CN104718075A - Polymer films containing microspheres - Google Patents
Polymer films containing microspheres Download PDFInfo
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- CN104718075A CN104718075A CN201280076287.5A CN201280076287A CN104718075A CN 104718075 A CN104718075 A CN 104718075A CN 201280076287 A CN201280076287 A CN 201280076287A CN 104718075 A CN104718075 A CN 104718075A
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- microsphere
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- polypropylene
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/14—Details; Accessories therefor
- A61J1/20—Arrangements for transferring or mixing fluids, e.g. from vial to syringe
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/14—Details; Accessories therefor
- A61J1/20—Arrangements for transferring or mixing fluids, e.g. from vial to syringe
- A61J1/2093—Containers having several compartments for products to be mixed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/14—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/14—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces
- B32B5/145—Variation across the thickness of the layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/101—Glass
Abstract
Polymer films having hollow microspheres to simultaneously reduce the coefficient of friction and residue on ignition, and methods of making films and containers from the films. In a general embodiment, the present disclosure provides a film including at least one layer having hollow microspheres mixed within the layer. The microspheres can be in a concentration ranging from about 250 ppm to about 750 ppm within the layer.
Description
Background technology
The present invention relates generally to polymer film.Particularly get on very well, the present invention relates to and there is the slip/anti-adhesion characteristic of improvement and the polymer film of low residue on ignition.
Multilayer film is widely used in multiple industry, such as, comprise for supplying in food or the wrapping container of medical science solution.Extruding film forming multilayer one institute want characteristic be its toughness or use or transport in can damage-resistant.Another want characteristic for intensity manufacture stripping formula strip of paper used for sealing and the permanent strip of paper used for sealing of permanent closure container can be wanted with the institute being suitable for applying.Another want characteristic for providing the barrier of the such as gas of oxygen, carbon dioxide or steam to maintain the stability of contained solution.
Known multilayer film can be made up of vistanex, and it has and makes its unworkable great friction coefficient in the fabrication process.Slip agents overcomes the natural gum viscosity of vistanex, and therefore it can smoothly move by transforming and packaging facilities.Current use silica is as the slip agents in the layer of plastic foil or antitack agent.But the existence of silica may cause residue on ignition to exceed comprising the pharmacopeia limit of many countries of Japan, Korea S and China.
Summary of the invention
The present invention relates to the polymer film with microsphere and the method preparing film and the container be made up of described film.In a generic embodiment, the invention provides a kind of film, it comprises the layer that one or more is mixed with hollow microspheres or " bubble " in layer.For example, microsphere can roughly Homogeneous phase mixing in appointing in one or more part of layer.The concentration range of microsphere in described layer can be about 250ppm to about 3000ppm.
In one embodiment, microsphere is made up of soda lime Pyrex.Microsphere can have the diameter within the scope of about 10 μm to about 300 μm.Microsphere can have the density within the scope of about 0.1g/cc to about 1.2g/cc in addition.
In one embodiment, the rete with microsphere comprises the silica be mixed in described layer in addition.The concentration range of silica in described layer can be about 1000ppm to about 2000ppm.
In another embodiment, the invention provides the multilayer film comprising top layer, barrier layer and stripping formula sealant.Top layer and stripping formula sealant are attached to core layer in the opposition side of barrier layer.Top layer comprises with at least one in stripping formula sealant the hollow glass microspheres be mixed in layer.
In one embodiment, top layer comprises such as following component: polypropylene random copolymer, polypropylene homopolymer, nylon (nylon), styrene-ethylene-butylene-styrene block copolymer, copolyester ether block copolymer or its combination.Barrier layer can comprise such as following component: polyamide 6, polyamide 6,6/6,10 copolymers, amorphous polyamide or its combination.
In one embodiment, shell formula sealant and comprise such as following material: homophase polymers, matrix gathering compound or its combination.For example, the admixture that formula sealant can comprise polypropylene and styrene-ethylene-butylene-styrene block copolymer is shelled.In another example, shell formula sealant and can comprise another polyolefin with different melting points, such as the second polypropylene or LLDPE.
In one embodiment, film comprises and makes at least one in top layer and stripping formula sealant be attached to one or more articulamentum of barrier layer.Articulamentum can comprise such as following component: maleinization LLDPE, maleinization polypropylene homopolymer, maleinization polypropylene copolymer or its combination.
In one embodiment, core layer to be positioned in barrier layer and top layer and the formula of stripping sealant between at least one.Core layer can comprise such as following component: the polypropylene of polypropylene homopolymer, Propylene-ethylene random copolymer, syndiotactic propylene-ethylene copolymer, polypropylene elastomer, the elastomer based on propylene, the elastomer based on ethene, styrene-ethylene-butylene-styrene block copolymer, ethylene-propylene rubber upgrading or its combination.
In an alternative embodiment, the invention provides multi-chamber container, it comprises the main body defined by film.Described main body comprises at least two chambers separated by peelable seals, and wherein film comprises the layer that at least one is mixed with microsphere in layer.
In another embodiment, the invention provides a kind of container, it comprise along at least one share enclose the first side wall and the second sidewall that edge is sealed to define fluid chamber.First and/or second sidewall comprises multilayer film, and it comprises top layer, the first articulamentum, the barrier layer being close to the first articulamentum arrangement, the second articulamentum being close to barrier layer arrangement, core layer and sealant.Top layer and/or sealant comprise the glass microspheres be mixed in layer.
