CN113619242A - Biodegradable high-barrier paper-plastic packaging composite film and preparation method thereof - Google Patents
Biodegradable high-barrier paper-plastic packaging composite film and preparation method 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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0021—Combinations of extrusion moulding with other shaping operations combined with joining, lining or laminating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- 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
- B32B27/10—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 paper or cardboard
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/14—Printing or colouring
- B32B38/145—Printing
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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
- 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
- B65D65/40—Applications of laminates for particular packaging purposes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/12—Coating on the layer surface on paper layer
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7163—Biodegradable
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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Abstract
The invention provides a biodegradable high-barrier paper-plastic packaging composite film and a preparation method thereof, the biodegradable high-barrier paper-plastic packaging composite film sequentially comprises an ink layer, a paper layer, a barrier coating, an adhesive layer and a PLA layer from the outside to the inside, wherein the PLA layer is modified by a thermoplastic elastomer, the temperature resistance and toughness of the PLA layer can be improved after modification, the heat sealing performance of the PLA layer is ensured, and the packaging requirements of different contents and different weights are met; the barrier coating can ensure that the final finished product has good barrier property and the shelf life of the contents is prolonged. The biodegradable high-barrier paper-plastic packaging composite film has the advantages of exquisite printing appearance, good display effect and the like, is made of degradable materials, can be biodegraded after being used, and has no pollution to the environment.
Description
Technical Field
The invention belongs to the field of packaging materials, and particularly relates to a biodegradable high-barrier paper-plastic packaging composite film and a preparation method thereof.
Background
The traditional plastic products become common consumables in life of people due to the characteristics of lightness and low price. However, since the plastic products are difficult to degrade, the plastic products left after being discarded can bring serious harm to the environment, namely the plastic products are commonly called as 'white pollution'. According to the analysis of Kearney, only 8% of plastics are currently recycled in the world, and 800 million tons of plastic waste enter the ocean every year. The total amount of global plastic usage is about 30% from the packaging article, which number amounts to 1.1 million tons in 2019. By 2050, plastic production is expected to increase dramatically, and this number is predicted to reach 7 billion tons. If no countermeasures are taken, this would result in 6.44 million tons of plastic entering the landfill annually. With the increasing proportion of the packaging in the global plastic and the increasing awareness of consumers, consumers demand enterprises to change.
In the conventional plastic package, high polymer films such as PE (polyethylene), PET (polyethylene terephthalate), PP (polypropylene), PVC (polyvinyl chloride), and PA (nylon) are generally used as base materials, and among these high polymer films, PE, PET, PP, and PVC all belong to non-biodegradable high polymer materials, and PA is a degradable material, but its degradation period is generally over 30 years. These high molecular materials are not suitable for the development of the new generation of degradable plastic packaging.
In the research and development of degradable plastics, the current main global trend is starch-based plastics, PLA, PBAT. The PLA (polylactic acid) is pollution-free in the production process, reliable in biosafety, good in mechanical property and easy to process, the degraded products are carbon dioxide and water, the environment cannot be influenced, the PLA is a well-known degradable material with the greatest development prospect, and the PLA can be used for manufacturing food packages, medical packages, agricultural mulching films and the like.
However, PLA has the disadvantages of poor heat resistance, low softening temperature, difficult film formation, brittle and breakable quality, general barrier property and the like. If these problems are solved by the modification method, the cost is greatly increased. This is also the main reason why PLA plastic articles are not currently used on a large scale.
At present, the current situation of relevant researches of PLA at home and abroad is as follows:
(1) the PLA technology has higher barrier and still starts at home
PLA (polylactic acid) is a polymer obtained by polymerizing lactic acid produced by biological fermentation as a main raw material. The single lactic acid molecule has one hydroxyl group and one carboxyl group, and a plurality of lactic acid molecules are combined together, the hydroxyl group is subjected to dehydration condensation with the carboxyl group of other molecules, and the carboxyl group is subjected to dehydration condensation with the hydroxyl group of other molecules to form polylactic acid.
There are two main methods for preparing PLA, i.e., lactide ring-opening polymerization method and direct polycondensation method, and the ring-opening polymerization method is mainly used in industry. The synthesis and purification of the intermediate lactide are core technologies and difficulties in the existing PLA process flow, the reaction conditions are severe, the process is complex, the technical requirements are high, the production cost is high, and the method is a main technical barrier for expanding the PLA production of domestic enterprises. At present, the PLA productivity is mainly concentrated overseas, and the domestic PLA is still in a starting stage.
