CN114434929A - Degradable film of disposable bag for bio-pharmaceuticals and application thereof - Google Patents
Degradable film of disposable bag for bio-pharmaceuticals and application thereof Download PDFInfo
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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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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
- B32B27/06—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
- B32B27/306—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
- 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
- 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
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- 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
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
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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
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2497/00—Characterised by the use of lignin-containing materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention belongs to the field of new materials, and discloses a degradable film of a disposable bag for bio-pharmaceuticals and application thereof. The film comprises 5 layers in total from outside to inside in sequence of a protective layer, a first adhesive layer, a high barrier layer, a second adhesive layer and a liquid contact layer. The degradable film of some examples of the invention has high biodegradation speed, simultaneously has excellent biocompatibility, strength, toughness and high barrier property, and meets the harsh requirements of disposable bags for bio-pharmaceuticals; by using a large amount of completely biodegradable materials and optimizing the composition, the composite material has excellent biodegradability/compostability on the premise of considering excellent mechanical property, high barrier property and biocompatibility, and the disposable bag made of the composite material can be directly buried and composted after being sterilized.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a degradable film of a disposable bag for bio-pharmaceuticals and application thereof.
Background
In recent years, the market of imitation pharmaceuticals is rapidly developed in China, and pharmaceutical enterprises in China are launched into the market of biological pharmaceuticals. In the biopharmaceutical field, rapid development of products is crucial. Conventional stainless steel systems have not been able to support rapid development and conversion of different batches of products. Disposable products are better able to solve the above problems, and are becoming the first choice for developing new drugs in the biopharmaceutical industry. At present, the overall market scale of the global biopharmaceutical disposable consumables is about 1000 million yuan, while the Chinese market accounts for 150 million yuan, and the annual speed is increased by about 20%.
The disposable bag is used as an important consumable material of a biological pharmaceutical enterprise and mainly comprises a liquid storage bag, a liquid preparation bag, a cell reaction bag and the like. For the bags with potential infectivity after use, the bags are generally sent to a designated place for incineration treatment after high-pressure steam or dry heat sterilization; for bags that are not potentially infectious after use, they are typically sterilized, incinerated, or sent to a landfill for disposal. However, plastic wastes generate a large amount of harmful gases and fumes upon incineration, which aggravate air pollution and greenhouse effect. In addition, the films used in bags for biopharmaceuticals are generally made of petroleum-based polymers, such as polyethylene, polypropylene, etc., which are difficult to degrade when buried in soil, remain for decades, which is a serious hazard to the soil and further threaten human health and safety through the food chain. Therefore, it is imperative to develop a biodegradable disposable bag. Most of biodegradable materials are prepared from bio-based raw materials and can be degraded into harmless substances in natural environment, so that dependence of people on petroleum can be reduced, and CO in the atmosphere can not be caused2The net gain.
In 2020, the government of China put forward the aim of striving to achieve carbon peak reaching in 2030 and carbon neutralization in 2060. The wide popularization and use of the biodegradable material have positive promotion effect on realizing the aim at an early time. As the film used as the key raw material of the disposable bag, the technical development difficulty is very high, and domestic film-making enterprises have no related experience, so that more than 95 percent of the films used by domestic disposable consumable manufacturing enterprises come from imports at present. However, the films are demanding in terms of overall performance, so these imported films are almost entirely made of mature petroleum-based resins, with few attempts at bio-based resins. For example, the film needs to have excellent biocompatibility without significantly affecting the active ingredients of the drug solution; the film needs to have excellent mechanical properties, so that the manufactured bag body is safe and firm in the transportation and use processes, and leakage cannot occur; the film is also required to have excellent gas and water vapor barrier properties, to ensure controllability of the liquid environment in the biopharmaceutical process, and the like. These requirements all present challenges to the use of bio-based raw material resins, so no relevant research or report on degradable films for biopharmaceutical processes has been made worldwide to date.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a degradable film of a disposable bag for bio-pharmaceuticals and application thereof.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided:
the utility model provides a degradable film of disposable bag for bio-pharmaceuticals, by outer 5 layers of 5 in total that include protective layer, first adhesive layer, high barrier layer, second adhesive layer and liquid contact layer in proper order to interior, wherein:
the protective layer is made of a blend of polybutylene adipate/terephthalate, polybutylene succinate and polyglycolic acid;
the first adhesive layer and the second adhesive layer are made of an adhesive resin;
the high barrier layer is made of full-biodegradable vinyl alcohol copolymer;
the liquid contact layer is made of linear low density polyethylene modified with biodegradable fillers.
