CN115556448B - Multilayer film for bioprocess bag and application thereof - Google Patents

Multilayer film for bioprocess bag and application thereof Download PDF

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Publication number
CN115556448B
CN115556448B CN202211096737.9A CN202211096737A CN115556448B CN 115556448 B CN115556448 B CN 115556448B CN 202211096737 A CN202211096737 A CN 202211096737A CN 115556448 B CN115556448 B CN 115556448B
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layer
polyethylene
density
polyolefin elastomer
thickness
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CN115556448A (en
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王坤
秦孙星
邹杨
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Shanghai Lechun Biotechnology Co ltd
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Shanghai Lechun Biotechnology Co ltd
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D29/00—Sacks or like containers made of fabrics; Flexible containers of open-work, e.g. net-like construction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • 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
    • B32B2439/00—Containers; Receptacles
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention belongs to the field of new materials, and discloses a multilayer film for a biological process bag and application thereof. The multilayer film for the biological process bag comprises an outermost layer and an innermost layer, wherein at least one barrier layer and at least one elastic layer are arranged between the outermost layer and the innermost layer, and the average melting temperature of the outermost layer is at least 20 ℃ higher than that of the innermost layer. The multilayer films of some examples of the present invention combine excellent strength, toughness, rub resistance, puncture resistance, and high barrier properties; in the bag making process, if a process of adopting 4 layers of films for simultaneous welding is involved, the outer surfaces among the films can not be bonded, and the welding strength of the obtained 2 welding edges can be ensured to be firm, so that the harsh requirements of the biopharmaceutical process on the disposable bag are met.

Description

Multilayer film for bioprocess bag and application thereof
Technical Field
The invention belongs to the field of new materials, and particularly relates to a multilayer film for a biological process bag and application thereof.
Background
The life sciences industry is considered a high tech, high capital, and high growth industry. The global biopharmaceutical market will increase from dollars 2860 to dollars 7680 to 2030 in 2019, while the chinese biopharmaceutical market will increase from dollars 3120 to cents 13030 to 2030 in 2019. The global and chinese biopharmaceutical ratios in 2019 were 22% and 19%, respectively, whereas the figure in 2030 would reach 37% and 41%, respectively. It has been estimated that the overall market size of global biopharmaceutical equipment plus consumables is around $200 billion, increased by over 10%, with equipment accounting for about 46% and consumables accounting for about 54%.
The disposable bag is used as an important consumable of a biopharmaceutical enterprise, and comprises a liquid storage bag, a liquid preparation bag, a cell reaction bag and the like, and is mainly used in the biopharmaceutical process procedures of culture medium preparation, buffer solution preparation, cell culture, stock solution filling and the like.
The multi-layer film is used as a core raw material of the disposable bag, and the multi-layer film is assembled with other accessories such as pipelines, joints and the like into a complete bag through a welding process. In the welding process of the two multi-layer films, the inner surfaces of the two films are required to be attached together, then the films are placed into constant temperature heat welding or pulse welding equipment, and the inner surfaces of the two films are melted and fused into a whole through heat transfer under the action of pressure, so that the welding edge of the disposable bag is formed. Where the welded edge is weak as a disposable bag, sufficient strength is required to reduce the risk of leakage of the bag due to the greater pressure of the internal liquid on the welded edge during use. During the welding process, only the inner surface of the film is allowed to melt, while the outer surface of the film is not melted, otherwise, the outer surface is melted and deformed and attached to the welding mold, thereby causing damage to the appearance of the bag and reduction in the strength of the weld edge. In addition, in the bag making process of the multilayer film, some bag-type local parts need four layers of multilayer films to be welded simultaneously, and two welding edges are formed simultaneously at the moment; in this process, there may be a case where the outer surface of one film is in contact with the outer surface of the other film, and if the outer surfaces of the multi-layered films are melted during the welding process, the outer surfaces of the two films may be bonded together, so that the two films may be torn apart if the weight is low, but there may be a risk of surface defects and insufficient strength, and the outer surfaces of the two films may be difficult to tear apart if the weight is high, thereby causing the bag to be scrapped. Therefore, the formulation and structural design of the multilayer film is extremely critical to ensure that the outer surface of the film does not melt during the welding process of the multilayer film, thereby not introducing significant appearance defects and potential leakage risks to the bag. The prior art has no relatively mature technical scheme and can be adjusted according to limited experience.
The biopharmaceutical process bag has very strict requirements on membrane materials, and has very strict requirements on dissolution, water resistance, solvent resistance, bending resistance, puncture resistance, barrier property and the like of the membrane. If the disposable bag is repeatedly bent, punctured by foreign objects, or even falls into bags in the process of bag making, transportation and use, the bag body is inevitably damaged to different degrees, and thus larger leakage risk is possibly brought. Considering the purity, irradiation resistance and extrusion processability of the raw materials comprehensively, polyethylene will be the preferred material for preparing the outermost layer of the film. Therefore, the main material of disposable bags for biotechnology on the market is mostly polyethylene or a combination with polyolefin elastomer. However, the larger temperature difference between the inner and outer layers determines that the melting temperature of the polyethylene of the outermost layer is high enough, and means that the density and modulus of the outermost layer are larger, so that the rigidity of the whole film is improved, and the flexibility is reduced. This can significantly reduce certain mechanical properties of the film material, such as impact resistance, rub resistance, etc., and make it difficult to meet the integrity of the bag under extreme conditions. For example, when the bag is used at a client, the bag body is repeatedly rubbed due to the unfolding or the installation of the bag, or the bag filled with liquid falls from a certain height during the operation of a person, and if the flexibility and the impact resistance of the bag body film are insufficient, the risk of liquid leakage is extremely high. In the prior art, in order to obtain a film with better toughness, it is generally necessary to use Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE, ultra low density polyethylene). The special membrane for the disposable bioreactor disclosed in CN109677071A comprises an ultralow-density polyethylene layer arranged on the innermost layer of a membrane body, a low-density polyethylene layer arranged on the outermost layer, an ethylene/vinyl alcohol copolymer layer arranged in the middle of the membrane body and an adhesive layer arranged between two adjacent layers. The multilayer film disclosed in CN104995029a comprises a core layer, and an outer layer, wherein: the outer layer and the core layer are integral with the tie layer, the core layer comprising (C) an ethylene vinyl alcohol copolymer having an ethylene content of 25-48 mole percent, alone or in combination with (D) an ionomeric acid ethylene copolymer, the outer layer comprising (E) a polyolefin having a density of 0.910g/cm 3 to 0.940g/cm 3 or (F) a copolymer of ethylene and an alpha-olefin having a density of 0.870g/cm 3 to 0.910g/cm 3, or a mixture thereof, the tie layer comprising (G) a polyolefin copolymer grafted with a carboxylic acid or carboxylic acid anhydride, alone or in combination with (H) a polyolefin copolymer, while avoiding the use of polyethylene materials as the core layer. These techniques all use high amounts of Low Density Polyethylene (LDPE) and Linear Low Density Polyethylene (LLDPE) to achieve better flexibility. High performance multilayer films are also a key technology limiting our biological development.