The polylactic acid technology in China is mainly researched and developed by the cooperation of enterprises and scientific research institutions. Shanghai Tongjiliang company is from Tongjie university, adopts direct polycondensation production process, and has the production capacity of lactic acid-polylactic acid. The Zhejiang sea lactide technology is from Changchun chemical institute, the lactide is successfully produced, partial self-supply can be realized, the company is accumulated by relying on biotechnology and continuously extends to the upstream and downstream industrial chains of polylactic acid, but the company lacks the production of raw material lactic acid at present and needs to purchase enterprises such as national Jindan science and technology. Jindan science and technology and Nanjing university cooperate, an organic guanidine catalysis process is adopted, an attempt is made to get through a lactic acid-lactide industrial chain, the pilot test result is better, and the cost is expected to be continuously reduced along with the improvement of engineering capacity. The technology of Chinese food science and technology comes from Belgiglade, the cooperation of the two has established a whole industrial chain production base of corn-lactic acid-lactide-polylactic acid in Anhui, the company has mastered the lactide production process and processing technology, and the lactide production project is steadily advancing. Therefore, the technical difficulty of PLA is mainly in lactide, and many domestic enterprises are actively developing the lactide production technology, trying to break through the technical barriers of the PLA industry, breaking through the whole industrial chain of lactic acid-lactide-polylactic acid and enhancing the cost advantage.
(2) The application of PLA is limited, and modification research is urgent
Although PLA has many advantages, there are also many disadvantages in real world applications: such as poor toughness, lack of elasticity and flexibility, hard and brittle texture, relatively low melt strength, too slow a crystallization rate, etc., limit the usefulness of PLA in many applications. The chemical structure of PLA contains a large number of ester bonds, so that the PLA has poor hydrophilicity, the degradation rate needs to be controlled, and the like. And the PLA has higher price, which increases the cost of raw materials and limits the commercial popularization of the PLA. Therefore, aiming at the defects, modification of PLA becomes the main research direction of related researchers at home and abroad in recent years, so as to improve the material performance and degrade the product cost. At present, physical modification research is mainly used at home and abroad in this aspect.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a biodegradable high-barrier paper-plastic packaging composite film and a preparation method thereof, the composite film is made of degradable materials, can be biodegraded after use, and has no pollution to the environment, and the composite film comprises a PLA layer modified by a thermoplastic elastomer, which can improve the temperature resistance and toughness, ensure the heat sealing performance, and meet the packaging requirements of different contents and different weights.
In order to achieve the purpose, the invention adopts the technical scheme that:
a biodegradable high-barrier paper-plastic packaging composite film comprises an ink layer, a paper layer, a barrier coating, an adhesive layer and a PLA layer which are sequentially arranged from the outside to the inside; the PLA layer is obtained by heating PLA particles by a casting machine, adding a degradable thermoplastic elastomer, fully mixing and then extruding to form a film, wherein the degradable thermoplastic elastomer is PBAT and PPC.
The PLA layer comprises the following components in parts by weight: 55-60 parts of PLA, 15-20 parts of PBAT, 5-10 parts of PPC and 0.5-2 parts of a compatilizer or chain extender; the compatilizer is a bifunctional compatilizer KT20 or EsunBio5004K, and the chain extender is a BASF epoxy chain extender ADR 4468.
The ink layer is degradable water-based ink; the paper layer is kraft paper, wood pulp paper or glassine paper.
The barrier coating is a PVA film.
The adhesive layer is solvent-free polyurethane adhesive.
The preparation method of the biodegradable high-barrier paper-plastic packaging composite film comprises the following steps:
1) preparing a PVA solution, coating the PVA solution on one surface of the paper layer, and drying to obtain a barrier coating;
2) printing an ink layer on the other surface of the paper layer;
3) adding PLA particles and a compatilizer or a chain extender into a casting machine, uniformly mixing, heating to enable the PLA particles to reach a molten state, then adding PBAT and PPC, fully mixing, and extruding through a flat sheet-shaped die to form a film to obtain a PLA layer;
4) and bonding the barrier coating with the PLA layer by using a solvent-free polyurethane adhesive to obtain the biodegradable high-barrier paper-plastic packaging composite film.
The specific operation of the step 1) is as follows: adding 50-80 parts of PVA powder, 10-20 parts of plasticizer and 3-10 parts of heat stabilizer into 60-80 parts of 80-95 ℃ deionized water according to mass fraction, and uniformly mixing to prepare a PVA solution; defoaming, cooling, filtering and extruding the PVA solution to obtain a solution; coating the solution on a paper layer at 40-60 ℃ until the thickness of a wet film is 300-500 microns, drying at 60-100 ℃, and hot-pressing to flatten the paper to obtain a barrier coating; wherein the plasticizer is sorbitol or triethanolamine, and the heat stabilizer is laurate or zinc stearate; drying time is 1-5 minutes, and hot pressing is carried out on paper by adopting a flattening roller.