In some examples of degradable films, the protective layer uses PBAT and PBS with melt indexes of 1.0-15.0 g/10min at 190 ℃ and 2.16Kg test conditions.
Further, in some examples of the degradable film, the PBAT and the PBS used in the protective layer respectively have melt indexes of 2.0-8.0 g/10min at 190 ℃ and under the test condition of 2.16 Kg.
In some examples of degradable films, the PGA has a melt index of 1.0 to 15.0 g/10min at 250 ℃ under a 2.16Kg test.
Further, in some examples of the degradable film, the PGA has a melt index of 2.0 to 8.0 g/10min at 250 ℃ under a 2.16Kg test.
In some examples of degradable films, the adhesive resin has a melt index of 1.0 to 10.0 g/10min at 190 ℃ under a 2.16Kg test.
Further, in some examples of the degradable film, the adhesive resin has a melt index of 2.0-8.0 g/10min at 190 ℃ under a 2.16Kg test.
In some examples of the degradable film, the first adhesive layer and the second adhesive layer are made of an anhydride-modified adhesive resin of a full biodegradable type.
In some examples of degradable films, the fully biodegradable vinyl alcohol copolymer has a melt index of 1.0 to 15.0 g/10min at 190 ℃ under a 2.16Kg test.
Further, in some examples of the degradable film, the fully biodegradable vinyl alcohol copolymer has a melt index of 2.0-8.0 g/10min at 190 ℃ under a 2.16Kg test condition.
In some examples of degradable films, the biodegradable filler is a mixture of lignin and thermoplastic starch, the mixing ratio of thermoplastic starch and lignin is 100: 0 to 70: 30.
further, in some examples of the degradable film, the biodegradable filler is a mixture of lignin and thermoplastic starch, and the mixing ratio of the thermoplastic starch and the lignin is 100: 0 to 75: 25.
in some examples of degradable films, the liquid contact layer has a ratio of linear low density polyethylene to biodegradable filler of 90 parts by weight: 10 to 50: 50.
further, in some examples of the degradable film, the ratio of the linear low density polyethylene to the biodegradable filler in the liquid contact layer is 70: 30 to 50: 50.
in some examples of degradable films, the linear low density polyethylene has a melt index of 1.0 to 10.0 g/10min at 190 ℃ under a 2.16Kg test.
Further, in some examples of the degradable film, the linear low density polyethylene has a density of 2.0 to 8.0 g/10min at 190 ℃ under a 2.16Kg test.
In some examples of the degradable film, the linear low density polyethylene has a density of 0.87 to 0.915 g/cm3。
In some examples of degradable films, the weight ratio of poly (butylene adipate/terephthalate), poly (butylene succinate), and poly (glycolic acid) in the protective layer is PBAT: PBS: PGA = (40 to 70): (10-40): (5-30).
In some examples of degradable films, the weight ratio of poly (butylene adipate/terephthalate), poly (butylene succinate), and poly (glycolic acid) in the protective layer is PBAT: PBS: PGA = (50 to 65): (20-30): (15-25).
In some examples of the degradable film, the first adhesive layer and the second adhesive layer are made of an anhydride-modified adhesive resin of a full biodegradable type.
In some examples of degradable films, the fully biodegradable vinyl alcohol copolymer is selected from the group consisting of Nichigo G-Polymer ™ series resins.
The thickness of each layer is adjusted according to different specific application occasions.
In some examples of the degradable film, the protective layer has a thickness of 10 μm to 100 μm.
In some examples of the degradable film, the first adhesive layer has a thickness of 10 μm to 50 μm.
In some examples of degradable films, the high barrier layer has a thickness of 5 μm to 40 μm.
In some examples of the degradable film, the second adhesive layer has a thickness of 10 μm to 50 μm.
In some examples of degradable films, the liquid contact layer has a thickness of 140 μm to 500 μm.