It is a very challenging task to develop a multi-layer film for bioprocesses with sufficient toughness, impact resistance and good weldability.
Disclosure of Invention
The present invention aims to overcome at least one of the disadvantages of the prior art and to provide a multilayer film for bioprocess bags and the use thereof.
The technical scheme adopted by the invention is as follows:
in a first aspect of the invention, there is provided:
the multilayer film for the biological process bag comprises an outermost layer and an innermost layer, wherein at least one barrier layer and at least one elastic layer are arranged between the outermost layer and the innermost layer, the barrier layer is bonded with adjacent layers through bonding layers, other adjacent layers are directly bonded or bonded with each other through bonding layers, and the average melting temperature of the outermost layer is at least 20 ℃ higher than that of the innermost layer.
In some examples of multilayer films for bioprocess bags, the outermost layer is made from a blend of polyethylene a and polyethylene B, wherein the polyethylene a has a density of 0.900 to 0.938 g/cm 3 and the polyethylene B has a density of 0.939 to 0.964 g/cm 3; and/or
The elastic layer is made of a blend of a styrene block copolymer C and a polyolefin elastomer D, the styrene content of the styrene block copolymer C is 50% -80%, and the density of the polyolefin elastomer D is 0.890-0.915 g/cm 3; and/or
The innermost layer is made of a blend comprising a polyolefin elastomer D having a density of 0.890 to 0.915 g/cm 3 and a polyolefin elastomer E having a density of 0.860 to 0.889 g/cm 3.
In some examples of multilayer films for bioprocess bags, the weight part ratio of polyethylene a to polyethylene B in the outermost layer is 95:5 to 50:50; and/or
In the elastic layer, the weight part ratio of the styrene block copolymer C to the polyolefin elastomer D is 95:5 to 5:95; and/or
In the innermost layer, the weight part ratio of the polyolefin elastomer D to the polyolefin elastomer E is 95:5 to 50:50.
In some examples of multilayer films for bioprocess bags, the weight part ratio of polyethylene a to polyethylene B in the outermost layer is 90:10 to 70:30; and/or
In the elastic layer, the weight part ratio of the styrene block copolymer C to the polyolefin elastomer D is 90:10 to 50:50; and/or
In the innermost layer, the weight part ratio of the polyolefin elastomer D to the polyolefin elastomer E is 90:10 to 70:30.
In some examples of multi-layer films for bioprocess bags, the polyethylene a is a low density polyethylene or a linear low density polyethylene; and/or
The polyethylene B is low-density polyethylene or high-density polyethylene; and/or
The styrene block copolymer C is a styrene-butadiene copolymer; and/or
The polyolefin elastomer D and the polyolefin elastomer E are copolymers of ethylene and alpha-olefin containing 4-10 carbon atoms; and/or
The barrier layer is an ethylene-vinyl alcohol copolymer; and/or
The adhesive layer is an anhydride modified ethylene copolymer.
In some examples of multi-layer films for bioprocess bags, the thickness of the outermost layer is 30 μm to 100 μm; and/or
The thickness of the elastic layer monolayer is 10-80 mu m; and/or
The thickness of the barrier layer is 5-40 mu m; and/or
The thickness of the single layer of the bonding layer is 10-40 mu m; and/or
The thickness of the innermost layer is 100-300 mu m.
In some examples of multi-layer films for bioprocess bags, the multi-layer film has a tensile strength of not less than 16 Mpa; and/or
Elongation at break not less than 350%; and/or
The dart impact strength is not lower than 1600g; and/or
The number of pinholes generated after 900 times of rubbing test is not more than 1 per piece; and/or
Puncture strength is not lower than 35N; and/or
The water vapor transmission rate is not more than 3.0 g/m 2. Day; and/or
The oxygen transmission rate is not more than 3.0 cm 3/m2. Day.
In some examples of multi-layer films for bioprocess bags, the multi-layer film is an outermost layer, a barrier layer, a stretch layer, and an innermost layer in that order from the outside to the inside; and/or
The multilayer film comprises an outermost layer, a flexible layer, a barrier layer and an innermost layer from outside to inside in sequence; and/or
The multilayer film comprises an outermost layer, a toughening layer, a barrier layer, a toughening layer and an innermost layer from outside to inside.
In some examples of multilayer films for bioprocess bags, the adhesive layer is a maleic anhydride modified ethylene copolymer.
In a second aspect of the invention, there is provided:
A disposable bag for biological medicine is prepared from the multi-layer film for the biological process bag.
The beneficial effects of the invention are as follows:
The multilayer films of some examples of the present invention combine excellent strength, toughness, rub resistance, puncture resistance, and high barrier properties; in the bag making process, if a process of adopting 4 layers of films for simultaneous welding is involved, the outer surfaces among the films can not be bonded, and the welding strength of the obtained 2 welding edges can be ensured to be firm, so that the harsh requirements of the biopharmaceutical process on the disposable bag are met.
The multilayer films of some examples of the present invention employ a blend of polyolefin elastomer D having a density of 0.890 to 0.915 g/cm 3 with polyolefin elastomer E having a density of 0.860 to 0.889 g/cm 3. The polyolefin elastomer D is softer, has lower melting temperature and better heat-sealing welding performance. The polyolefin elastomer E has better flexibility and lower melting temperature compared with the polyolefin elastomer D, and can be welded at lower temperature; however, its tackiness is relatively high and excessive use of the polyolefin elastomer E increases the difficulty in the film processing during production. Therefore, it is necessary to scientifically match the ratio of the polyolefin elastomer D and the polyolefin elastomer E in the innermost layer of the multilayer film, so that the melting temperature of the innermost layer is low, and the viscosity is not too high to affect the production; in addition, the overall feel and softness of the multilayer film can also be adjusted by the ratio of polyolefin elastomer D to polyolefin elastomer E.