In another embodiment, the invention provides the method manufacturing film.Described method comprise by microsphere mixing be dispersed throughout in one or more polymer.For example, microsphere can roughly be dispersed in polymer.Described method comprises in addition by extruded polymer film forming.Film can form container subsequently.
Advantage of the present invention is for providing the film of the sliding properties with improvement.
Another advantage of the present invention is for providing the film of the anti-adhesion characteristic with improvement.
Another advantage of the present invention has the improvement film of acceptable low residue on ignition for providing.
Another advantage of the present invention manufactures improving one's methods of container for providing.
Further feature and advantage are described in herein, and will according to following detailed description of the invention and obviously graphic.
Accompanying drawing explanation
Fig. 1 is the viewgraph of cross-section of monofilm in one embodiment of the present of invention.
Fig. 2 is the viewgraph of cross-section of five tunics in one embodiment of the present of invention.
Fig. 3 is the viewgraph of cross-section of six tunics in one embodiment of the present of invention.
Fig. 4 is the view of the container be made up of the film in one embodiment of the present of invention.
Fig. 5 is the view of the multi-chamber container be made up of the film in one embodiment of the present of invention.
Detailed description of the invention
The present invention relates to the polymer film with microsphere and the method preparing film and the container be made up of described film.In a generic embodiment, the invention provides a kind of film, it comprises the layer that at least one is mixed with hollow microspheres in layer.The invention provides the monofilm and multilayer film that are applicable to packaging applications.Film in the embodiment of the present invention has slip and the anti-adhesion characteristic of improvement, keeps toughness and/or stripping formula sealability simultaneously.
In the generic embodiment that Fig. 1 illustrates, the invention provides film 10, it is included in layer the layer being mixed with microsphere.Microsphere can be uniformly distributed in appointing in one or more part of layer.Microsphere can use any applicable technology (such as extrusion technique) to add/be mixed in the layer of film 10.Should be appreciated that, the film by extruding with the continuous sublayer of same material makes microsphere only be distributed in the selected part of another homosphere, and one of described sublayer is containing microsphere and one or more sublayer does not have any microsphere.
Layer can comprise the microsphere of any suitable amount.For example, the concentration range of microsphere in layer can be about 250ppm to about 3000ppm, and such as about 250ppm is to about 700ppm, about 350ppm to about 650ppm, about 400ppm to about 600ppm or about 450ppm to about 550ppm.The example of indivedual values of microsphere concentration is about 250ppm, 300ppm, 350ppm, 400ppm, 450ppm, 500ppm, 550ppm, 600ppm, 650ppm, 700ppm, 750ppm, 1000ppm, 2000ppm, 3000ppm etc.
In another embodiment, the layer with microsphere comprises the silica be mixed in described layer in addition.For example, silica can be the amorphous synthetic silica with cubic shaped.Silica can have the density within the scope of about 2.2g/cc to about 2.3g/cc.Silica also can have the average diameter of about 4 μm to about 5 μm.
Silica can any suitable amount be present in described layer.For example, the concentration range of silica in layer can be 1000ppm to about 2000ppm, and all 1100ppm are according to appointment to about 1900ppm, about 1200ppm to about 1800ppm, about 1300ppm to about 1700ppm or about 1400ppm to about 1600ppm.The example of indivedual values of silica concentration is about 1000ppm, 1100ppm, 1300ppm, 1400ppm, 1500ppm, 1600ppm, 1700ppm, 1800ppm, 1900ppm, 2000ppm etc.
Should be understood that indivedual microsphere concentration value and indivedual silica concentration value also can be the definition of the limit of scope.For example, the concentration disclosing 300ppm and 450ppm also should be considered as the scope disclosing 300ppm to 450ppm.This is also applicable to any combination of the specific value mentioned in the present invention.
In one embodiment, microsphere is hollow.Microsphere can be made up of soda lime Pyrex.Microsphere also can be made up of pottery.The applicable example of microsphere comprises iM30K (18 micron average diameter, density 0.60g/cc, crushing strength 28000psi) from 3M and K46 (40 micron average diameter, density 0.46g/cc, crushing strength 6000psi) microsphere.Microsphere can have any applicable average diameter or width.For example, the average diameter range of microsphere can be about 10 μm to about 300 μm, such as about 50 μm to about 250 μm, or about 100 μm to about 200 μm.The example of indivedual values of the average diameter of microsphere is about 10 μm, 25 μm, 50 μm, 75 μm, 100 μm, 125 μm, 150 μm, 175 μm, 200 μm, 225 μm, 250 μm, 275 μm, 300 μm etc.In addition, can the microsphere of fusion different-diameter in layer.
Microsphere also can have any applicable density.For example, the grain density scope of microsphere can be about 0.1g/cc to about 1.2g/cc, and such as about 0.2g/cc is to about 1.10g/cc, about 0.3g/cc to about 0.9g/cc, about 0.4g/cc to about 0.8g/cc or about 0.5g/cc to about 0.7g/cc.The example of indivedual values of microsphere density is about 0.1g/cc, 0.15g/cc, 0.2g/cc, 0.25g/cc, 0.3g/cc, 0.35g/cc, 0.4g/cc, 0.45g/cc, 0.5g/cc, 0.55g/cc, 0.6g/cc, 0.65g/cc, 0.7g/cc, 0.75g/cc, 0.8g/cc, 0.85g/cc, 0.9g/cc, 0.95g/cc, 1g/cc, 1.05g/cc, 1.1g/cc, 1.15g/cc, 1.2g/cc etc.
