. If an unsealed (runaway) area forms next to the obstacle, this area is measured. For measurements made, two metrics are used to quantify the caulking capacity (or caulking quality) of a sealant. iu The first metric is the maximum height of the rectangular obstacle that can be perfectly sealed (hermetically), referred to hereinafter as the final perfect seal thickness; the second metric is the rate of escalation of the escaper area with respect to the increase in the height of the obstacle, hereinafter referred to as the escaper growth rate. By definition, when comparing two sealants, the one with the best caulking ability will be characterized by a larger final perfect seal thickness and a smaller leaker growth rate.
Referring to Figure 10, the caulking test method introduces a gap with a flat cable near the sealing region to simulate a contaminant during the heat seal process. By introducing a gap using a ribbon cable 100 of a certain thickness during sealing of the films 102, 104, the unsealed area 106 is measured using
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MEXICAN INSTITUTE OF INDUSTRIAL FOOD
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Optical microscopy. As illustrated in Figure 10, it is difficult to seal at the edge of the gap. Therefore, the unsealed area 106 is located from the edge 108 of the ribbon cable 100 to the edge 110 of the sealed area 112. A smaller reading of the unsealed area represents better caulking ability and increased ability to provide a watertight seal. The results of this test depend on a number of parameters such as sealant thickness and sealing temperature / pressure. Several specimens for each sample are evaluated at different thicknesses of contaminants. The tests are carried out using the same sealant layer thickness when comparing different sealant formulations. In a trace of the unsealed area against contaminant thickness as illustrated in Figure 11, caulking capacity parameters can be determined from the slope and final contaminant thickness for a perfect seal. Final Perfect Seal Thickness is the thickness of contaminant in a non-zero-seal area, which is calculated by extrapolating the curve to the non-zero-seal area. In this figure, the unsealed area is plotted as a function of contaminant thickness. The contaminant thickness is the thickness of the flat cable. The data are fitted by linear regression (eg, a least squares fit) with the caulk slope being the slope of the fitted line. The final seal thickness is the thickness of the contaminant in a non-seal area of zero. Figure 12A provides traces for various formulations. The
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INDUSTRIAL Figure 12B shows the caulking slope da ,.<sub>l</sub>«JÍi.feraGt.es samples. In order to understand the scope of these data, control samples are tested together with the organoclay and calcium carbonate samples. Comparable samples include Surlyn 1601 and Surlyn / EVA physical mix.
As noted above, the lower the caulking slope, the better the caulking. Without the presence of organoclay, Surlyn has the best caulking. With the addition of organoclay in the sealant formulation, all samples containing organoclay demonstrated similar, if not better, caulking ability to Surlyn. For a system that combines organoclay with calcium carbonate, all physical mixes have better caulking than organoclay-only film, and better caulking than Surlyn. These physical mixtures indicate the synergistic effect between organoclay and calcium carbonate that attributes to a sealer performing better.
The samples were also evaluated by linear oscillatory rheology test. Stress sweep tests were first carried out at a frequency of 1 rad / s to determine the linear viscoelastic region. Subsequently, oscillating rheology frequency sweep tests of 100 to 0.1 rad / s were performed at stresses within the linear viscoelastic region. All rheological tests were carried out on an RDS II Rheometer using 25 mm parallel plates of
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INSTITUTO AiLTJCíUO DEIA? Ko; -; .- .; a ;, '¡fCUS'. 'IlAL' diameter, under atmosphere of N<sub>2</sub>. Data were acquired at four different temperatures: 130 ° C, 160 ° C, 190 ° C, and 220 ° C, and subsequently moved using the time-temperature superposition principle (t-TS) to form the reduced curves at one temperature. reference temperature of 130 ° C.
In such experiments, solid-like behavior was evaluated from the G 'and G traces against reduced frequency (ω * β<sub>Ψ</sub>). The viscoelastic behavior of the system in ω is characterized by the storage modulus or elastic modulus G '(ω), and the loss modulus or viscous modulus, G (ω), which respectively characterize the contributions similar to solid and similar to fluid to the measured effort response. The two viscoelastic parameters are used to detect the solid-like behavior and the relaxation time (inverse of the crossing of G 'and G) and the slope of the curve of G' against o * a<sub>T</sub> at very low values of u * a<sub>T</sub> (frequency). Longer relaxation times (or less slope) tend to result in increased solid-like character with high storage energy of high elastic solid phase to recover, and therefore better caulking. Figures 13A and B provide traces of G 'and G against frequency (m * a<sub>T</sub>) for a number of compositions. Rheology response of all CC / OC compounds are similar, but quite different from sealant only with OC. For the DC / OC sealant, G 'became almost frequency independent at very low frequencies, which correlates
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
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-57 with solid-like behavior (better caulking). The results of these traces are provided in Table 4 and Figure 14. Since the crossing of G 'and G was not detected in all samples, the parameter of G' / a<sub>T</sub>or used to assess correlations with caulking ability.