The outermost layer of the multilayer films of some examples of the present invention employs a blend of polyethylene A having a density of 0.900 to 0.938 g/cm 3 and polyethylene B having a density of 0.939 to 0.964 g/cm 3. Polyethylene a has a higher hardness and a higher melting temperature than the innermost layer, but the difference between them is smaller than 25 ℃, and under certain special welding process conditions the outermost layer is at risk of melting. Therefore, polyethylene B with higher density is needed to further increase the melting temperature of the outermost layer, so that the difference between the melting temperatures of the outermost layer and the innermost layer is more than 25 ℃, and the requirement of bag making is met. However, when the content of the polyethylene B is too high, the multilayer film is hard, and obvious sharp corners or folds are easy to generate in the use process; and the attaching property and shape following property of the disposable bag to the external environment in the using process can be affected, so that the process difficulty in the using process of the bag can be increased. Therefore, the proportion of polyethylene A and polyethylene B of the outermost layer of the multilayer film needs to be scientifically matched, so that the melting temperature of the outermost layer is higher, and the melting temperature difference between the outermost layer and the innermost layer is more than 25 ℃, thereby effectively widening the temperature window for bag making welding; meanwhile, the hardness of the outermost layer is reasonably controlled, and the final hand feeling of the film and the adhesion of the disposable bag to the outside in the use process are not affected.
The multilayer films of some examples of the present invention have a elastomeric layer that employs a blend of a styrenic block copolymer having a C styrene content of 50% to 80% and a polyolefin elastomer having a D density of 0.890 to 0.915 g/cm 3. The styrene block copolymer C is a styrene-butadiene copolymer obtained by copolymerizing styrene and butadiene. The presence of the butadiene block imparts excellent toughness and impact resistance to the copolymer. Meanwhile, the styrene block content is more than 50%, so that the overall processability of the copolymer is obviously improved. But the multilayer film is prepared from materials of different layers through different extruders and multilayer coextrusion processes; in order to obtain a film with uniform and stable interlayer distribution and excellent appearance, it is necessary to ensure good matching of the flowability between layers of different materials. If 100% of the styrene-based block copolymer C is used as the material of the elastic layer, excellent flow matching with other layers is difficult to achieve, and the polyolefin elastomer D needs to be added to further improve the flow matching between the elastic layer and the other layers, so that the appearance and quality stability of the obtained film product are ensured. Therefore, it is required to scientifically match the ratio of the styrene-based block copolymer C and the polyolefin elastomer D of the elastic layer of the multilayer film, not only to match the fluidity of the elastic layer during extrusion processing with other layers, but also to impart excellent toughness, impact resistance and rub resistance to the multilayer film.
In summary, the average melting temperature difference between the innermost layer material and the outermost layer material of the multilayer film is 20 ℃, preferably more than 25 ℃, so that the innermost layer material can be well welded into a whole in the welding process, and the outermost layer material cannot be melted, thereby greatly widening the welding temperature window in the bag making process, reducing the difficulty of the bag making process and greatly improving the reliability of the bag body. Meanwhile, the existence of the elastic layer endows the multilayer film with excellent toughness and impact strength, so that the prepared disposable bag is more reliable and can bear challenges brought to the bag body by some extreme operating conditions.
Drawings
FIG. 1 is a photograph of the multilayer film of example 1.
FIG. 2 is a photograph of a comparative example 5 multilayer film.
Fig. 3 is a photograph of the multilayer film of example 2 after multiple bends.
Fig. 4 is a photograph of the multi-layer film of comparative example 2 after multiple bends.
Fig. 5 is a photograph of the multilayer film of example 1 after four heat seals.
Fig. 6 is a photograph of a four-layer heat-sealed multilayer film of comparative example 1.
Detailed Description
The inventor researches find that the innermost layer can be well fused and bonded into a whole in the welding process by controlling the average melting temperature of the outermost layer of the multilayer film to be at least 20 ℃ higher than the average melting temperature of the innermost layer. By adjusting the formulation of the innermost and outermost polyethylene materials, satisfactory results are obtained. The other functional layers are further combined to obtain the multi-layer film for the biological process bag with excellent performance.
In a first aspect of the invention, there is provided:
the multilayer film for the biological process bag comprises an outermost layer and an innermost layer, wherein at least one barrier layer and at least one elastic layer are arranged between the outermost layer and the innermost layer, the barrier layer is bonded with adjacent layers through bonding layers, other adjacent layers are directly bonded or bonded with each other through bonding layers, and the average melting temperature of the outermost layer is at least 20 ℃ higher than that of the innermost layer.
The melting temperature of the polymer is often a range of values, and in the present invention, the average melting temperature refers to the mathematical average of the upper and lower temperatures within the range.
In some examples of multilayer films for bioprocess bags, the outermost layer is made from a blend of polyethylene a and polyethylene B, wherein the polyethylene a has a density of 0.900 to 0.938 g/cm 3 and the polyethylene B has a density of 0.939 to 0.964 g/cm 3. Polyethylene a and polyethylene B have different densities and melting points, polyethylene a being relatively low in density and melting point and polyethylene B being relatively high in density and melting point. The outermost layer prepared by blending the two has better toughness and higher average melting temperature.
By adjusting the mixing ratio of the polyethylene A and the polyethylene B, the toughness and the average melting temperature of the outermost layer can be adjusted to a certain extent so as to meet corresponding requirements. In some examples of multilayer films for bioprocess bags, the weight part ratio of polyethylene a to polyethylene B in the outermost layer is 95:5 to 50:50.
In some examples of multilayer films for bioprocess bags, the weight part ratio of polyethylene a to polyethylene B in the outermost layer is 90:10 to 70:30.