In another embodiment, the layer with microsphere comprises the nano material be mixed in layer in addition.Nano material can be such as nanotube and nanoclay.Size is comprised significantly lower than the general about particle of common-size of several microns of grinding mineral equivalent used at present in polymer film according to the nano material of the embodiment of the present invention.According to one embodiment of present invention, the average-size of nano material is in about 10 to about 500 nanometer range.
In another embodiment (illustrated in fig. 2), the invention provides five tunics with top layer 20, barrier layer 24 and stripping formula sealant 28.Top layer 20 and/or stripping formula sealant 28 can comprise the microsphere be scattered in layer of any suitable amount.Top layer 20 and stripping formula sealant 28 can directly or indirectly be attached to barrier layer 24 in the opposition side of barrier layer 24.
Top layer 20, barrier layer 24 and stripping formula sealant 28 can have any applicable thickness independently of one another.For example, top layer 20 can have the thickness within the scope of about 25 μm to about 75 μm.For example, barrier layer 24 can have the thickness within the scope of about 10 μm to about 50 μm.Stripping formula sealant 28 can have the thickness within the scope of about 50 μm to about 150 μm.
In each layer microsphere varying concentrations and determined by certain layer.For example, top layer 20 can be and is less than about 25 μm of thick and microsphere concentration had within the scope of about 1000ppm to about 2000ppm.
Random copolymer polypropylene, homopolymer polypropylene, nylon, styrene-ethylene-butylene-styrene block copolymer, polyester, copolyester ether or its combination can be contained in top layer 20.Barrier layer 24 can contain one or more polyamide (" PA ") (nylon), such as polyamide 6, polyamide 6,6/6,10 copolymers, amorphous polyamide or its combination.Or barrier layer 24 can contain other barrier material, such as ethylene-vinyl alcohol copolymer (" EVOH ").EVOH barrier layer be particularly suited for wherein container by the application without undergoing moist heat sterilization.In one embodiment, film can containing the evoh layer be clipped between aramid layer.
Applicable polypropylene random copolymer comprise flint mountain resource company (Flint Hills Resources) with HUNTSMAN trade mark, Borealis AG (Borealis) with BORMED or BORPURE trade mark and Total SA (TOTAL) with PPM trademark Soynatto person.Applicable polypropylene homopolymer comprise flint mountain resource company with
trademark Soynatto person.Applicable nylon comprise EMS with
with
trademark Soynatto person.Applicable styrene-ethylene-butylene-styrene block copolymer comprises Ke Teng Polymer Company (Kraton Polymers) with KRATON trademark Soynatto person.
Sealant 28 can be homophase polymers or matrix-phase polymer system.As described in the EP0875231 that is incorporated herein by reference, applicable homophase polymers comprises polyolefin, and more preferably polypropylene, and most preferably propylene and ethylene copolymer.
Be applicable to matrix-phase polymer system and will have at least two kinds of components.Two kinds of components can be blended together or can the manufacture of two benches reactor method.Usually, two kinds of components will have different melting points.Be that in the situation of amorphous component, its glass transition temperature is by the fusing point lower than other component in a kind of component.The example being applicable to matrix-phase polymer system comprises the component of polyolefin homopolymer or copolymer and the second component of styrene and hydrocarbon copolymer.Another applicable matrix phase system comprises polyolefinic admixture, such as polypropylene and polyethylene, or there is the polypropylene (crystallization) of high isotactic index and there is the polypropylene (amorphous) of lower isotactic index, or polypropylene homopolymer and propylene and alpha olefin copolymer.The limiting examples being applicable to matrix-phase polymer system is described in United States Patent (USP) the 7th, in 678, No. 097.
Applicable polyolefin comprises by containing 2 to 20 carbon atoms and the more preferably homopolymers that obtains of the alpha-olefine polymerizing of 2 to 10 carbon atoms and copolymer.Therefore, applicable polyolefin comprises polymer and the copolymer of propylene, ethene, butene-1, amylene-1,4-methyl-1-pentene, hexene-1, heptene-1, octene-1, nonylene-1 and decylene-1.Polyolefin most preferably is the homopolymers of propylene or copolymer or poly homopolymers or copolymer.
Polyacrylic applicable homopolymers can have the stereochemistry of amorphous, isotactic, a rule, non-rule, half isotactic or stereoblock.At one of the present invention, more preferably in form, polypropylene will have about 20 joule/gram to about 220 joule/gram, more preferably from about 60 joule/gram to about 160 joule/gram and most preferably from about 80 joule/gram to the low heat of fusion of about 130 joule/gram.In a preferred form of the present invention, also need polypropylene homopolymer to have and be less than about 165 DEG C and more preferably from about 130 DEG C to about 160 DEG C, the most preferably from about melting temperature of 140 DEG C to about 150 DEG C.In a preferred form of the present invention, single site catalyst is used to obtain polypropylene homopolymer.
Be applicable to propylene copolymer to obtain with the alpha-olefin polymerization with 2 to 20 carbon atoms by making propylene monomer.At one more preferably in form of the present invention, propylene and ethene with about 1 % by weight to about 20 % by weight of copolymer weight, more preferably from about 1 % by weight to about 10 % by weight and most preferably 2 % by weight to about 5 % by weight amount copolymerization.Propylene and ethylene copolymer can be random or block copolymer.