Table 4. Rheological Results
<td></td><td>G 'G cross over relaxation time at 130 ° C (s)</td><td>Flow activation energy (KJ / mol)</td><td>Pending (G '/ aTm)</td>
<td>EVA (Ateval811)</td><td> 0.66</td><td> 57.7</td><td> 0.71</td>
<td>Surlyn 1601</td><td> 0.33</td><td> 68.9</td><td> 0.71</td>
<td>OC movie</td><td> 0.26</td><td> 53.3</td><td> 0.67</td>
<td>Movie 7</td><td> -</td><td> 54.8</td><td> 0.16</td>
<td>Movie 8</td><td> -</td><td> 46.4</td><td> 0.22</td>
<td>Movie 9</td><td> -</td><td> 41.9</td><td> 0.25</td>
<td>Movie 10</td><td> -</td><td> 56.3</td><td> 0.20</td>
Correlation between caulking ability and rheology parameters
Figure 14A provides a plot of the ratio of the caulking slope against G '/ a<sub>T</sub>a> for multiple samples. Lower values of G '/ a<sub>T</sub>which correspond to higher solid-like behavior and better caulking capacity with higher storage energy. Figure 14B provides a plot of the ratio of final seal thicknesses against G '/ a<sub>T</sub>or for multiple samples. OC / CC samples were found to have the best caulk and the pure polymer physical mix had the worst.
Figure 15 provides a trace of the caulking slope and G '/ a<sub>T</sub>or for value sealants. Values more
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MEXICAN INSTITUTE OF PROPERTY
INDUSTRIAL
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G '/ a bass<sub>T</sub>my caulking slope C'ürrtisponden- --con-behavior similar to a major solid. OC / CC samples have the best performance for composition and pure polymer physical mixtures have the worst. Similarly, with respect to final perfect seal thickness, OC / CC samples exhibit the best performance while the pure polymer physical mixture exhibits the worst.
Example 7
Thermal Conductivity Estimation
The Differential Scanning Calorimetry (DSC) method was used to estimate thermal conductivity of the sealant containing OC and CC. Pellets of different physical sealant mixes were extruded and injection molded into test bars. A small sample of approximately 4 mg in size was cut from the test bar and encapsulated in standard DSC trays. DSC was carried out with TA Instruments Q100 equipment. Prior to testing, a 10 ° C / min heating cycle was performed to erase the thermal history of the physical mixture. The test was carried out in three subsequent cycles of heat-cooling-heat experiments between 30 ° C and 160 ° C, with various rates of heating and cooling. The first cycle was run at a rate of 5 ° C / min, the second cycle at 10 ° C / min, and the third cycle rate at 20 ° C / min. As shown in Figure 16, DSC scans contain EVA signals that have one crystal region and LLDPE exhibits two crystal regions.
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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
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-./TX »<? Ü ñas, exhibited as exothermic peaks. J5ñEaT '"samples of EVA / LLDPE / OC and EVA / LLDPE / OC + CC exhibited two crystalline regions: a large and broad melting peak around 80 ° C that correlates with EVA and LLDPE co-monomer, and a smaller and sharper peak at around 120 ° C corresponding to LLDPE. Thermal conductivity from this measurement was reported.
Thermal conductivity is the magnitude of heat transmitted, due to unit temperature gradient, under unit conditions in a normal direction to a unit area surface. It is measured as heat flow rate (watts) over distance (meter) and temperature gradient (Kelvin), and is reported in unit watts (meter * Kelvin), simplified as k (w / m * K). Table 5 lists the thermal conductivity on sealant films containing LLDPE only, OC only, CC only, and different OC / CC combinations. Sealant formulations with LLDPE only, OC only, or CC only had thermal conductivity in the range of 0.34 to 0.40 w / m * K. When both OC and CC are present in the sealant formulation, the thermal conductivity increased significantly to a range of 0.80 to 1.00 w / m * K. This takes into account for around more than 100% improvement. It was clearly demonstrated that the combination of OC with CC provides a synergistic effect, and therefore improves the much higher thermal conductivity compared to sealant containing only CC or OC.