In some examples of multilayer films for bioprocess bags, the elastomeric layer is made from a blend of a styrenic block copolymer C having a styrene content of 50% to 80% and a polyolefin elastomer D having a density of 0.890 to 0.915 g/cm 3. The elastic layer with the composition has better compatibility and can improve the toughness of the whole membrane material.
By adjusting the mixing ratio of the styrenic block copolymer C and the polyolefin elastomer D, the flowability of the elastic layer at the time of extrusion processing can be matched with other layers, ensuring excellent appearance of the film, while also imparting excellent toughness, impact resistance and rub resistance to the multilayer film. In some examples of the multilayer film for bioprocess bags, the elastomeric layer comprises a styrenic block copolymer C and a polyolefin elastomer D in a weight ratio of 95:5 to 5:95.
In some examples of the multilayer film for bioprocess bags, the elastomeric layer comprises 90 parts by weight of a styrenic block copolymer C and a polyolefin elastomer D: 10 to 50:50.
In some examples of multilayer films for bioprocess bags, the innermost layer is made from a blend comprising a polyolefin elastomer D having a density of 0.890 to 0.915 g/cm 3 and a polyolefin elastomer E having a density of 0.860 to 0.889 g/cm 3.
By adjusting the proportion of the polyolefin elastomer D and the polyolefin elastomer E, the average melting temperature of the innermost layer can be lower, and the viscosity is not too large to influence the production; in addition, the overall feel and softness of the multilayer film can also be adjusted by the ratio of polyolefin elastomer D to polyolefin elastomer E. In some examples of multilayer films for bioprocess bags, the weight part ratio of polyolefin elastomer D to polyolefin elastomer E in the innermost layer is 95:5 to 50:50.
In some examples of multilayer films for bioprocess bags, the weight part ratio of polyolefin elastomer D to polyolefin elastomer E in the innermost layer is 90:10 to 70:30.
In some examples of multilayer films for bioprocess bags, the outermost layer is made of a blend of polyethylene a and polyethylene B, wherein the polyethylene a has a density of 0.900 to 0.938 g/cm 3 and the polyethylene B has a density of 0.939 to 0.964 g/cm 3, the weight ratio of polyethylene a to polyethylene B in the outermost layer being 95:5 to 50:50; the elastic layer is made of a blend of a styrene block copolymer C and a polyolefin elastomer D, wherein the styrene content of the styrene block copolymer C is 50% -80%, the density of the polyolefin elastomer D is 0.890-0.915 g/cm 3, and in the elastic layer, the weight ratio of the styrene block copolymer C to the polyolefin elastomer D is 95:5 to 5:95; the innermost layer is made of a blend containing a polyolefin elastomer D with a density of 0.890-0.915 g/cm 3 and a polyolefin elastomer E with a density of 0.860-0.889 g/cm 3, and in the elastic layer, the weight part ratio of a styrene block copolymer C to the polyolefin elastomer D is 95:5 to 5:95.
In some examples of multi-layer films for bioprocess bags, the polyethylene a is a low density polyethylene or a linear low density polyethylene.
In some examples of multi-layer films for bioprocess bags, the polyethylene B is a low density polyethylene or a high density polyethylene.
In some examples of multilayer films for bioprocess bags, the styrenic block copolymer C is a styrene-butadiene copolymer.
In some examples of multilayer films for bioprocess bags, the polyolefin elastomer D and the polyolefin elastomer E are both copolymers of ethylene and an alpha olefin having 4 to 10 carbon atoms.
The barrier layer is made of an acceptable film material with high barrier properties, which in some examples of multi-layer films for bioprocess bags is an ethylene-vinyl alcohol copolymer.
The adhesive layer has the function of better bonding the layers, and can be omitted under the condition that adjacent layers are high in compatibility and easy to fuse. In some examples of multilayer films for bioprocess bags, the adhesive layer is an anhydride modified ethylene copolymer. The combined adhesive layer has better compatibility.
In some examples of multilayer films for bioprocess bags, the adhesive layer is a maleic anhydride modified ethylene copolymer.
The thickness of each layer can be set according to different needs.
In some examples of the multi-layer film for a bioprocess bag, the thickness of the outermost layer is 30 μm to 100 μm.
In some examples of multi-layer films for bioprocess bags, the thickness of the elastomeric layer monolayer is 10 μm to 80 μm.
In some examples of multilayer films for bioprocess bags, the barrier layer has a thickness of 5 μm to 40 μm.
In some examples of multi-layer films for bioprocess bags, the thickness of the adhesive layer monolayer is 10 μm to 40 μm.
In some examples of multi-layer films for bioprocess bags, the innermost layer has a thickness of 100 μm to 300 μm.
In some examples of the multi-layer film for bioprocess bags, the tensile strength of the multi-layer film is not less than 16 Mpa.
In some examples of the multi-layer film for bioprocess bags, the elongation at break is not less than 350%.
In some examples of multi-layer films for bioprocess bags, the dart impact strength is not less than 1600g.
In some examples of multi-layer films for bioprocess bags, the number of pinholes created after 900 rub tests is no more than 1 per sheet.
In some examples of multi-layer films for bioprocess bags, the puncture strength is not less than 35N.
In some examples of multi-layer films for bioprocess bags, the water vapor transmission rate is no more than 3.0 g/m 2 day.
In some examples of multi-layer films for bioprocess bags, the oxygen transmission does not exceed 3.0 cm 3/m2. Day.
In some examples of multilayer films for bioprocess bags, the multilayer film is an outermost layer, a barrier layer, a stretch layer, and an innermost layer in that order from the outside to the inside.
In some examples of multi-layer films for bioprocess bags, the multi-layer film is an outermost layer, a barrier layer, a toughening layer and an innermost layer in sequence from outside to inside, and the layers are bonded together through an adhesive layer.
In some examples of multilayer films for bioprocess bags, the multilayer film is an outermost layer, a stretch layer, a barrier layer, and an innermost layer in that order from the outside to the inside.
In some examples of multilayer films for bioprocess bags, the multilayer film is an outermost layer, a stretch layer, a barrier layer, a stretch layer, and an innermost layer in that order from the outside to the inside.
The technical characteristics can be combined at will under the condition of no mutual exclusion so as to meet the requirements of different applications.
In a second aspect of the invention, there is provided:
A disposable bag for biological medicine is prepared from the multi-layer film for the biological process bag.