Also can use the admixture of polypropylene and alpha olefin copolymer, wherein the carbon number of the alpha-olefin of propylene copolymer is variable.For example, the admixture of propylene and alpha olefin copolymer is contained in the present invention, and one of them copolymer has 2 carbon alpha-olefins and another copolymer has 4 carbon alpha-olefins.Also 2 to 20 carbon can be used and any combination of the more preferably alpha-olefin of 2 to 8 carbon.Therefore, the admixture of propylene and alpha olefin copolymer is contained in the present invention, and wherein the first and second alpha-olefins have following combination of carbon numbers: 2 and 6,2 and 8, and 4 and 6,4 and 8.Also be encompassed in admixture and use two or more polypropylene and alpha olefin copolymer.Alloy catalytic program can be used to obtain and to be applicable to polymer.Applicable Alathon comprises density and is greater than 0.915g/cc person and comprises low density polyethylene (LDPE) (" LDPE "), Medium Density Polyethylene (" MDPE ") and high density polyethylene (HDPE) (" HDPE ").
By making vinyl monomer and there are 3 to 20 carbon, more preferably 3-10 carbon and most preferably the alpha-olefine polymerizing of 4 to 8 carbon obtain applicable ethylene copolymer.Also need ethylene copolymer to have to be less than about 0.915g/cc measured by ASTM D-792 and be more preferably less than about 0.910g/cc and be even more preferably less than the density of about 0.900g/cc.Described polymer is commonly referred to very low density polyethylene (VLDPE) or ultra-low density polyethylene (ULDPE).Ethyleneα-olefincopolymer preferably uses single site catalyst and even more preferably metallocene catalytic system manufacture.Think that single site catalyst has catalyst position that is spatially single and equivalence in electronics, contrary with known Qi Gena-Natta (Ziegler-Natta) the type catalyst with mixed catalyst site.The ethylene ' alpha '-olefin of described single site catalysis by the Dow Chemical Company (Dow) with trade mark
duPont Dow Elastomers (DuPont Dow) is with trade mark
and Exxon Corporation (Exxon) is with trade mark
sell.These copolymers should be called m-ULDPE in this article sometimes.
Applicable ethylene copolymer also comprises the EVAc that alkyl acrylate copolymer that ethene and acrylic acid low-carbon alkyl ester copolymer, ethene and low-carbon alkyl replace and vinyl acetate content are about 8 % by weight to about 40 % by weight of copolymer.Term " acrylic acid low-carbon alkyl " refers to the comonomer with the chemical formula described in Fig. 1:
R group refers to the alkyl with 1 to 17 carbon.Therefore, term " acrylic acid low-carbon alkyl " includes, but is not limited to methyl acrylate, ethyl acrylate, butyl acrylate etc.
Term " alkyl acrylate that alkyl replaces " refers to the comonomer with the chemical formula described in Fig. 2:
R
1and R
2for there is the alkyl of 1-17 carbon and same carbon number can being had or there is different carbon number.Therefore, term " alkyl acrylate that alkyl replaces " includes, but is not limited to methyl methacrylate, EMA, ethyl methyl acrylate, ethyl acrylate, butyl methacrylate, ethyl propylene acid butyl ester etc.
The polybutadiene be applicable to comprises 1,2-and the Isosorbide-5-Nitrae-addition compound product (it should be referred to as polybutadiene) of 1,3-butadiene.At one more preferably in form of the present invention, described polymer is 1, the 2-addition compound product (it should be called 1,2 polybutadiene) of 1,3 butadiene.At one even more preferably in form of the present invention, the polymer paid close attention to be between rule 1,2-polybutadiene and even more preferably low-crystallinity, rule 1,2 polybutadiene.In a preferred form of the present invention, low-crystallinity, a rule 1, the degree of crystallinity that 2 polybutadiene are less than 50% by having, be more preferably less than about 45%, be even more preferably less than about 40%, degree of crystallinity even more preferably will be about 13% to about 40%, and most preferably from about 15% to about 30%.In a preferred form of the present invention, low-crystallinity, rule 1,2 polybutadiene will have the melting temperature measuring about 70 DEG C to about 120 DEG C according to ASTM D 3418.Applicable resin comprises JSR (Japan SYnthetic Rubber Co. Ltd (Japan Synthetic Rubber)) with brand name: JSR RB 810, JSR RB 820 and JSR RB 830 seller.
Applicable polyester comprises the polycondensation product of dicarboxylic acids or polycarboxylic acids and dihydroxy alcohol or poly-hydroxyl alcohol or alkylene oxide.In a kind of preferred form of the present invention, polyester is polyester ether.Be applicable to polyester ether react acquisition by 1,4-CHDM, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and polytetramethylene glycol ether and be commonly referred to as PCCE.Be applicable to PCCE to be sold with trade mark ECDEL by Yi Shi Man (Eastman).Applicable polyester comprises polyester elastomer in addition, and it is the block copolymer of the scleroma crystalline region section of polybutylene terephthalate and second section of soft (amorphous) PTMEG.Described polyester elastomer by DuPont Chemicals (DuPont Chemical Company) with trade mark
sell.