The specific operation of the step 3) is as follows: adding PLA particles and a compatilizer or a chain extender into a casting machine, mixing for 20-30 min, heating to 170-180 ℃, then cooling to 140-160 ℃, adding PBAT and PPC, mixing for 1-2 h, and extruding through a flat sheet-shaped die to form a film, wherein the film forming temperature is 40-60 ℃.
The specific operation of bonding in the step 4) is as follows: at room temperature, rolling a component A of the solvent-free polyurethane adhesive on the PLA layer, spraying a component B at 35-45 ℃, and pressing the barrier coating on the PLA layer, wherein the pressing temperature is room temperature-60 ℃;
or mixing the component A and the component B of the solvent-free polyurethane adhesive at 35-45 ℃, spraying the mixture on a PLA layer, and pressing the separation coating on the PLA layer at room temperature-60 ℃;
or, the single-component solvent-free polyurethane adhesive is coated on the PLA layer in a roller coating or spraying manner, and the barrier coating is pressed on the PLA layer, wherein the pressing temperature is room temperature to 60 ℃.
And curing is carried out after bonding in the step 4), wherein the curing process conditions are as follows, the temperature is 40-60 ℃, and the time is 30-72 hours.
Compared with the prior art, the invention has the beneficial effects that:
the biodegradable high-barrier paper-plastic packaging composite film provided by the invention sequentially comprises an ink layer, a paper layer, a barrier coating, an adhesive layer and a PLA layer from the outside to the inside, wherein the PLA layer is modified by a thermoplastic elastomer, and the temperature resistance and toughness of the PLA layer can be improved after modification, so that the heat sealing performance of the PLA layer can be ensured, and the packaging requirements of different contents and different weights can be met. The barrier coating can ensure that the final finished product has good barrier property and the shelf life of the contents is prolonged. The biodegradable high-barrier paper-plastic packaging composite film has the advantages of exquisite printing appearance, good display effect and the like, is made of degradable materials, can be biodegraded after being used, has no pollution to the environment, accords with the global commitment book of new plastic economy, is expected to be exported to countries and regions where degradable plastic products such as Europe and America are applied in a large scale except for domestic sale, and has good market prospect.
Further, the PLA layer in the invention is modified by the thermoplastic elastomer, in the modification of the PLA, the ratio of the PLA particles and the thermoplastic elastomer is balanced with the toughness, the heat sealing performance and the cost of the PLA film after film forming by optimizing parameters, and the production and processing cost is controlled on the premise of ensuring the toughness and the heat sealing performance.
Furthermore, the selection of paper and ink in the invention ensures that the final product has good printing performance and appearance effect, and can be naturally degraded at normal temperature and normal pressure.
Furthermore, the selection of the solvent-free adhesive and the control of the process parameters in the invention ensure that the compounded material has good compounding fastness, surface smoothness and stiffness.
The preparation method of the biodegradable high-barrier paper-plastic packaging composite film provided by the invention is based on the degradable characteristics of paper and polylactic acid (PLA) in natural environment, adopts a solvent-free composite process to compound the PLA film and the paper through pretreatment of materials, adjustment of material proportion, control of process parameters and the like, and finally solves the problems of insufficient temperature resistance, flexibility, barrier property and the like through modification of the PLA film and preparation of a barrier coating. According to the invention, no organic solvent or solvent type ink is used in the preparation process, the green printing technology is applied in the whole preparation process, good prevention and control means are provided before and after production, the generation of organic waste gas can be effectively reduced, the production process is pollution-free, and the environmental protection requirement is met. The key technology of the invention is PLA modification processing technology, on the basis of the traditional blending mode, an extrusion tape casting process is adopted, PLA particles are heated to a certain temperature by a tape casting machine, and the degradable thermoplastic elastomer is added, fully mixed and extruded into a film through a flat sheet-shaped neck mold. The method has the advantages that the prepared PLA film has higher thickness precision and better transparency, the toughness and the heat sealing performance of the PLA film are obviously improved while the mechanical performance of the PLA is ensured, the production efficiency is high, the cost is reduced, the economy is good, and the method is favorable for mass production. Compared with the traditional copolymerization and blending, has obvious advantages.