Specifically, the biological process bag can be obtained by cutting a biological process bag with a multilayer film and then welding.
In the present invention, abbreviations used have the following meanings:
LDPE: low density polyethylene
HDPE: high density polyethylene
LLDPE: linear low density polyethylene
POP: polyolefin elastomer
EVOH: ethylene-vinyl alcohol copolymer
SBC: styrene-butadiene copolymers.
The multilayer film of the present invention can be prepared according to the existing method, and in particular can be prepared by a multilayer coextrusion technology, including but not limited to a multilayer coextrusion casting technology, a multilayer coextrusion blowing technology, and a multilayer coextrusion blowing technology.
Styrenic block copolymers are a class of thermoplastic elastomers that have excellent elastic properties, and are very excellent in stretchability, puncture resistance, rub resistance, and the like after being formed into films, as compared to most polyethylene materials. The styrene block copolymer is formed by copolymerizing styrene and butadiene serving as monomers, and if the styrene content is lower than 50%, the material is difficult to process into a film; if the styrene content is higher than 80%, the processability is obviously improved, but the material is relatively rigid, and the prepared film hardly exerts a good elastic toughness effect.
The invention is further described below with reference to examples. It should be understood that these descriptions are merely provided to further illustrate the features and advantages of the present invention and are not intended to limit the scope of the claims.
Example 1
The structure is totally 7 layers, and the structure is from outside to inside: the outermost layer/adhesive layer-1/elastic layer/adhesive layer-2/barrier layer/adhesive layer-3/innermost layer;
Wherein the outermost layer is composed of a blend of LDPE with a density of 0.928 g/cm 3 and HDPE with a density of 0.954 g/cm 3, the weight ratio of the former to the latter being 70/30;
The elastic layer is composed of a blend of SBC with styrene content of 60.0% and POP with density of 0.902 g/cm 3, and the weight ratio of the former to the latter is 80/20;
The innermost layer is composed of a blend of POP with density of 0.902 g/cm 3 and POP with density of 0.877g/cm 3, the weight ratio of the former to the latter is 80/20;
The barrier layer is composed of 100% EVOH;
Adhesive layer-1, adhesive layer-2 and adhesive layer-3 all have the same composition and are composed of polyethylene modified with 100% maleic anhydride;
The thickness of the outermost layer was 50. Mu.m, the thickness of the adhesive layer-1 was 15. Mu.m, the thickness of the elastic layer was 50. Mu.m, the thickness of the adhesive layer-2 was 25. Mu.m, the thickness of the barrier layer was 25. Mu.m, the thickness of the adhesive layer-3 was 25. Mu.m, the thickness of the innermost layer was 190. Mu.m, and the total thickness was 380. Mu.m.
Example 2
The structure is totally 7 layers, and the structure is from outside to inside: the outermost layer/adhesive layer-1/barrier layer/adhesive layer-2/elastic layer/adhesive layer-3/innermost layer;
Wherein the outermost layer is composed of a blend of LLDPE with a density of 0.931 g/cm 3 and HDPE with a density of 0.960 g/cm 3, the weight ratio of the former to the latter being 80/20;
The elastic layer is composed of a blend of SBC with styrene content of 60.0% and POP with density of 0.904 g/cm 3, wherein the weight ratio of the former to the latter is 70/30;
The innermost layer is composed of a blend of POP with density of 0.904 g/cm 3 and POP with density of 0.872g/cm 3, wherein the weight ratio of the former to the latter is 85/15;
The barrier layer is composed of 100% EVOH;
Adhesive layer-1, adhesive layer-2 and adhesive layer-3 all have the same composition and are composed of polyethylene modified with 100% maleic anhydride;
The thickness of the outermost layer was 40. Mu.m, the thickness of the adhesive layer-1 was 25. Mu.m, the thickness of the barrier layer was 25. Mu.m, the thickness of the adhesive layer-2 was 25. Mu.m, the thickness of the elastic layer was 60. Mu.m, the thickness of the adhesive layer-3 was 15. Mu.m, the thickness of the innermost layer was 190. Mu.m, and the total thickness was 380. Mu.m.
Example 3
The structure is 9 layers in total, and from outside to inside is: the outermost layer/bonding layer-1/elastic layer-1/bonding layer-2/barrier layer/bonding layer-3/elastic layer-2/bonding layer-4/innermost layer;
Wherein the outermost layer is composed of a blend of LDPE with a density of 0.928 g/cm 3 and HDPE with a density of 0.954 g/cm 3, the weight ratio of the former to the latter being 80/20;
The elastic layer-1 and the elastic layer-2 are completely the same in composition, and are both composed of a blend of SBC with 65.0% of styrene and POP with the density of 0.899 g/cm 3, wherein the weight ratio of the SBC to the POP is 60/40;
The innermost layer is composed of a blend of POP with density of 0.899 g/cm 3 and POP with density of 0.864g/cm 3, the weight ratio of the former to the latter being 90/10;
The barrier layer is composed of 100% EVOH;
adhesive layer-1, adhesive layer-2, adhesive layer-3 and adhesive layer-4 all comprised of 100% maleic anhydride modified polyethylene;
The thickness of the outermost layer was 60. Mu.m, the thickness of the adhesive layer-1 was 15. Mu.m, the thickness of the elastic layer-1 was 30. Mu.m, the thickness of the adhesive layer-2 was 25. Mu.m, the thickness of the barrier layer was 25. Mu.m, the thickness of the adhesive layer-3 was 25. Mu.m, the thickness of the elastic layer-2 was 30. Mu.m, the thickness of the adhesive layer-4 was 15. Mu.m, and the thickness of the innermost layer was 175. Mu.m, and the total thickness was 400. Mu.m.