Applicable polyamide comprises the ring-opening reaction producer by the lactams with 4-12 carbon.Therefore this group polyamide comprises nylon 6, nylon 10 and nylon 12.The polyamide that the fatty polyamide of condensation reaction generation of the fatty polyamide that the condensation reaction that acceptable polyamide also comprises the diamines of carbon number in 2 to 13 scopes produces, the diacid of carbon number in 2 to 13 scopes, the condensation reaction of dimer fatty acid produce, and the copolymer containing acid amides.Therefore, the fatty polyamide be applicable to comprises such as nylon66 fiber, nylon 6,10 and dimer fatty acid polyamide.
Applicable styrene and hydrocarbon copolymer comprise styrene and the multiple styrene (comprising the styrene of alkyl replacement and the styrene of halogen substiuted) be substituted.Alkyl can contain 1 to about 6 carbon atoms.The cinnamic particular instance be substituted comprise AMS, Beta-methyl styrene, vinyltoluene, 3-methyl styrene, 4-methyl styrene, 4-isopropyl styrene, 2,4-DMS, chloro styrene, to chlorostyrene, adjacent bromstyrol, the chloro-4-methyl styrene of 2-etc.Styrene most preferably.
Cinnamic hydrocarbon part and hydrocarbon copolymer comprise conjugated diene.Available conjugated diene is for containing 4 to about 10 carbon atoms and more generally 4 to 6 atoms.Example comprises 1,3-butadiene, 2-methyl isophthalic acid, 3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, chlorobutadiene, 1,3-pentadiene, 1,3-hexadiene etc.Also the mixture of these conjugated dienes can be used, the mixture of such as butadiene and isoprene.Preferred conjugated diene is isoprene and 1,3-butadiene.
Styrene and hydrocarbon copolymer can be the block copolymer comprising diblock, three blocks, many blocks and starblock.The particular instance of diblock copolymer comprises styrene-butadiene, styrene-isoprene, and its hydrogenated derivatives.The example of triblock polymer comprises s-B-S, styrene-isoprene-phenylethene, AMS-butadiene-AMS and AMS-isoprene-AMS and its hydrogenated derivatives.
The selective hydration of above-mentioned block copolymer is undertaken by multiple well-known method, and the catalyst being included in such as Buddhist nun's Ruan nickel (Raney nickel), noble metal (such as platinum, palladium etc.) and soluble transition metal catalyst exists lower hydrogenation.Spendable applicable hydrogenization method be wherein to be dissolved in inert hydrocarbon diluent (such as cyclohexane) containing the polymer of diene or copolymer and by the presence of a soluble hydrogenation catalyst with the method for H-H reaction and hydrogenation.Described program description is in United States Patent (USP) the 3rd, and 113, No. 986 and the 4th, 226, No. 952, its disclosure is incorporated herein by reference.
The hydrogenated block copolymer of particularly suitable is the hydrogenated block copolymer of styrene-isoprene-phenylethene, such as styrene-(ethylene/propene)-styrenic block polymers.When polystyrene-polybutadiene-polystyrene block copolymer is through hydrogenation, products therefrom is similar to the regular copolymer block (" EB ") of ethene and 1-butylene.As described above, when adopted conjugated diene is isoprene, gained hydrogenated products is similar to the regular copolymer block (" EP ") of ethene and propylene.An example of commercially available selective hydration copolymer is
g-1652, it is Hydrogenated SBS three block comprising 30% styrene end block, and mid-block equivalent is the copolymer of ethene and 1-butylene.This hydrogenated block copolymer is commonly referred to SEBS.Other applicable SEBS or SIS copolymer by Larry, storehouse company (Kurrarry) with trade mark
with
sell.Also may need to use styrene and the hydrocarbon block copolymer of grafting upgrading by grafting α, β-unsaturated monocarboxylic or dicarboxylic acids reagent on selective hydration block copolymer mentioned above.
With the block copolymer of α, β-unsaturated monocarboxylic or the grafting conjugated diene of dicarboxylic acids reagent and vinyl aromatic compounds.Carboxylic acid reagent comprises can graft to carboxylic acid itself on selective hydration block copolymer and its functional derivatives (such as acid anhydride, acid imide, slaine, ester etc.).With the total weight of block copolymer and carboxylic acid reagent, graft polymers generally will containing having an appointment 0.1 % by weight to about 20 % by weight, and preferred about 0.1 % by weight to about 10 % by weight grafted carboxylic acid.Be suitable for monocarboxylic particular instance and comprise acrylic acid, methacrylic acid, cinnamic acid, butenoic acid, acrylic anhydride, PAA, calcium acrylate and Magnesium Acrylate Prepared etc.Dicarboxylic acids and its example being suitable for derivative comprise maleic acid, maleic anhydride, fumaric acid, mesaconic acid, itaconic acid, citraconic acid, itaconic anhydride, citraconic anhydride, monomethyl cis-butenedioic acid, maleic acid list sodium etc.Styrene and hydrocarbon block copolymer can oily upgradings, such as by Shell Chemical Co (Shell Chemical Company) with name of product
the SEBS of the oily upgrading that G2705 sells.
As further shown in Figure 2, multilayer film can comprise one or more articulamentum 22 and 26 for top layer 20 and/or sealant 28 being attached to barrier layer 24.Articulamentum 22 and 26 can contain any applicable sticky material, and such as maleinization LLDPE, maleinization polypropylene homopolymer, maleinization polypropylene copolymer, maleinization are based on polyacrylic TPO or its combination.