In order to meet the requirement of the disposable bag for the bio-pharmaceuticals, the mechanical property of the film is correspondingly adjusted.
In some examples of degradable films, the tensile strength of the degradable film is not less than 18 Mpa.
In some examples of degradable films, the degradable film has an elongation at break of no less than 350%.
In some degradable film examples, the degradable film has a water vapor transmission rate of no more than 2.6 g/m2.day。
In some examples of degradable films, the degradable films have an oxygen transmission of no more than 1.5 cm3/m2.day.bar。
In some examples of degradable films, the degradable films have a degradation rate of not less than 60% under the GB/T19277.1-2011 standard test.
In some examples of the degradable film, the degradable film has a tensile strength of not less than 18 MPa, an elongation at break of not less than 350%, and a water vapor transmission of not more than 2.6 g/m2Day, oxygen transmission not exceeding 1.5 cm3/m2.day.bar。
The invention has the beneficial effects that:
the degradable film of some examples of the invention has high biodegradation speed, simultaneously has excellent biocompatibility, strength, toughness and high barrier property, and meets the harsh requirements of disposable bags for bio-pharmaceuticals.
In some embodiments of the degradable film of the present invention, the protective layer, the first adhesive layer, the high barrier layer, and the second adhesive layer are all made of completely biodegradable materials; the liquid contact layer is made of a polyethylene material having a very high solvent inertness as a main material for contacting different liquids in the biopharmaceutical process, and a certain amount of thermoplastic starch/lignin is mixed into the polyethylene to form a destructive biodegradable material. The multilayer structure of the degradable film and the material formula of each layer are scientifically designed, so that the degradable film has excellent biodegradability/compostability on the premise of considering excellent mechanical property, high barrier property and biocompatibility, and the disposable bag made of the degradable film can be directly buried for composting after being sterilized after being used.
Detailed Description
In the present invention, the abbreviations used have the following meanings:
PBAT: poly (butylene adipate terephthalate)
PBS: polybutylene succinate
PGA: polyglycolic acid
LLDPE: linear low density polyethylene
TPS: thermoplastic starch.
The utility model provides a degradable film for disposable bag for bio-pharmaceuticals, the film has 5 layer structures, by outer protective layer, first adhesive layer, high barrier layer, second adhesive layer, liquid contact layer including in proper order to interior.
The outermost layer is a protective layer which mainly plays the roles of improving the strength of the film, resisting scraping and protecting the film. The middle layer is a high barrier layer and mainly plays a role in high barrier to oxygen, carbon dioxide and other gases. The innermost layer is the liquid contact layer, which mainly serves for heat sealing, cushioning and solvent inertness. The first adhesive layer mainly serves to bond the protective layer and the high barrier layer. The second adhesive layer serves primarily to bond the high barrier layer to the liquid contact layer.
The protective layer is made of a blend of polybutylene adipate/terephthalate (PBAT), polybutylene succinate (PBS) and polyglycolic acid (PGA). Among them, PBAT has excellent biodegradability, ductility, and impact resistance, providing flexibility of the protective layer. The PBS has excellent degradation performance, good biocompatibility and heat resistance, and excellent processing performance, and can obviously improve the processability of the protective layer. PGA has good gas barrier properties, biocompatibility, and degradability, and is extremely high in mechanical strength, and can provide a protective layer with desired strength and high barrier properties. The inventor researches and discovers that a protective layer obtained by blending the three resins according to a specific proportion has excellent biodegradability, rigidity-toughness balance and high barrier property, and meets the harsh requirements of disposable bags for the bio-pharmaceuticals.
The materials of the first bonding layer and the second bonding layer are all completely biodegradable anhydride modified bonding resin.
The high barrier layer is made of full-biodegradable vinyl alcohol copolymer.
The material of the liquid contact layer is Linear Low Density Polyethylene (LLDPE) modified by biodegradable fillers.
The protective layer comprises PBAT, PBS and PGA in parts by weight (40-70): (10-40): (5-30), preferably (50-60): (20-30): (15-25).
The melt index of PBAT in the protective layer under the test conditions of 190 ℃ and 2.16Kg is 1.0-15.0 g/10min, preferably 2.0-8.0 g/10 min. Suitable PBAT are sold by BASF Corporation, for example under the trademark ecoflex (more specifically, ecoflex C1200).