Example 4
The structure is 6 layers in total, from outside to inside: the outermost layer/elastic layer/adhesive layer-1/barrier layer/adhesive layer-2/innermost layer;
Wherein the outermost layer is composed of a blend of LLDPE with a density of 0.926 g/cm 3 and HDPE with a density of 0.960 g/cm 3, the weight ratio of the former to the latter being 75/25;
The elastic layer is composed of a blend of SBC with styrene content of 60.0% and POP with density of 0.902 g/cm 3, and the weight ratio of the former to the latter is 50/50;
The innermost layer is composed of a blend of POP with density of 0.902 g/cm 3 and POP with density of 0.872g/cm 3, wherein the weight ratio of the former to the latter is 80/20;
The barrier layer is composed of 100% EVOH;
adhesive layer-1 and adhesive layer-2 are all composed of 100% maleic anhydride modified polyethylene;
The thickness of the outermost layer was 50. Mu.m, the thickness of the elastic layer was 70. Mu.m, the thickness of the adhesive layer-1 was 25. Mu.m, the thickness of the barrier layer was 25. Mu.m, the thickness of the adhesive layer-2 was 25. Mu.m, the thickness of the innermost layer was 200. Mu.m, and the total thickness was 395. Mu.m.
Example 5
The structure is 6 layers in total, from outside to inside: the outermost layer/adhesive layer-1/barrier layer/adhesive layer-2/elastic layer/innermost layer;
Wherein the outermost layer is composed of a blend of LDPE having a density of 0.925 g/cm 3 and HDPE having a density of 0.952 g/cm 3, the weight ratio of the former to the latter being 50/50;
The elastic layer is composed of a blend of SBC with 65.0% of styrene and POP with density of 0.895 g/cm 3, and the weight ratio of the former to the latter is 60/40;
the innermost layer is composed of a blend of POP with density of 0.895 g/cm 3 and POP with density of 0.872g/cm 3, and the weight ratio of the former to the latter is 90/10;
The barrier layer is composed of 100% EVOH;
adhesive layer-1 and adhesive layer-2 are all composed of 100% maleic anhydride modified polyethylene;
The thickness of the outermost layer was 40. Mu.m, the thickness of the adhesive layer-1 was 25. Mu.m, the thickness of the barrier layer was 25. Mu.m, the thickness of the adhesive layer-2 was 25. Mu.m, the thickness of the elastic layer was 60. Mu.m, the thickness of the innermost layer was 215. Mu.m, and the total thickness was 390. Mu.m.
Example 6
The structure is totally 7 layers, and the structure is from outside to inside: the outermost layer/elastic layer-1/adhesive layer-1/barrier layer/adhesive layer-2/elastic layer-2/innermost layer;
wherein the outermost layer is composed of a blend of LLDPE having a density of 0.935 g/cm 3 and HDPE having a density of 0.956 g/cm 3, the weight ratio of the former to the latter being 80/20;
The elastic layer-1 and the elastic layer-2 are completely the same in composition and are both composed of a blend of SBC with styrene content of 60.0% and POP with density of 0.904 g/cm 3, wherein the weight part ratio of the SBC to the POP is 50/50;
The innermost layer is composed of a blend of POP with density of 0.904 g/cm 3 and POP with density of 0.870g/cm 3, and the weight ratio of the former to the latter is 75/25;
The barrier layer is composed of 100% EVOH;
adhesive layer-1 and adhesive layer-2 are all composed of 100% maleic anhydride modified polyethylene;
The thickness of the outermost layer was 60. Mu.m, the thickness of the elastic layer-1 was 25. Mu.m, the thickness of the adhesive layer-1 was 25. Mu.m, the thickness of the barrier layer was 25. Mu.m, the thickness of the adhesive layer-2 was 25. Mu.m, the thickness of the elastic layer-2 was 25. Mu.m, the thickness of the innermost layer was 215. Mu.m, and the total thickness was 400. Mu.m.
Comparative example 1
The structure is 6 layers in total, from outside to inside: the outermost layer/elastic layer/adhesive layer-1/barrier layer/adhesive layer-2/innermost layer;
Wherein the outermost layer is composed of LLDPE with 100% density of 0.923 g/cm 3;
The elastic layer is composed of a blend of SBC with 65.0% of styrene and POP with density of 0.902 g/cm 3, and the weight ratio of the former to the latter is 20/80;
The innermost layer is composed of a blend of POP with density of 0.902 g/cm 3 and POP with density of 0.882g/cm 3, the weight ratio of the former to the latter being 95/5;
The barrier layer is composed of 100% EVOH;
adhesive layer-1 and adhesive layer-2 are all composed of 100% maleic anhydride modified polyethylene;
The thickness of the outermost layer was 50. Mu.m, the thickness of the elastic layer was 70. Mu.m, the thickness of the adhesive layer-1 was 25. Mu.m, the thickness of the barrier layer was 25. Mu.m, the thickness of the adhesive layer-2 was 25. Mu.m, the thickness of the innermost layer was 200. Mu.m, and the total thickness was 395. Mu.m.
Comparative example 2
The structure is 6 layers in total, from outside to inside: the outermost layer/elastic layer/adhesive layer-1/barrier layer/adhesive layer-2/innermost layer;
Wherein the outermost layer is composed of HDPE having a density of 0.960 g/cm 3;
the elastic layer is composed of a blend of SBC with styrene content of 60.0% and POP with density of 0.904 g/cm 3, and the weight ratio of the former to the latter is 50/50;
The innermost layer is composed of a blend of POP with density of 0.904 g/cm 3 and POP with density of 0.877g/cm 3, the weight ratio of the former to the latter is 90/10;
The barrier layer is composed of 100% EVOH;
adhesive layer-1 and adhesive layer-2 are all composed of 100% maleic anhydride modified polyethylene;
the thickness of the outermost layer was 70 μm, the thickness of the elastic layer was 50 μm, the thickness of the adhesive layer-1 was 25 μm, the thickness of the barrier layer was 25 μm, the thickness of the adhesive layer-2 was 25 μm, the thickness of the innermost layer was 200 μm, and the total thickness was 395 μm.
Comparative example 3
The structure is 5 layers in total, from outside to inside: outermost/adhesive layer-1/barrier/adhesive layer-2/innermost;
Wherein the outermost layer is composed of a blend of LDPE having a density of 0.925 g/cm 3 and HDPE having a density of 0.952 g/cm 3, the weight ratio of the former to the latter being 60/40;
the innermost layer is composed of a blend of POP with density of 0.895 g/cm 3 and POP with density of 0.872g/cm 3, and the weight ratio of the former to the latter is 90/10;
The barrier layer is composed of 100% EVOH;
adhesive layer-1 and adhesive layer-2 are all composed of 100% maleic anhydride modified polyethylene;
The thickness of the outermost layer was 60 μm, the thickness of the adhesive layer-1 was 25 μm, the thickness of the barrier layer was 25 μm, the thickness of the adhesive layer-2 was 25 μm, the thickness of the innermost layer was 255 μm, and the total thickness was 390 μm.