In alternate embodiment illustrated in figure 3, the invention provides the film comprising top layer 30, barrier layer 36 and sealant 40.Top layer 30 and sealant 40 can be attached to barrier layer 36 on the opposition side of barrier layer 36.Top layer 30 can contain polypropylene homopolymer, polypropylene random copolymer, based on polyacrylic TPO, polyamide (nylon), styrene-ethylene-butylene-styrene block copolymer, copolyester ether block copolymer or its combination.
As further shown in Figure 3, film can comprise the core layer 32 be positioned between top layer 30 and barrier layer 36 in addition.Core layer 32 can contain Propylene-ethylene random copolymer, syndiotactic propylene-ethylene copolymer, polypropylene elastomer, polypropylene homopolymer, the elastomer based on propylene, the elastomer based on ethene, styrene-ethylene-butylene-styrene block copolymer, the polypropylene of ethylene-propylene rubber upgrading or its combination.Applicable propylene-ethylene copolymers comprise Exxon Corporation (Exxon) with VISTAMAXX trade mark, the Dow Chemical Company (Dow) with VERSIFY trade mark, Total SA (TOTAL) with ATOFINA trade mark and company of Basel (Basell) with PROFAX trademark Soynatto person.Film can comprise one or more articulamentum 34 and 38 that top layer 30, stripping formula sealant 40, barrier layer 36 and/or core layer 34 are attached to each other in addition.
Film in the embodiment of the present invention can be used for preparing any fitted vessel, such as, for holding the material of such as medicine or medical cpds or solution.In the embodiment illustrated in figure 4, the invention provides container 50, it comprises the first side wall 52 and the second sidewall (not shown) relative with the first side wall, and two sidewalls peripherally seam 54 are sealed to define fluid chamber.Container 50 can comprise one or more port pipe 56 and 58, and it is for filling the content with emptying receptacles 50.
One or more sidewall any of container 50 can one manufacture in monofilm by mentioned earlier or multilayer film.Should also be clear that container 50 can sealing be formed in its openend by the tubular film extruded.In this case, peripheral seam 54 can be made up of two of a pipe opposite end seam.Container 50 can be configured, and makes seam in the top of container and bottom or along its vertical side.
In the alternate embodiment shown in Fig. 5, the invention provides multi-chamber container 70, it comprises the main body 72 defined by film.Multi-chamber container 70 comprises two chambers 74 and 76.Should be appreciated that, in alternative embodiments, in container, two or more chamber can be provided.Chamber 74 and 76 is the separately storages being designed for material and/or solution.
In the illustrated embodiment, any part of container 70 is made by film, and described film such as above-detailed comprises the layer that one or more is mixed with microsphere in layer.Container 70 can be made up of two panels film, and described film such as forms permanent strip of paper used for sealing along its edge heat seal.In the illustrated embodiment, two panels film is used.Described diaphragm seals along the periphery of container 70 at edge 80,82,84 and 86 place.Between diaphragm, provide peelable seals 88 to form chamber 74 and 76.Certainly, if provide additional chambers, then extra peelable seals can be provided.
Container 70 and peelable seals 88 can be built by the film with stripping formula sealant according to embodiments of the invention.Stripping formula sealant can allow to form peelable seals and permanent strip of paper used for sealing.Therefore, permanent side strip of paper used for sealing 80,82,84 and 86 and peelable seals 88 can be formed by the same layer of film.
As illustrated in fig. 5, container 70 can comprise one or more port 90,92,94 and 96 in addition.Port 90,92,94 and 96 provides and being communicated with of chamber 74 and 76 inside, but may be positioned at any appropriate location on container 70.These ports allow to chamber 74 and 76 interpolation fluid or from chamber 74 and 76 removing fluids.Port 90,92,94 and 96 also can comprise the film (not shown) punctured by the sleeve pipe of such as administration device or furcella.
Should be appreciated that, one or many person in described port can the form of molded structure provide, and described structure has and to be particularly suited for and container seals (in described situation, port structure is sometimes referred to as " hopper ") or directly and the surface that seals of wall between thin slice.Should also be clear that described port can comprise valve or similar enclosed construction but not simple film.The example of described alternative port structure comprises United States Patent (USP) the 6th, and that describes in the medicine port described in 994, No. 699 and No. 2005/0083132nd, U.S. Patent Publication case multiplely accesses port, and it is incorporated herein by reference separately.
Depending on the method for the manufacture of container, filling port may be unnecessary.For example, if container is for being manufactured by continuous plastic film roll, then can be longitudinal folding by film, form the first permanent strip of paper used for sealing, fill the first compartment with solution, then form peelable seals, fill the second compartment, form permanent strip of paper used for sealing etc.
Example
For example and not as restriction, following instance is the explanation of multiple embodiment of the present invention.
Example 1
Augment with glass (hollow) microsphere or replace the silica as film additive, to reduce residue on ignition, keeping the brilliance slip/anti-adhesion characteristic of film simultaneously.Using some characteristics with the film of glass microspheres with only there is the film of silica as slip agents compare.The feature of microsphere and silica is shown in table 1.