Drawings
FIG. 1 is a schematic structural diagram of a biodegradable high-barrier paper-plastic packaging composite film according to the present invention;
wherein: 1 is an ink layer, 2 is a paper layer, 3 is a barrier coating, 4 is an adhesive layer, and 5 is a PLA layer.
Detailed Description
The present invention is described in further detail below.
Referring to fig. 1, the biodegradable high-barrier paper-plastic packaging composite film provided by the invention comprises an ink layer 1, a paper layer 2, a barrier coating layer 3, an adhesive layer 4 and a PLA layer 5 which are sequentially arranged from the outside to the inside; the PLA layer 5 is obtained by modifying a degradable thermoplastic elastomer into a film, wherein the degradable thermoplastic elastomer is PBAT and PPC.
In order to ensure the biodegradation effect, the selected materials of the invention are all green and environment-friendly materials, wherein the ink layer 1 is degradable water-based ink, for example, WPH series degradable water-based ink products of Guangdong Jiajing science and technology corporation can be used, and the products obtain a certification certificate of the biodegradable materials, namely European Union OK composite certification. The paper layer 2 can be kraft paper, wood pulp paper or glassine paper. The selection of paper and printing ink ensures that the final product has good printing performance and appearance effect, and can be naturally degraded at normal temperature and normal pressure. The adhesive layer 4 is a solvent-free polyurethane adhesive, can be a single-component adhesive or a two-component adhesive, can realize the adhesion and connection of media under the condition of no solvent, is a potential adhesive which is green and environment-friendly and can be used for food packaging and the like, and can ensure that the compounded material has good compounding fastness, surface flatness and stiffness.
In the invention, the PVA film is selected as the barrier coating 3, the PVA has unique strong cohesiveness, involucra flexibility, smoothness, oil resistance, solvent resistance, protective colloid property, gas barrier property and wear resistance, and is used as a fiber raw material and also used for producing products such as coating, adhesive, paper processing agent, emulsifier, dispersant, film and the like in a large quantity, and the application range of the PVA is in the industries such as textile, food, medicine, construction, wood processing, paper making, printing, packaging, agriculture, steel, polymer chemical industry and the like. The PVA powder, the plasticizer and the heat stabilizer are added into the deionized water together to prepare the PVA solution for coating, so that the barrier coating 3 is obtained, and the final finished product can be ensured to have good barrier property and the quality guarantee period of the content is prolonged. In addition, PVA can be decomposed and degraded by specific bacteria in soil, and has the performance of environmental protection.
PLA has many advantages, but also has many disadvantages: for example, PLA has poor toughness, lacks elasticity and flexibility, has hard texture and high brittleness, and the like, so the invention selects the thermoplastic elastomers (PBAT and PPC) to modify the PLA, and the specific mixture ratio is as follows: 55-60 parts of PLA, 15-20 parts of PBAT, 5-10 parts of PPC and 0.5-2 parts of compatilizer or chain extender. The compatilizer is a bifunctional compatilizer KT20 or EsunBio5004K, and the chain extender is a BASF epoxy chain extender ADR 4468.
PLA (polylactic acid) polylactic acid, also called polylactide, is a polyester polymer obtained by polymerizing lactic acid as a main raw material, is a novel biodegradable material, and has good glossiness, transparency and hand feeling, but poor temperature resistance and insufficient strength. PBAT belongs to thermoplastic biodegradable plastic, is a copolymer of butanediol adipate and butanediol terephthalate, has the characteristics of PBA and PBT, and has better ductility and elongation at break as well as better heat resistance and impact property; in addition, the biodegradable plastic has excellent biodegradability, and is one of the best degradable materials which are very active in the research of the current biodegradable plastics and are applied to the market. The polypropylene carbonate (PPC), also called polymethyl ethylene carbonate, is a completely degradable environment-friendly plastic synthesized by taking carbon dioxide and propylene oxide as raw materials. PPC, PLA and PBAT all belong to aliphatic resin, are biodegradable materials, and have obvious characteristics of the three raw materials. The softening point of PPC is low and is only 33-35 ℃, but the toughness is good; PLA has a softening point of 58 ℃, good rigidity, but poor toughness; the two properties are complementary, and the PPC modified PLA is an ideal material, but the compatibility of the two is extremely poor. If both are blended with PBAT, the complementarity is also strong, but compatibility remains a significant problem.