Comparative example 4
The structure is 6 layers in total, from outside to inside: the outermost layer/adhesive layer-1/barrier layer/adhesive layer-2/elastic layer/innermost layer;
wherein the outermost layer is composed of a blend of LDPE having a density of 0.925 g/cm 3 and HDPE having a density of 0.956 g/cm 3, the weight ratio of the former to the latter being 50/50;
The elastic layer is composed of POPs with the density of 0.904 g/cm 3;
The innermost layer is composed of a blend of POP with density of 0.904 g/cm 3 and POP with density of 0.872g/cm 3, wherein the weight ratio of the former to the latter is 90/10;
The barrier layer is composed of 100% EVOH;
adhesive layer-1 and adhesive layer-2 are all composed of 100% maleic anhydride modified polyethylene;
the thickness of the outermost layer was 60. Mu.m, the thickness of the adhesive layer-1 was 25. Mu.m, the thickness of the barrier layer was 25. Mu.m, the thickness of the adhesive layer-2 was 25. Mu.m, the thickness of the elastic layer was 50. Mu.m, the thickness of the innermost layer was 205. Mu.m, and the total thickness was 390. Mu.m.
Comparative example 5
The structure is totally 7 layers, and the structure is from outside to inside: the outermost layer/elastic layer-1/adhesive layer-1/barrier layer/adhesive layer-2/elastic layer-2/innermost layer;
wherein the outermost layer is composed of a blend of LLDPE having a density of 0.935 g/cm 3 and HDPE having a density of 0.956 g/cm 3, the weight ratio of the former to the latter being 80/20;
The elastic tough layer-1 and the elastic tough layer-2 are completely the same in structure and are all composed of SBC with 100% of styrene content of 60.0%;
The innermost layer is composed of a blend of POP with density of 0.904 g/cm 3 and POP with density of 0.870g/cm 3, wherein the weight ratio of the former to the latter is 95/5;
The barrier layer is composed of 100% EVOH;
adhesive layer-1 and adhesive layer-2 are all composed of 100% maleic anhydride modified polyethylene;
The thickness of the outermost layer was 60. Mu.m, the thickness of the elastic layer-1 was 25. Mu.m, the thickness of the adhesive layer-1 was 25. Mu.m, the thickness of the barrier layer was 25. Mu.m, the thickness of the adhesive layer-2 was 25. Mu.m, the thickness of the elastic layer-2 was 25. Mu.m, the thickness of the innermost layer was 215. Mu.m, and the total thickness was 400. Mu.m.
Performance testing of different film materials
The multilayer films prepared in examples 1 to 6 and comparative examples 1 to 5 were subjected to performance tests mainly comprising film appearance, four-layer heat sealing property, multi-bending property, mechanical property, barrier property.
The appearance of the film is tested according to the internal standard of an enterprise, the film is observed with naked eyes under a lamp inspection table, if the appearance of the film is uniform, no obvious irregular lines, protrusions or depressions are formed, the film is qualified, and otherwise, the film is unqualified.
The four-layer heat sealing performance is tested according to the internal standard of an enterprise, the four films are divided into two groups, the inner surfaces of the two films in each group are respectively bonded, then the two groups of films are stacked and put into welding equipment for welding, and after welding, whether the outer surfaces of the two groups of films, which are contacted with each other, are mutually adhered or not is checked under the condition that the welding strength of each group of welding edges is ensured to meet the requirement; if the outer surfaces of the four layers which are contacted after heat sealing are not adhered, the two layers can be separated easily, the two layers are qualified, otherwise, the two layers are disqualified.
The multi-bending performance is tested according to the internal standard of an enterprise, specifically, a film with the size of 50cm is folded for 4 times, and whether sharp corners are generated at the folding position or not is observed; then the film is unfolded, and the states of sharp corners and bending positions are checked. If the film has obvious sharp corners and the bent parts have obvious crease and blushing phenomena, the film is regarded as unqualified, otherwise, the film is regarded as qualified.
Tensile strength and elongation at break were measured according to ASTM D882.
Puncture strength was measured according to ASTM F1306 standard.
The rubbing properties, characterized by the number of pinholes produced by the film after rubbing, were measured according to ASTM F392 (method B).
Impact resistance, characterized by dart impact strength, is measured according to ASTM D1709 (method a).
The water vapor transmission performance was measured according to ASTM F1249.
Oxygen transmission performance was tested according to ASTM D3985 standard.
The test results are shown in Table 1 and FIGS. 1 to 6.
TABLE 1
Note that: s represents an embodiment, e.g., S1 refers to embodiment 1; d represents a comparative example, e.g., D1 represents comparative example 1; "+" indicates pass and "-" indicates fail.
FIG. 1 is a photograph of the multilayer film of example 1, from which it can be seen that the film material has uniform transparency, good appearance, and a flat surface.
Fig. 2 is a photograph of the multilayer film of comparative example 5, and it can be seen from the figure that the uniformity of the film material is poor, and the film material has a granular feel.
Fig. 3 is a photograph of the multi-layer film of example 2 after multiple bends, and it can be seen from the figure that the film material folds after multiple bends are round and have no significant blushing.
Fig. 4 is a photograph of the multilayer film of comparative example 2 after multiple bending, and it can be seen from the figure that the film material folds are evident after multiple bending, blush, and have a tendency to split.
FIG. 5 is a photograph of a four-layer heat-sealed multilayer film of example 1, wherein after four-layer heat-sealing, the 1/2-layer film is heat-sealed well, the 3/4-layer film is heat-sealed well, and the 2/3-layer films are not adhered to each other and can be well separated.
FIG. 6 is a photograph of a comparative example 1 multilayer film after four heat seals, 1/2 film heat seals well, 3/4 film heat seals well, but 2/3 films are heat sealed and not separated and not acceptable.
As can be seen from the data in table 1 and fig. 1 to 6:
1) The multilayer film for biotechnology application (examples 1-6) prepared by the invention has excellent appearance, four-layer heat sealing performance, multi-bending performance, mechanical performance and barrier performance, and has excellent market application prospect.