The melt index of PBS in the protective layer is 1.0-15.0 g/10min, preferably 2.0-8.0 g/10min under the test condition of 190 ℃ and 2.16 Kg. Suitable PBS's are sold, for example, by Mitsubishi Chemical Performance Polymers, Inc. under the trademark BioPBS's (more specifically, BioPBS FD92 PM).
The PGA in the protective layer has a melt index of 1.0-15.0 g/10min, preferably 2.0-8.0 g/10min, at 250 ℃ and under the test condition of 2.16 Kg. Suitable PGAs are for example available under the trade mark Kuredux®(more precisely, Kuredux)®100E35) Sold by KUREHA Corporation.
The melt indexes of the fully biodegradable anhydride modified adhesive resin in the first adhesive layer and the second adhesive layer are both 1.0-10.0 g/10min, preferably 2.0-8.0 g/10min under the test conditions of 190 ℃ and 2.16 Kg. Suitable adhesive resins are sold, for example, under the trade name BTR8002P by Mitsubishi Chemical.
The melt index of the fully biodegradable vinyl alcohol copolymer in the high barrier layer under the test conditions of 190 ℃ and 2.16Kg is 1.0-15.0 g/10min, preferably 2.0-8.0 g/10 min. Suitable vinyl alcohol copolymers are sold, for example, by Mitsubishi Chemical under the trademark Nichigo G-Polymer ™ (more specifically, Nichigo G-Polymer OKS-8095P).
The biodegradable filler in the liquid contact layer is thermoplastic starch (TPS) which is single or comprises partial lignin, and the weight ratio of the TPS to the lignin is 100: 0 to 70: 30.
the LLDPE in the liquid contact layer has a density of 0.87-0.915 g/cm3The melt index under the test condition of 2.16Kg at 190 ℃ is 1.0-10.0 g/10min, preferably 2.0-8.0 g/10 min. Suitable LLDPE are sold, for example, by the DOW Chemical Company under the trademark Attane ™ (more specifically Attane ™ 4404G).
The weight ratio of LLDPE and biodegradable filler of the liquid contact layer is 90: 10 to 50: 50.
the thickness of the protective layer is 10-100 μm.
The thickness of the first adhesive layer is 10-50 μm.
The thickness of the high barrier layer is 5-40 μm.
The thickness of the second adhesive layer is 10 μm to 50 μm.
The liquid contact layer has a thickness of 140 μm to 500 μm.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that such description is merely illustrative of the features and advantages of the present invention, and is not intended to limit the scope of the claims.
Unless otherwise specified, in the following examples:
the melt index of the PBAT used is about 4.0 g/10min under the test conditions of 190 ℃ and 2.16Kg, and the specific grade is ecoflex C1200.
PBS used had a melt index of about 4.0 g/10min at 190 ℃ under the 2.16Kg test conditions, and was designated BioPBS-FD 92 PM.
The melt index of the PGA used is about 5.0 g/10min under the test conditions of 250 ℃ and 2.16Kg, and the specific mark is Kuredux® 100E35。
The melt index of the fully biodegradable adhesive resin used is about 3.0 g/10min under the test conditions of 190 ℃ and 2.16Kg, and the specific mark is BTR 8002P.
The fully biodegradable vinyl alcohol copolymer used had a melt index of about 2.0G/10 min at 190 ℃ under the test conditions of 2.16Kg, and was designated G-Polymer ™ OKS-8095P.
The LLDPE used had a density of 0.902 g/cm3The melt index at 190 ℃ under 2.16Kg test conditions was about 4.0G/10 min, with the specific designation of Attane ™ 4404G.
The preparation method of the degradable film for the disposable bag for the bio-pharmaceuticals can comprise multiple existing forms of multilayer coextrusion casting, multilayer coextrusion film blowing, extrusion compounding, extrusion laminating and the like. Taking multilayer coextrusion casting as an example, the method mainly comprises the following steps:
the method comprises the following steps: adding various raw material particles into respective material suction channels corresponding to the multilayer co-extrusion casting lines respectively, and automatically feeding the raw material particles into respective extruders in proportion through an accurate metering system;
step two: melting and plasticizing the raw materials in respective screws at a set extrusion temperature, and then layering and converging at a T-shaped die head to cast a multilayer film;
step three: and cooling, rolling, slitting and packaging the cast multilayer film to obtain a degradable film finished product.