Table 1
| iM30K | Silica (Borealis AG's data) | |
| Composition | Soda lime borosilicate | Amorphous synthetic silica |
| Shape | There is the glass hollow ball of thin-walled | Cube |
| Real density | 0.60g/cc | 2.2-2.3μm |
| Average diameter | 18μm | 4-5μm |
Extrude and the different compound characterized containing 500ppm 3M iM30K glass microspheres (replacing 1800ppm silica) and film.
Compound describes:
-compound 1A=polypropylene (" PP ") (Borealis AG RE906CF)+500ppm 3M iM30K glass microspheres
-compound 1B=contains the polypropylene (Borealis AG RE216CF) of 1800ppm silica
-compound 2A=shells polypropylene (Borealis AG RE906CF)+500ppm 3MiM30K glass microspheres in formula strip of paper used for sealing
-compound 2B=Wittenburg Cawiton PR4851A ternary compound
Residue on ignition (" RoI ") result (according to Pharmacopoeia Coreana method, the 8th edition) in units of wt%:
-compound 1A:0.08%
-compound 1B:0.25%
-compound 2A:0.06%
-compound 2B:0.14%
Film
Table 2: film describes (casting extruding)
Coefficient of friction result (according to Baxter proprietary method):
Top layer/top layer:
-No. 1 film: 0.48-0.52
-No. 2 films: 0.48
Strip of paper used for sealing/strip of paper used for sealing:
-No. 1 film: 0.61-0.65
-No. 2 films: 0.60
RoI result (according to Pharmacopoeia Coreana method, the 8th edition) in units of wt%:
-No. 1 film: 0.15%
-No. 2 films: 0.06%
Conclusion:
No. 2 films with microsphere and No. 1 film without microsphere have similar friction/sliding characteristic, and RoI reduces 2.5 times.
Example 2
Prepare a series of polypropylene screen to prove the impact on film coefficient of friction (CoF) and turbidity of the different size of microsphere and concentration.In film 1-9, the matrix of each is BORMED RD804CF, namely available from the medical science film grade polypropylene random copolymer of Borealis AG (BorealisAG); The matrix of film 19 is Borealis AG RE216CF.Following table describes film and gained coefficient of friction.
The concentration of these data reflection hollow microspheres provides acceptable turbidity and provides almost equal coefficient of friction to reduce with much bigger solid silica concentration, and additive quality significantly reduces the expection essence minimizing of caused residue on ignition.
Example 3
Prepare another series polypropylenes/polyethylene/thermoplastic elastomer films to prove the impact of the microsphere of different size and concentration on film coefficient of friction (CoF).The matrix of film 20 is for comprising the admixture of 60% polypropylene random copolymer (Borealis AG RD804CF), 15% LLDPE (Stamylex 1026F) and 25% styrene-ethylene-butylene-styrene block copolymer (SEBS).In film 10-18, the matrix of each is identical with the matrix of film 20, but polypropylene random copolymer is Borealis AG RE216CF.Following table describes film and gained turbidity and coefficient of friction.
The concentration of these data reflection hollow microspheres provides acceptable turbidity and provides almost equal coefficient of friction to reduce with much bigger solid silica concentration, and significantly reduces the expection essence minimizing of caused residue on ignition because of institute's adding material quality.
Should be understood that one of ordinary skill in the art easily know multiple change and the amendment of currently preferred embodiment as herein described by showing.Described change and amendment can be made and do not deviate from spirit and the category of present subject matter, and not reducing its expection advantage.Therefore wish that following claims contains described change and amendment.
Claims (36)
1. a polymer film, it comprises the layer that at least one is mixed with hollow microspheres in layer.
2. film according to claim 1, wherein said microsphere is present in described layer with the concentration within the scope of about 250ppm to about 3000ppm.
3. film according to claim 1, the described layer wherein with described microsphere comprises the silica be mixed in described layer in addition.
4. film according to claim 3, wherein said silica is present in described layer with the concentration within the scope of about 1000ppm to about 2000ppm.
5. film according to claim 1, the described layer wherein with described microsphere comprises the nano material be mixed in described layer.
6. film according to claim 1, wherein said microsphere comprises soda lime Pyrex.
7. film according to claim 1, the diameter of wherein said microsphere is within the scope of about 10 μm to about 300 μm.
8. film according to claim 1, the grain density of wherein said microsphere is within the scope of about 0.1g/cc to about 1.2g/cc.
9. film according to claim 8, the grain density of wherein said microsphere is within the scope of about 0.1g/cc to about 0.5g/cc.
10. film according to claim 1, wherein said microsphere is uniformly distributed in fact in whole described layer.
11. films according to claim 1, wherein said microsphere to be placed in the superficial layer of described film and uneven distribution, makes the microsphere concentration in the part on the surface being close to described film in described layer substantially beyond the mean concentration of microsphere in described layer.
12. films according to claim 11, wherein said superficial layer comprises multiple sublayer, the described part being close to described film surface in wherein said layer comprises at least one in the described sublayer containing microsphere, and in wherein said sublayer at least another one in fact not containing microsphere.
13. 1 kinds of multilayer films, it comprises top layer, barrier layer and sealant, and wherein said top layer and described sealant are attached to core layer in the opposition side of described barrier layer and in wherein said top layer and described stripping formula sealant, at least one comprises the hollow glass microspheres be mixed in described layer.
14. films according to claim 13, the content of wherein said microsphere is enough to make the coefficient of friction of described film to reduce at least 50%, measured by ISO 8295.