When PLA, PPC and PBAT modified films are prepared, the compatibility is poor, and various properties of the film, such as appearance and physical properties (tensile strength, breaking strength, ductility and processability), are seriously affected. Therefore, to improve various properties of the film, a proper compatilizer needs to be added for pretreatment, so as to improve the dispersibility and flowability of the material and the compatibility with downstream resin. The compatilizer has the following properties of enhancing the compatibility in a formula system, assisting the molding of the granules and increasing the toughness and strength of the granules. 2. The mechanical properties of toughness, tensile strength and the like of the product are improved, and the properties of glossiness, light transmittance, load bearing resistance and the like of the film are improved. 3. By increasing the dispersibility and compatibility of the formula system, the purposes of increasing the using amount of the filler, reducing the overall cost and improving partial performance are achieved.
The bifunctional compatibilizer KT20 (Shenyang Ketong plastics science and technology Co., Ltd.) is a terpolymer of ethylene, maleic anhydride and glycidyl ester with high molecular weight. KT20 can influence the mechanical properties, thermal properties, dynamic rheological properties and microscopic morphology of PLA and PBAT blend, the maleic anhydride and epoxy functional groups contained in the blend can be chemically bonded with PLA and PBAT, KT20 can inhibit the promotion effect of PBAT on PLA cold crystallization, improve the compatibility of PLA and PBAT, improve the interfacial bonding force of the blend two-phase system, and the KT20 with proper dosage can obviously improve the comprehensive mechanical properties of the material.
The PLA/PBAT compatibilizer EsunBio5004K (Shenzhen Guanghua Webber, Inc.) has the following advantages: 1. the material is degradable, and is low-carbon and environment-friendly; 2. good compatibility with material matrix; 3. the processing performance is good, the process range is wide, the forming is easy, the water gap is not broken, the cooling and shaping are quick, and the demoulding is easy; 4. the product has good surface glossiness; 5. the product has low shrinkage, good dimensional stability and strong anti-warping capability. The compatibilizer EsunBio5004K is mainly applied to compatibilization modification of PLA and PBAT, can improve the interface strength of the PBAT and the PLA, can also be used for adding a filler to the PLA, adding a glass fiber to the PLA and the like, improves the bonding force between the filler and the PLA interface, improves the compatibility, and meanwhile, has an obvious toughening effect on the PLA without influencing the degradation of the PLA. Can be used for biodegradable film material, biodegradable injection molding material, etc.
The BASF epoxy chain extender ADR 4468 (Shanghai nano plastic alloy science and technology Limited) is a copolymer containing epoxy functional groups, nine active groups of epoxy groups on each molecule and reactive groups (hydroxyl, carboxyl, amino and thioether groups) of thermoplastic engineering plastics are subjected to a linking reaction to form a branched molecular structure, degraded molecular chains are recoupled in the processes of synthesis, processing, repeated processing and recovery to improve the weight average molecular weight, so that the mechanical property, the thermal property, the processing property and the optical balance of the material are improved or recovered; and the performance of the recycled plastic can be close to that of the original raw material. The following effect will occur after addition of ADR 4468: 1. chain extension capability, namely, improving the molecular weight, increasing the strength and viscosity of a melt, improving the mechanical property of the material, and improving the processing stability and the mechanical property of a returned material; 2. compatibility-improving compatibility between different polycondensate materials.
Example 1
The preparation method of the biodegradable high-barrier paper-plastic packaging composite film provided by the invention comprises the following steps:
1) adding 50 parts of PVA powder, 15 parts of plasticizer sorbitol and 3 parts of thermal stabilizer laurate into 70 parts of 90 ℃ deionized water according to mass fraction, and uniformly mixing to prepare a PVA solution; defoaming, cooling, filtering and extruding the PVA solution to obtain a solution; coating the solution on the paper layer (2) at 40 ℃ until the wet film thickness is 300 microns, drying at 60 ℃ for 5 minutes, and flattening the paper by using a flattening roller to obtain a barrier coating (3);
2) printing degradable water-based ink on the other side of the kraft paper by adopting a gravure printing technology;
3) adding 55 parts by weight of PLA particles and 1 part by weight of bifunctional compatibilizer KT20 into a casting machine, mixing for 20min, heating to 175 ℃, enabling the PLA particles to reach a molten state, then cooling to 140 ℃, adding 18 parts by weight of PBAT and 10 parts by weight of PPC, mixing for 2h, and extruding through a flat sheet-shaped neck mold to form a film, wherein the film forming temperature is 50 ℃, so as to obtain a PLA layer 5;
4) the method is characterized in that the barrier coating is bonded with the PLA layer through a solvent-free polyurethane adhesive, and the method comprises the following specific steps: at room temperature, rolling a component A of the solvent-free polyurethane adhesive on the PLA layer, spraying a component B at 45 ℃, and pressing the barrier coating on the PLA layer, wherein the pressing temperature is 40 ℃; after bonding, carrying out curing treatment at the curing temperature of 40 ℃ for 72 h; the biodegradable high-barrier paper-plastic packaging composite film is obtained.