Example 1
The protective layer is made of a blend of PBAT, PBS and PGA, and the weight ratio of PBAT, PBS and PGA in the protective layer is 55: 25: 20; the temperature of the screw is set to be 200-220-235-250 ℃ in sections;
100% of full-biodegradable tackifying resin is used for the first bonding layer and the second bonding layer, and the set temperature of the screw in sections is 190-210-230 ℃;
100% of fully biodegradable vinyl alcohol copolymer is used as the high barrier layer, and the segmented set temperature of the screw is 190-210-230 ℃;
the liquid contact layer uses a blend of LLDPE and TPS, the weight ratio of LLDPE to TPS is 70: 30, the temperature of the screw is set to be 190-210-230 ℃ in a segmented manner;
the thickness of the protective layer was 80 μm, the thickness of the first adhesive layer was 25 μm, the thickness of the high barrier layer was 20 μm, the thickness of the second adhesive layer was 25 μm, the thickness of the liquid contact layer was 170 μm, and the total thickness was 320 μm.
Example 2
The protective layer is made of a blend of PBAT, PBS and PGA, and the weight ratio of PBAT, PBS and PGA in the protective layer is 50: 30: 20; the temperature of the screw is set to be 200-220-235-250 ℃ in sections;
100% of full-biodegradable tackifying resin is used for the first bonding layer and the second bonding layer, and the set temperature of the screw in sections is 190-210-230 ℃;
100% of fully biodegradable vinyl alcohol copolymer is used as the high barrier layer, and the segmented set temperature of the screw is 190-210-230 ℃;
the liquid contact layer uses a blend of LLDPE and TPS, and the weight ratio of the LLDPE to the TPS in the liquid contact layer is 60: 40, the temperature of the screw is set to 190-210-230 ℃ in a segmented mode.
The thickness of the protective layer was 90 μm, the thickness of the first adhesive layer was 20 μm, the thickness of the high barrier layer was 25 μm, the thickness of the second adhesive layer was 20 μm, the thickness of the liquid contact layer was 170 μm, and the total thickness was 325 μm.
Example 3
The protective layer uses the blend of PBAT, PBS and PGA, and the weight ratio of PBAT, PBS and PGA in the protective layer is 60: 25: 15; the temperature of the screw is set to be 200-220-235-250 ℃ in sections;
100% of full-biodegradable tackifying resin is used for the first bonding layer and the second bonding layer, and the set temperature of the screw in sections is 190-210-230 ℃;
100% of fully biodegradable vinyl alcohol copolymer is used as the high barrier layer, and the segmented set temperature of the screw is 190-210-230 ℃;
the liquid contact layer uses a blend of LLDPE and TPS, and the weight part ratio of the LLDPE to the TPS in the liquid contact layer is 50: 50; the temperature of the screw is set to 190-210-230 ℃ in a segmented manner.
The thickness of the protective layer was 100 μm, the thickness of the first adhesive layer was 20 μm, the thickness of the high barrier layer was 25 μm, the thickness of the second adhesive layer was 20 μm, the thickness of the liquid contact layer was 155 μm, and the total thickness was 320 μm.
Example 4
The protective layer is made of a blend of PBAT, PBS and PGA, and the weight ratio of PBAT, PBS and PGA in the protective layer is 55: 30: 15; the segmented set temperature of the screw is 200-220-235-250 ℃;
100% of full-biodegradable tackifying resin is used for the first bonding layer and the second bonding layer, and the set temperature of the screw in sections is 190-210-230 ℃;
100% of fully biodegradable vinyl alcohol copolymer is used as the high barrier layer, and the segmented set temperature of the screw is 190-210-230 ℃;
the liquid contact layer uses LLDPE, TPS, a lignin blend, LLDPE, TPS, and the weight ratio of lignin is 60: 28: 12, the temperature of the screw is set to 190-.