15. films according to claim 13, wherein said top layer comprises the component be selected from by the following group formed: polypropylene random copolymer, polypropylene homopolymer, nylon, styrene-ethylene-butylene-styrene block copolymer, copolyester ether block copolymer and its combination.
16. films according to claim 13, wherein said sealant comprises the material be selected from by the following group formed: homophase polymers, matrix gathering compound and its combination.
17. films according to claim 13, wherein said sealant comprises admixture or the fusions of the first polypropylene and styrene-ethylene-butylene-styrene block copolymer, and described first polypropylene has the first fusing point.
18. films according to claim 17, wherein said sealant comprises the second polyolefin be selected from by the following group formed in addition: polypropylene and polyethylene, and described second polyolefinic fusing point is different from described first fusing point.
19. films according to claim 13, wherein said barrier layer comprises the component be selected from by the following group formed: polyamide 6, polyamide 6,6/ polyamide 6,10 copolymers, amorphous polyamide and its combination.
20. films according to claim 13, wherein said barrier layer comprises ethylene-vinyl alcohol copolymer.
21. films according to claim 20, wherein said barrier layer comprises the sublayer that two have polyamide component in addition, and described sublayer is placed on the opposition side of the sublayer containing described ethylene-vinyl alcohol copolymer.
22. films according to claim 13, it comprises at least one in addition makes at least one in described top layer and described sealant be attached to the articulamentum of described barrier layer.
23. films according to claim 22, wherein said articulamentum comprises the component be selected from by the following group formed: maleinization LLDPE, maleinization polypropylene homopolymer, maleinization polypropylene copolymer and its combination.
24. films according to claim 13, it comprises the core layer be positioned in described barrier layer and described top layer and described sealant between at least one in addition.
25. films according to claim 24, wherein said core layer comprises the component be selected from by the following group formed: the polypropylene of polypropylene homopolymer, Propylene-ethylene random copolymer, polypropylene elastomer, the elastomer based on propylene, the elastomer based on ethene, styrene-ethylene-butylene-styrene block copolymer, ethylene-propylene rubber upgrading and its combination.
26. films according to claim 13, wherein said microsphere is present in described layer with the concentration within the scope of about 250ppm to about 3000ppm.
27. films according to claim 13, the described layer wherein with described microsphere comprises the silica be mixed in described layer in addition.
28. films according to claim 27, wherein said silica is present in described layer with the concentration within the scope of about 1000ppm to about 2000ppm.
29. films according to claim 13, wherein said microsphere comprises soda lime Pyrex.
30. films according to claim 13, the diameter of wherein said microsphere is within the scope of about 10 μm to about 300 μm.
31. films according to claim 13, the grain density of wherein said microsphere is within the scope of about 0.1g/cc to about 1.2g/cc.
32. films according to claim 31, the grain density of wherein said microsphere is within the scope of about 0.1g/cc to about 0.5g/cc.
33. 1 kinds of multi-chamber containers, it comprises:
The main body defined by film, described main body comprises at least two chambers separated by peelable seals, and described film comprises the layer that at least one is mixed with microsphere in layer.
34. 1 kinds of containers, its comprise along at least one share enclose the first side wall and the second sidewall that edge is sealed to define fluid chamber, in wherein said first and second sidewalls, at least one comprises multilayer film, and described film comprises:
Top layer;
First articulamentum;
The barrier layer that contiguous described first articulamentum is settled;
The second articulamentum that contiguous described barrier layer is settled;
Core layer; With
Sealant, in wherein said top layer and described sealant, at least one comprises the glass microspheres be mixed in described layer.
35. 1 kinds of methods manufacturing film, described method comprises:
Hollow microspheres is made to be mixed in whole polymer;
Described extruded polymer is become a skim.
36. methods according to claim 35, it comprises in addition and forms container by described film.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2012/054591 WO2014042614A1 (en) | 2012-09-11 | 2012-09-11 | Polymer films containing microspheres |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104718075A true CN104718075A (en) | 2015-06-17 |
Family
ID=46940598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280076287.5A Pending CN104718075A (en) | 2012-09-11 | 2012-09-11 | Polymer films containing microspheres |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP2895327A1 (en) |
| JP (1) | JP2015530441A (en) |
| KR (1) | KR20150054866A (en) |
| CN (1) | CN104718075A (en) |
| AU (1) | AU2012389847A1 (en) |
| CA (1) | CA2884303A1 (en) |
| HK (1) | HK1208009A1 (en) |
| MX (1) | MX2015003147A (en) |
| WO (1) | WO2014042614A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112123902A (en) * | 2020-09-02 | 2020-12-25 | 安徽国风塑业股份有限公司 | BOPP film capable of being directly compounded with paper and plastic and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018030954A (en) * | 2016-08-25 | 2018-03-01 | パナソニックＩｐマネジメント株式会社 | Polyolefin resin composition, polyolefin resin molded body using the same, and cleaner using the same |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2895327A1 (en) | 2015-07-22 |
| JP2015530441A (en) | 2015-10-15 |
| MX2015003147A (en) | 2015-12-16 |
| CA2884303A1 (en) | 2014-03-20 |
| HK1208009A1 (en) | 2016-02-19 |
| KR20150054866A (en) | 2015-05-20 |
| WO2014042614A1 (en) | 2014-03-20 |
| AU2012389847A1 (en) | 2015-04-09 |
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