Example 2
The preparation method of the biodegradable high-barrier paper-plastic packaging composite film provided by the invention comprises the following steps:
1) adding 60 parts of PVA powder, 10 parts of plasticizer triethanolamine and 5 parts of heat stabilizer laurate into 60 parts of deionized water at 95 ℃ according to mass fraction, and uniformly mixing to prepare a PVA solution; defoaming, cooling, filtering and extruding the PVA solution to obtain a solution; coating the solution on a paper layer (2) at 50 ℃ with the wet film thickness of 400 microns, drying at 100 ℃ for 1 minute, and flattening the paper by using a flattening roller to obtain a barrier coating (3);
2) printing degradable water-based ink on the other side of the wood pulp paper by adopting a gravure printing technology;
3) adding 58 parts of PLA particles and 2 parts of compatilizer EsunBio5004K into a casting machine according to parts by weight, mixing for 30min, heating to 170 ℃ to enable the PLA particles to be in a molten state, cooling to 150 ℃, adding 20 parts of PBAT and 8 parts of PPC, mixing for 1.5h, extruding through a flat sheet-shaped die to form a film, wherein the film forming temperature is 40 ℃, and thus obtaining a PLA layer 5;
4) the method is characterized in that the barrier coating is bonded with the PLA layer through a solvent-free polyurethane adhesive, and the method comprises the following specific steps: mixing the component A and the component B of the solvent-free polyurethane adhesive at 35 ℃, immediately spraying the mixture on a PLA layer, and pressing a barrier coating on the PLA layer, wherein the pressing temperature is room temperature; after bonding, carrying out curing treatment at 50 ℃ for 48 h; the biodegradable high-barrier paper-plastic packaging composite film is obtained.
Example 3
The preparation method of the biodegradable high-barrier paper-plastic packaging composite film provided by the invention comprises the following steps:
1) adding 80 parts of PVA powder, 20 parts of plasticizer triethanolamine and 10 parts of heat stabilizer zinc stearate into 80 parts of deionized water at 80 ℃ according to mass fraction, and uniformly mixing to prepare a PVA solution; defoaming, cooling, filtering and extruding the PVA solution to obtain a solution; coating the solution on the paper layer (2) at 60 ℃ with the wet film thickness of 500 microns, drying at 80 ℃ for 3 minutes, and flattening the paper by using a flattening roller to obtain a barrier coating (3);
2) printing degradable water-based ink on the other side of the glassine paper by adopting a gravure printing technology;
3) adding 60 parts by weight of PLA particles and 0.5 part by weight of BASF epoxy chain extender ADR 4468 into a casting machine, mixing for 25min, heating to 180 ℃ to enable the PLA particles to be in a molten state, cooling to 160 ℃, adding 15 parts by weight of PBAT and 5 parts by weight of PPC, mixing for 1h, extruding through a flat sheet-shaped die to form a film, wherein the film forming temperature is 60 ℃, and thus obtaining a PLA layer 5;
4) the method is characterized in that the barrier coating is bonded with the PLA layer through a solvent-free polyurethane adhesive, and the method comprises the following specific steps: coating or spraying a single-component solvent-free polyurethane adhesive on the PLA layer in a roller way, and pressing the barrier coating on the PLA layer at the pressing temperature of 60 ℃; curing treatment is carried out after bonding, wherein the curing temperature is 60 ℃, and the curing time is 30 hours; the biodegradable high-barrier paper-plastic packaging composite film is obtained.
Through performance tests, the biodegradable high-barrier paper-plastic packaging composite film has excellent water vapor and oxygen barrier performance and excellent oil/grease/alcohol resistance; a water vapor permeability of 80 to 90% RH (g/m) at 38 DEG C2(d) has an oxygen transmission rate of 0 to 0.02% RH (cm) at 23 DEG C3/m2/d)。
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A biodegradable high-barrier paper-plastic packaging composite film is characterized in that: comprises an ink layer (1), a paper layer (2), a barrier coating (3), an adhesive layer (4) and a PLA layer (5) which are arranged from the outside to the inside in sequence; the PLA layer (5) is obtained by heating PLA particles by a casting machine, adding a degradable thermoplastic elastomer, fully mixing and then extruding to form a film, wherein the degradable thermoplastic elastomer is PBAT and PPC.