The protective layer has a thickness of 90 μm, the first adhesive layer has a thickness of 25 μm, the high barrier layer has a thickness of 25 μm, the second adhesive layer has a thickness of 25 μm, the liquid contact layer has a thickness of 150 μm, and the total thickness is 315 μm.
Example 5
The protective layer is made of a blend of PBAT, PBS and PGA, and the weight ratio of the PBAT, the PBS and the PGA in the protective layer is 65: 20: 15; the temperature of the screw is set to be 200-220-235-250 ℃ in sections;
100% of full-biodegradable tackifying resin is used for the first bonding layer and the second bonding layer, and the set temperature of the screw in sections is 190-210-230 ℃;
100% of fully biodegradable vinyl alcohol copolymer is used as the high barrier layer, and the segmented set temperature of the screw is 190-210-230 ℃;
the liquid contact layer uses LLDPE, TPS, a lignin blend, LLDPE, TPS, and the weight ratio of lignin is 60: 30: 10, the temperature of the screw is set to 190-210-230 ℃ in a segmented manner.
The thickness of the protective layer was 100 μm, the thickness of the first adhesive layer was 25 μm, the thickness of the high barrier layer was 25 μm, the thickness of the second adhesive layer was 25 μm, the thickness of the liquid contact layer was 140 μm, and the total thickness was 315 μm.
Comparative example 1
The protective layer uses a blend of PBAT and PBS, and the weight ratio of PBAT to PBS in the protective layer is 80: 20; the temperature of the screw is set to be 200-220-235-250 ℃ in sections;
100% of full-biodegradable tackifying resin is used for the first bonding layer and the second bonding layer, and the set temperature of the screw in sections is 190-210-230 ℃;
100% of fully biodegradable vinyl alcohol copolymer is used as the high barrier layer, and the segmented set temperature of the screw is 190-210-230 ℃;
the liquid contact layer uses a blend of LLDPE and TPS, the weight ratio of LLDPE to TPS is 70: 30, the temperature of the screw is set to 190-.
The thickness of the protective layer was 80 μm, the thickness of the first adhesive layer was 25 μm, the thickness of the high barrier layer was 20 μm, the thickness of the second adhesive layer was 25 μm, the thickness of the liquid contact layer was 170 μm, and the total thickness was 320 μm.
Comparative example 2
The protective layer uses a blend of PBAT, PBS and PGA, and the weight ratio of the PBAT, the PBS and the PGA in the protective layer is 30: 30: 40; the temperature of the screw is set to be 200-220-235-250 ℃ in sections;
100% of full-biodegradable tackifying resin is used for the first bonding layer and the second bonding layer, and the set temperature of the screw in sections is 190-210-230 ℃;
100 percent of full-biodegradable vinyl alcohol copolymer is used as the high barrier layer, and the segmented set temperature of the screw is 190-210-230 ℃;
the liquid contact layer uses a blend of LLDPE and TPS, and the weight ratio of the LLDPE to the TPS in the liquid contact layer is 60: 40, the temperature of the screw is set to 190-210-230 ℃ in a segmented mode.
The thickness of the protective layer was 90 μm, the thickness of the first adhesive layer was 20 μm, the thickness of the high barrier layer was 25 μm, the thickness of the second adhesive layer was 20 μm, the thickness of the liquid contact layer was 170 μm, and the total thickness was 325 μm.
Comparative example 3
The protective layer uses a blend of PBAT, PBS and PGA, and the weight ratio of the PBAT, the PBS and the PGA in the protective layer is 90: 5: 5; the temperature of the screw is set to be 200-220-235-250 ℃ in sections;
100% of full-biodegradable tackifying resin is used for the first bonding layer and the second bonding layer, and the set temperature of the screw in sections is 190-210-230 ℃;
100% of fully biodegradable vinyl alcohol copolymer is used as the high barrier layer, and the segmented set temperature of the screw is 190-210-230 ℃;
the liquid contact layer uses LLDPE, TPS, a lignin blend, LLDPE, TPS, and the weight ratio of lignin is 60: 30: 10, the temperature of the screw is set to 190-210-230 ℃ in a segmented manner.
The thickness of the protective layer was 100 μm, the thickness of the first adhesive layer was 25 μm, the thickness of the high barrier layer was 25 μm, the thickness of the second adhesive layer was 25 μm, the thickness of the liquid contact layer was 140 μm, and the total thickness was 315 μm.