2) The outermost layer of comparative example 1 was free of polyethylene material having a density of 0.939 to 0.964 g/cm 3, resulting in a lower average melting temperature of the outermost layer of the film, which caused the four films to adhere to each other and not separate from each other between the outer surfaces of the films in contact when subjected to the four heat-seal process, thereby resulting in rejection of the bag.
3) The outermost layer in comparative example 2 contains no polyethylene material with a density of 0.900-0.938 g/cm 3, but only contains polyethylene material with a density of 0.939-0.964 g/cm 3 and high rigidity, so that the whole film is hard, obvious crease and whitening phenomena are easy to generate after multiple folio, and the crease is prone to cracking. Therefore, the bending of the bag body can easily lead the film to generate sharp angles and folds in the processing and using processes of the disposable bag, thereby causing local defects and bringing potential leakage risks.
4) The structure of comparative example 3 does not contain an elastic layer, so that the mechanical properties such as tensile property, kneading property, impact resistance and the like of the film are obviously lower than those of examples 1 to 6. And the repeated bending performance of the film is also significantly affected. Eventually rendering it unsatisfactory for use in certain situations.
5) The elastic layer in comparative example 4 contains no styrene block copolymer with 50-80% of styrene content, so that the mechanical properties of the film, such as tensile property, kneading property, impact resistance and the like, are obviously lower than those of examples 1-6. And the repeated bending performance of the film is also significantly affected. Eventually rendering it unsatisfactory for use in certain situations.
6) The elastic layer in comparative example 5 does not contain polyolefin elastomer with density of 0.890-0.915 g/cm 3, so that the processing performance of the elastic layer and other layers is not matched, and finally the appearance of the film is uneven, obvious and irregular lines and other appearance defects exist, further the mechanical property of the film is possibly reduced, and the use requirement cannot be met.
The above description of the present invention is further illustrated in detail and should not be taken as limiting the practice of the present invention. It is within the scope of the present invention for those skilled in the art to make simple deductions or substitutions without departing from the concept of the present invention.

Claims (8)

1. The multilayer film for the biological process bag is characterized by comprising an outermost layer and an innermost layer, wherein at least one barrier layer and at least one elastic layer are arranged between the outermost layer and the innermost layer, the barrier layer is bonded with adjacent layers through bonding layers, other adjacent layers are directly bonded or are bonded with each other through bonding layers, and the average melting temperature of the outermost layer is at least 20 ℃ higher than that of the innermost layer;
The outermost layer is made of a blend of polyethylene A and polyethylene B, and the weight ratio of the polyethylene A to the polyethylene B is 95:5 to 50:50, wherein the density of the polyethylene A is 0.900-0.938 g/cm 3, and the density of the polyethylene B is 0.939-0.964 g/cm 3;
the elastic layer is made of a blend of a styrene block copolymer C and a polyolefin elastomer D, and the weight ratio of the styrene block copolymer C to the polyolefin elastomer D is 95:5 to 5:95, wherein the styrene content of the styrene block copolymer C is 50-80%, and the density of the polyolefin elastomer D is 0.890-0.915 g/cm 3;
The innermost layer is made of a blend comprising a polyolefin elastomer D with a density of 0.890-0.915 g/cm 3 and a polyolefin elastomer E with a density of 0.860-0.889 g/cm 3, the weight part ratio of the polyolefin elastomer D to the polyolefin elastomer E being 95:5 to 50:50.
2. The multilayer film for bioprocess bags according to claim 1, wherein the weight part ratio of polyethylene a and polyethylene B in the outermost layer is 90:10 to 70:30; and/or
In the elastic layer, the weight part ratio of the styrene block copolymer C to the polyolefin elastomer D is 90:10 to 50:50; and/or
In the innermost layer, the weight part ratio of the polyolefin elastomer D to the polyolefin elastomer E is 90:10 to 70:30.
3. The multilayer film for bioprocess bags according to claim 1 or 2, characterized in that the polyethylene a is a low density polyethylene or a linear low density polyethylene; and/or
The polyethylene B is low-density polyethylene or high-density polyethylene; and/or
The styrene block copolymer C is a styrene-butadiene copolymer; and/or
The polyolefin elastomer D and the polyolefin elastomer E are copolymers of ethylene and alpha-olefin containing 4-10 carbon atoms; and/or
The barrier layer is an ethylene-vinyl alcohol copolymer; and/or
The adhesive layer is an anhydride modified ethylene copolymer.
4. The multilayer film for bioprocess bags according to claim 1 or 2, characterized in that the thickness of the outermost layer is 30 μm to 100 μm; and/or
The thickness of the elastic layer monolayer is 10-80 mu m; and/or
The thickness of the barrier layer is 5-40 mu m; and/or
The thickness of the single layer of the bonding layer is 10-40 mu m; and/or
The thickness of the innermost layer is 100-300 mu m.
5. The multilayer film for bioprocess bags according to claim 1 or 2, characterized in that the tensile strength of the multilayer film is not lower than 16 Mpa; and/or
Elongation at break not less than 350%; and/or
The dart impact strength is not lower than 1600g; and/or
The number of pinholes generated after 900 times of rubbing test is not more than 1 per piece; and/or
Puncture strength is not lower than 35N; and/or
The water vapor transmission rate is not more than 3.0 g/m 2. Day; and/or
The oxygen transmission rate is not more than 3.0 cm 3/m2. Day.
6. The multilayer film for a bioprocess bag according to claim 1 or 2, wherein the multilayer film is an outermost layer, a barrier layer, a toughening layer and an innermost layer in this order from the outside to the inside; and/or
The multilayer film comprises an outermost layer, a flexible layer, a barrier layer and an innermost layer from outside to inside in sequence; and/or
The multilayer film comprises an outermost layer, a toughening layer, a barrier layer, a toughening layer and an innermost layer from outside to inside.
7. A multi-layer film for bioprocess bags according to claim 3, characterized in that the adhesive layer is a maleic anhydride modified ethylene copolymer.
8. A disposable bag for biopharmaceutical use, prepared from the multi-layer film for bioprocess bags of any one of claims 1 to 7.
CN202211096737.9A 2022-09-08 2022-09-08 Multilayer film for bioprocess bag and application thereof Active CN115556448B (en)

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