Table 5: Thermal conductivity measured by DSC
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MEXICAN BISTITUTC
OF THE INDUSTRIAL PROPERTY
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<td></td><td>k (w / m * K)</td>
<td>LLDPE only</td><td> 0.40</td>
<td>OC only</td><td> 0.40</td>
<td>CC only</td><td> 0.34</td>
<td>Movie 2</td><td> 0.80</td>
<td>Movie 3</td><td> 0.82</td>
<td>Movie 7</td><td> 1.00</td>
<td>Movie 8</td><td> 0.83</td>
Although embodiments of the invention have been illustrated and described, these embodiments are not intended to illustrate and describe all possible forms of the invention. Instead, the words used in the specification are words of description rather than limitation, and it is understood that various changes can be made without departing from the spirit and scope of the invention.
Contents52
88 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49 Sheet 50 Sheet 51 Sheet 52 Sheet 53 Sheet 54 Sheet 55 Sheet 56 Sheet 57 Sheet 58 Sheet 59 Sheet 60 Sheet 61 Sheet 62 Sheet 63 Sheet 64 Sheet 65 Sheet 66 Sheet 67 Sheet 68 Sheet 69 Sheet 70 Sheet 71 Sheet 72 Sheet 73 Sheet 74 Sheet 75 Sheet 76 Sheet 77 Sheet 78 Sheet 79 Sheet 80 Sheet 81 Sheet 82 Sheet 83 Sheet 84 Sheet 85 Sheet 86 Sheet 87 Sheet 88
22 members in 12 offices
Priority claims9
| Document | Office | Kind | Date |
|---|---|---|---|
| 12983732 | United States of America | – | |
| 98373211 | United States of America | A | |
| 98373211 | United States of America | A | |
| 2012020023 | United States of America | W | |
| 2012020023 | United States of America | W | |
| 12983732 | – | – | – |
| PCTUS2012020023 | – | – | – |
| US20110983732 | – | – | – |
| WO2012US20023 | – | – | – |
Members22
| Document | Office | Kind | |
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| US2012168340A1 | United States of America | A1 | |
| CA2823384A1 | Canada | A1 | |
| WO2012094281A2 | World Intellectual Property Organization (WIPO) | A2 | |
| US2012207997A1 | United States of America | A1 | |
| WO2012094281A3 | World Intellectual Property Organization (WIPO) | A3 | |
| AR084761A1 | Argentina | A1 | |
| AU2012204555A1 | Australia | A1 | |
| WO2013158731A1 | World Intellectual Property Organization (WIPO) | A1 | |
| EP2661368A2 | European Patent Office (EPO) | A2 | |
| CN103442886A | China | A | |
| JP2014507340A | Japan | A | |
| RU2013132865A | Russian Federation | A | |
| US8993080B2 | United States of America | B2 | |
| CN103442886B | China | B | |
| AU2012204555B2 | Australia | B2 | |
| RU2581085C2 | Russian Federation | C2 | |
| JP5952303B2 | Japan | B2 | |
| US9533472B2 | United States of America | B2 | |
| EP2661368B1 | European Patent Office (EPO) | B1 | |
| MX355447BThis record | Mexico | B | |
| PL2661368T3 | Poland | T3 | |
| BR112013017089A2 | Brazil | A2 |
1 legal event, as the office reported them to INPADOC
Events
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|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 355447
- Publication, DOCDB
- 355447
- Publication, EPODOC
- MX355447
- Application
- 2013007802
- Application, DOCDB
- 2013007802
- Application, EPODOC
- MX20130007802
Titles
- Spanish
- SELLADOR DESPRENDIBLE CONTENIENDO MEZCLAS FÍSICAS DE COMPUESTO TERMOPLÁSTICO PARA APLICACIONES DE EMPAQUETADURA.
Classification
- CPC, 14
- B32B27/08
- B32B7/06
- B32B27/20
- B32B2264/10
- B32B2264/104
- B32B2264/12
- B32B2307/302
- B32B2439/40
- B32B2439/46
- B65D75/5855
- B32B2307/31
- B65D77/2032
- B65D2575/3245
- Y10T428/1352
- IPC, 6
- B32B7 06
- B29D22 00
- B32B27 08
- B32B27 20
- B32B27 30
- B32B27 32