The degradable films prepared in examples 1 to 5 and comparative examples 1 to 3 were subjected to performance tests, which mainly included degradability, mechanical properties, water vapor permeability, and oxygen permeability, and the results are shown in the following table. Wherein, the degradability is tested according to GB/T19277.1-2011 standard, the tensile strength and the elongation at break are tested according to ASTM D882 standard, the water vapor permeability is tested according to ASTM F1249 standard, and the oxygen permeability is tested according to ASTM D3985 standard. The results are shown in Table 1.
TABLE 1
| Testing performance | S1 | S2 | S3 | S4 | S5 | D1 | D2 | D3 |
| Degradation Rate (%) | 66% | 69% | 73% | 70% | 68% | 66% | 67% | 68% |
| Tensile Strength (MPa) | 18.6 | 20.4 | 19.4 | 19.8 | 18.9 | 14.1 | 25.2 | 15.2 |
| Elongation at Break (%) | 405% | 366% | 372% | 385% | 392% | 465% | 206% | 488% |
| Water vapor transmission (g/m)2.day) | 1.8 | 1.6 | 2.0 | 2.2 | 2.5 | 3.0 | 1.9 | 2.6 |
| Oxygen transmission capacity (cm)3/m2.day.bar) | 0.6 | 0.5 | 0.5 | 0.6 | 1.2 | 2.9 | 0.4 | 2.2 |
Note: s denotes the examples, e.g. S1 denotes example 1; d denotes comparative example, and D1 denotes comparative example 1.
From the data in table 1, it can be seen that:
1) the degradable film (examples 1-5) for the disposable bag for bio-pharmaceuticals, which is prepared by the invention, has excellent biodegradability, mechanical property, water vapor barrier property and oxygen barrier property, and has a good market application prospect.
2) The protective layer of comparative example 1, which does not contain PGA rigid material, causes a significant decrease in tensile strength of the film, and the resulting bag has a possibility of leakage; and the absence of PGA also leads to a decrease in the overall gas barrier properties of the film, which is not suitable for application.
3) The protective layer in comparative example 2 has a hard film material due to the too high PGA content of 40%, and has an elongation at break of only about 200%, and the manufactured bag body is prone to wrinkle deformation and leakage, and is not suitable for application.
4) In comparative example 3, the proportion of PBAT was too high of 90%, and the tensile strength was lowered due to insufficient rigidity of the protective layer, which was not suitable for application.
The foregoing is a more detailed description of the invention and is not to be taken in a limiting sense. It will be apparent to those skilled in the art that simple deductions or substitutions without departing from the spirit of the invention are within the scope of the invention.
Claims (10)
1. A biodegradable film of a disposable bag for bio-pharmaceuticals, comprising: include protective layer, first adhesive layer, high barrier layer, second adhesive layer and liquid contact layer by outer 5 layers altogether in proper order to interior, wherein:
the protective layer is made of a blend of polybutylene adipate/terephthalate, polybutylene succinate and polyglycolic acid;
the first adhesive layer and the second adhesive layer are made of an adhesive resin;
the high barrier layer is made of full-biodegradable vinyl alcohol copolymer;
the liquid contact layer is made of linear low density polyethylene modified with biodegradable fillers.