2. The biodegradable high-barrier paper-plastic packaging composite film according to claim 1, characterized in that: the PLA layer (5) comprises the following components in parts by weight: 55-60 parts of PLA, 15-20 parts of PBAT, 5-10 parts of PPC and 0.5-2 parts of a compatilizer or chain extender; the compatilizer is a bifunctional compatilizer KT20 or EsunBio5004K, and the chain extender is a BASF epoxy chain extender ADR 4468.
3. The biodegradable high-barrier paper-plastic packaging composite film according to claim 1, characterized in that: the ink layer (1) is degradable water-based ink; the paper layer (2) is kraft paper, wood pulp paper or glassine paper.
4. The biodegradable high-barrier paper-plastic packaging composite film according to claim 1, characterized in that: the barrier coating (3) is a PVA film.
5. The biodegradable high-barrier paper-plastic packaging composite film according to claim 1, characterized in that: the bonding layer (4) is solvent-free polyurethane adhesive.
6. The preparation method of the biodegradable high-barrier paper-plastic packaging composite film as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
1) preparing a PVA solution, coating the PVA solution on one surface of the paper layer (2), and drying to obtain a barrier coating (3);
2) printing an ink layer (1) on the other surface of the paper layer (2);
3) adding PLA particles and a compatilizer or a chain extender into a casting machine, uniformly mixing, heating to enable the PLA particles to reach a molten state, then adding PBAT and PPC, fully mixing, and extruding through a flat sheet-shaped die to form a film to obtain a PLA layer (5);
4) the barrier coating (3) and the PLA layer (5) are bonded through the solvent-free polyurethane adhesive to obtain the biodegradable high-barrier paper-plastic packaging composite film.
7. The preparation method of the biodegradable high-barrier paper-plastic packaging composite film according to claim 6, wherein the preparation method comprises the following steps: the specific operation of the step 1) is as follows: adding 50-80 parts of PVA powder, 10-20 parts of plasticizer and 3-10 parts of heat stabilizer into 60-80 parts of 80-95 ℃ deionized water according to mass fraction, and uniformly mixing to prepare a PVA solution; defoaming, cooling, filtering and extruding the PVA solution to obtain a solution; coating the solution on the paper layer (2) at 40-60 ℃ until the thickness of a wet film is 300-500 microns, drying at 60-100 ℃ and hot-pressing to flatten the paper to obtain a barrier coating (3); wherein the plasticizer is sorbitol or triethanolamine, and the heat stabilizer is laurate or zinc stearate; drying time is 1-5 minutes, and hot pressing is carried out on paper by adopting a flattening roller.
8. The preparation method of the biodegradable high-barrier paper-plastic packaging composite film according to claim 6, wherein the preparation method comprises the following steps: the specific operation of the step 3) is as follows: adding PLA particles and a compatilizer or a chain extender into a casting machine, mixing for 20-30 min, heating to 170-180 ℃, then cooling to 140-160 ℃, adding PBAT and PPC, mixing for 1-2 h, and extruding through a flat sheet-shaped die to form a film, wherein the film forming temperature is 40-60 ℃.
9. The preparation method of the biodegradable high-barrier paper-plastic packaging composite film according to claim 6, wherein the preparation method comprises the following steps: the specific operation of bonding in the step 4) is as follows: at room temperature, rolling a component A of the solvent-free polyurethane adhesive on the PLA layer (5), spraying a component B at 35-45 ℃, and pressing the barrier coating (3) on the PLA layer, wherein the pressing temperature is room temperature-60 ℃;
or mixing the component A and the component B of the solvent-free polyurethane adhesive at 35-45 ℃, spraying the mixture on the PLA layer (5), and pressing the barrier coating (3) on the PLA layer, wherein the pressing temperature is room temperature-60 ℃;
or, the single-component solvent-free polyurethane adhesive is coated on the PLA layer (5) in a roll coating or spraying manner, and the barrier coating (3) is pressed on the PLA layer, wherein the pressing temperature is room temperature-60 ℃.