2. The degradable film of claim 1, wherein:
the melt indexes of PBAT and PBS used in the protective layer are respectively 1.0-15.0 g/10min at 190 ℃ under the test condition of 2.16 Kg; and/or
The melt index of the PGA under the test conditions of 250 ℃ and 2.16Kg is 1.0-15.0 g/10 min; and/or
The melt index of the adhesive resin under the test conditions of 190 ℃ and 2.16Kg is 1.0-10.0 g/10 min; and/or
The melt index of the fully biodegradable vinyl alcohol copolymer under the test conditions of 190 ℃ and 2.16Kg is 1.0-15.0 g/10 min; and/or
The biodegradable filler is a mixture of lignin and thermoplastic starch, and the mixing ratio of the thermoplastic starch to the lignin is 100: 0 to 70: 30, of a nitrogen-containing gas; and/or
In the liquid contact layer, the weight ratio of the linear low-density polyethylene to the biodegradable filler is 90: 10 to 50: 50; and/or
The melt index of the linear low-density polyethylene under the test condition of 190 ℃ and 2.16Kg is 1.0-10.0 g/10 min; and/or
The linear low density polyethylene has a density of 0.87 to 0.915 g/cm3。
3. The degradable film of claim 2, wherein:
the melt indexes of PBAT and PBS used in the protective layer are respectively 2.0-8.0 g/10min at 190 ℃ under the test condition of 2.16 Kg; and/or
The melt index of the PGA under the test conditions of 250 ℃ and 2.16Kg is 2.0-8.0 g/10 min; and/or
The melt index of the adhesive resin under the test conditions of 190 ℃ and 2.16Kg is 2.0-8.0 g/10 min; and/or
The melt index of the fully biodegradable vinyl alcohol copolymer is 2.0-8.0 g/10min at 190 ℃ under the test condition of 2.16 Kg; and/or
The biodegradable filler is a mixture of lignin and thermoplastic starch, and the mixing ratio of the thermoplastic starch to the lignin is 100: 0 to 75: 25; and/or
In the liquid contact layer, the weight part ratio of the linear low-density polyethylene to the biodegradable filler is 70: 30 to 50: 50; and/or
The linear low-density polyethylene has a melt index of 2.0-8.0 g/10min at 190 ℃ under the test condition of 2.16 Kg.
4. The degradable film according to any one of claims 1 to 3, wherein: in the protective layer, the weight ratio of the polybutylene adipate/terephthalate, the polybutylene succinate and the polyglycolic acid is PBAT: PBS: PGA = (40 to 70): (10-40): (5-30).
5. The degradable film according to any one of claims 1 to 3, wherein: the first adhesive layer and the second adhesive layer are made of an anhydride-modified adhesive resin of a fully biodegradable type.
6. The degradable film according to any one of claims 1 to 3, wherein: the fully biodegradable vinyl alcohol copolymer is selected from Nichigo G-Polymer ™ series resin.
7. The degradable film according to any one of claims 1 to 3, wherein: the thickness of the protective layer is 10-100 μm; and/or
The thickness of the first bonding layer is 10-50 μm; and/or
The thickness of the high barrier layer is 5-40 μm; and/or
The thickness of the second adhesive layer is 10-50 μm; and/or
The thickness of the liquid contact layer is 140-500 μm.
8. The degradable film of claim 4, wherein: in the protective layer, the weight ratio of the polybutylene adipate/terephthalate, the polybutylene succinate and the polyglycolic acid is PBAT: PBS: PGA = (50 to 65): (20-30): (15-25).
9. The degradable film according to any one of claims 1 to 3, wherein: of said degradable film
The tensile strength is not lower than 18 Mpa; and/or
The elongation at break is not less than 350 percent; and/or
The water vapor transmission capacity is not more than 2.6 g/m2Day; and/or
Oxygen permeability of not more than 1.5 cm3/m2Bar.day; and/or
The degradation rate under the GB/T19277.1-2011 standard test is not less than 60%.
10. A disposable bag for biopharmaceutical use comprising the degradable film of any of claims 1-9.
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| CN202210107146.0A CN114434929B (en) | 2022-01-28 | 2022-01-28 | Degradable film of disposable bag for bio-pharmaceuticals and application thereof |
| PCT/CN2022/136583 WO2023142684A1 (en) | 2022-01-28 | 2022-12-05 | Degradable thin film of disposable bag for biopharmacy and use thereof |
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| CN202210107146.0A CN114434929B (en) | 2022-01-28 | 2022-01-28 | Degradable film of disposable bag for bio-pharmaceuticals and application thereof |
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| WO2023142684A1 (en) * | 2022-01-28 | 2023-08-03 | 上海乐纯生物技术股份有限公司 | Degradable thin film of disposable bag for biopharmacy and use thereof |
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| RU2450934C2 (en) * | 2007-12-24 | 2012-05-20 | Чунгвае Корпорейшн | Multilayer film with high impermeability for article containing functional medical solutions |
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| CN114434929B (en) * | 2022-01-28 | 2022-09-16 | 上海乐纯生物技术有限公司 | Degradable film of disposable bag for bio-pharmaceuticals and application thereof |
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