10. The preparation method of the biodegradable high-barrier paper-plastic packaging composite film according to claim 6, wherein the preparation method comprises the following steps: and curing is carried out after bonding in the step 4), wherein the curing process conditions are as follows, the temperature is 40-60 ℃, and the time is 30-72 hours.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114228293A (en) * | 2021-12-20 | 2022-03-25 | 河北上东包装科技有限公司 | Degradable flexible packaging paper-plastic composite bag and production process thereof |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735587A (en) * | 2009-12-11 | 2010-06-16 | 内蒙古蒙西高新技术集团有限公司 | PPC (poly(propylene carbonate)), PBAT (poly(butylene adipate/terephthalate)) and PLA (poly(lactic acid)) blend and preparation method |
| WO2012067471A2 (en) * | 2010-11-19 | 2012-05-24 | Skc Co., Ltd. | Environmentally friendly multilayer film |
| CN106221165A (en) * | 2016-08-31 | 2016-12-14 | 深圳市虹彩新材料科技有限公司 | A kind of whole life cycle design of high-barrier and preparation method thereof |
| WO2018233888A1 (en) * | 2017-06-19 | 2018-12-27 | Basf Se | Biodegradable three-layered film |
| KR102083124B1 (en) * | 2019-07-17 | 2020-02-28 | 동원시스템즈 주식회사 | Laminated film to be applied to eco-friendly high barrier packaging |
| CN211280094U (en) * | 2019-12-20 | 2020-08-18 | 惠州市易韬围包装制品有限公司 | Biodegradable packaging bag |
| CN113025015A (en) * | 2021-03-04 | 2021-06-25 | 珠海横琴辉泽丰包装科技有限公司 | Biodegradable compostable environment-friendly material with low moisture permeability, and preparation method and application thereof |
| CN213861134U (en) * | 2020-11-23 | 2021-08-03 | 辜伟悦 | Novel biodegradable composite film material and packaging bag thereof |
-
2021
- 2021-08-09 CN CN202110907766.8A patent/CN113619242B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735587A (en) * | 2009-12-11 | 2010-06-16 | 内蒙古蒙西高新技术集团有限公司 | PPC (poly(propylene carbonate)), PBAT (poly(butylene adipate/terephthalate)) and PLA (poly(lactic acid)) blend and preparation method |
| WO2012067471A2 (en) * | 2010-11-19 | 2012-05-24 | Skc Co., Ltd. | Environmentally friendly multilayer film |
| CN106221165A (en) * | 2016-08-31 | 2016-12-14 | 深圳市虹彩新材料科技有限公司 | A kind of whole life cycle design of high-barrier and preparation method thereof |
| WO2018233888A1 (en) * | 2017-06-19 | 2018-12-27 | Basf Se | Biodegradable three-layered film |
| KR102083124B1 (en) * | 2019-07-17 | 2020-02-28 | 동원시스템즈 주식회사 | Laminated film to be applied to eco-friendly high barrier packaging |
| CN211280094U (en) * | 2019-12-20 | 2020-08-18 | 惠州市易韬围包装制品有限公司 | Biodegradable packaging bag |
| CN213861134U (en) * | 2020-11-23 | 2021-08-03 | 辜伟悦 | Novel biodegradable composite film material and packaging bag thereof |
| CN113025015A (en) * | 2021-03-04 | 2021-06-25 | 珠海横琴辉泽丰包装科技有限公司 | Biodegradable compostable environment-friendly material with low moisture permeability, and preparation method and application thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114228293A (en) * | 2021-12-20 | 2022-03-25 | 河北上东包装科技有限公司 | Degradable flexible packaging paper-plastic composite bag and production process thereof |
| CN114645488A (en) * | 2022-02-16 | 2022-06-21 | 江阴宝柏包装有限公司 | Paper-based recyclable composite material and preparation method thereof |
| CN114801268A (en) * | 2022-02-21 | 2022-07-29 | 青岛科技大学 | Biodegradable mulching film and preparation method thereof |
| CN114654843A (en) * | 2022-03-23 | 2022-06-24 | 重庆鼎桥科技有限公司 | Degradable composite membrane for medicine packaging machine and preparation method thereof |
| CN115042495A (en) * | 2022-04-29 | 2022-09-13 | 彤程化学（中国）有限公司 | Full-biodegradable high-water-vapor-barrier preservative film and preparation method thereof |
| CN115042495B (en) * | 2022-04-29 | 2024-06-07 | 彤程化学（中国）有限公司 | Full-biodegradation high-vapor barrier preservative film and preparation method thereof |
| CN114889298A (en) * | 2022-05-27 | 2022-08-12 | 汕头市强宇包装材料有限公司 | Aluminum-free high-barrier degradable composite paper for food and preparation method thereof |
| CN114889298B (en) * | 2022-05-27 | 2023-02-07 | 汕头市强宇包装材料有限公司 | Aluminum-free high-barrier degradable composite paper for food and preparation method thereof |
| CN114987941A (en) * | 2022-06-22 | 2022-09-02 | 汕头市强宇包装材料有限公司 | Production process and equipment of high-barrier degradable environment-friendly paper |
| CN116145466A (en) * | 2022-12-21 | 2023-05-23 | 江苏省农业科学院 | Composite root-blocking film for straw matrix disc and preparation method and application thereof |
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