CN113619242B - 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
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- 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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- 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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- 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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- 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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Abstract
The invention provides a biodegradable high-barrier paper-plastic packaging composite film and a preparation method thereof, wherein 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 surface to the inside, wherein the PLA layer is modified by a thermoplastic elastomer, and the temperature resistance and toughness of the biodegradable high-barrier paper-plastic packaging composite film can be improved after modification, the heat sealing performance of the biodegradable high-barrier paper-plastic packaging composite film 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 prolongs the shelf life of the content. 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 a degradable material, can be biodegradable 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 portability and low price. However, the plastic products are difficult to degrade, and the abandoned plastic products can bring serious harm to the environment, namely commonly called white pollution. According to Kerney's analysis, only 8% of plastics in the world are currently recycled, with 800 tens of thousands of tons of plastic waste entering the ocean each year. The total amount of plastic used was about 30% from packaging articles, a figure amounting to 1.1 hundred million tons in 2019. By 2050, plastic production is expected to increase substantially, and this number is predicted to reach 7 hundred million tons. If no countermeasures are taken, 6.44 million tons of plastic will be introduced into the landfill each year. With the increasing proportion of packaging in global plastics and increased consumer awareness, consumers are demanding enterprise changes.
The conventional plastic package generally adopts polymer films such as PE (polyethylene), PET (polyethylene terephthalate), PP (polypropylene), PVC (polyvinyl chloride), PA (nylon) and the like as base materials, wherein PE, PET, PP, PVC and the like in the polymer films belong to non-biodegradable polymer materials, and the PA is a degradable material, but the degradation period of the PA is generally more than 30 years. None of these polymeric materials are suitable for the development of new generation degradable plastic packages.
In terms of research and development of degradable plastics, the current global mainstream trend is starch-based plastics, PLA, PBAT. The PLA (polylactic acid) production process has no pollution, reliable biological safety, good mechanical property and easy processing property, and the degraded products are carbon dioxide and water, can not influence the environment, are the most recognized degradable materials with development prospect, and can be used for manufacturing food packaging, medical packaging, agricultural mulching films and the like.
PLA, however, also has disadvantages such as poor heat resistance, low softening temperature, poor film formation, brittle and brittle properties, and general barrier properties. If these problems are solved by the modification method, the cost is greatly increased. This is also a major reason that PLA plastic articles are not currently being used on a large scale.
At present, the current state of PLA related research at home and abroad:
(1) The PLA technology has higher barrier and is still started in China
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 the lactic acid molecules are together, the hydroxyl group is dehydrated and condensed with the carboxyl group of other molecules, and the carboxyl group is dehydrated and condensed with the hydroxyl group of other molecules, so that the polylactic acid is formed.
There are mainly two methods for preparing PLA, namely a lactide ring-opening polymerization method and a direct polycondensation method, and the ring-opening polymerization method is mainly adopted in industry. The synthesis and purification of the intermediate lactide are core technology and difficulty in the current PLA technological process, and the preparation method has the advantages of harsh reaction conditions, complex process, higher technical requirements and higher production cost, and is a main technical barrier for expanding the PLA productivity of domestic enterprises. At present, PLA productivity is mainly concentrated at overseas and still at a starting stage in China.
The state polylactic acid technology is mainly developed by the cooperation of enterprises and scientific research institutions. The Shanghai Hodgy company technology comes from the university of Tongji, adopts a direct polycondensation production process, and has the production capacity of lactic acid-polylactic acid. The Zhejiang sea positive lactide technology is from a vinca department of reaction, the lactide of the Zhejiang sea positive lactide technology is successfully produced, partial self-supply can be realized, the company depends on the accumulation in the aspect of biotechnology and continuously extends to the upstream and downstream industrial chains of polylactic acid, but the current company lacks raw material lactic acid production and needs to purchase to enterprises such as domestic Jindan technology and the like. The gold red technology and the Nanjing university cooperate to try to open the 'lactic acid-lactide' industrial chain by adopting an organic guanidine catalytic process, the pilot test result is good, and the cost is expected to be continuously reduced along with the improvement of engineering capability. The technology of middle grain is derived from Belgium Shi Ge Latt, the two technologies cooperate to establish a full-industry-chain production base of corn-lactic acid-lactide-polylactic acid in Anhui, and a company has mastered the lactide production technology and the processing technology, so that the lactide production project is steadily advancing. Therefore, the PLA technical difficulty is mainly that lactide, and many domestic enterprises are greatly developing lactide production technology in an attempt to break through the PLA industry technical barrier, open the whole industry chain of lactic acid-lactide-polylactic acid, and enhance the cost advantage.
(2) PLA application is limited, and modification research is urgent
Although PLA has many advantages, there are many disadvantages in real world applications: such as poor toughness, lack of elasticity and flexibility, hard and brittle texture, relatively low solution strength, too slow crystallization rate, etc., have limited their use in many applications. PLA contains a large number of ester bonds in its chemical structure, resulting in poor hydrophilicity, a controlled degradation rate, etc. And PLA is expensive, increasing raw material costs and limiting its commercial deployment. Therefore, aiming at the defects, the modification of PLA becomes the main research direction of related scientific researchers at home and abroad in recent years, so as to improve the material performance and degrade the product cost. At present, physical modification researches are mainly carried out at home and abroad.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a biodegradable high-barrier paper-plastic packaging composite film and a preparation method thereof, wherein the composite film is made of a degradable material, can be biodegraded after being used, has no pollution to the environment, and comprises a PLA layer modified by a thermoplastic elastomer, so that the temperature resistance and toughness of the composite film can be improved, the heat sealing performance of the composite film is ensured, and the packaging requirements of different contents and different weights are met.
In order to achieve the above purpose, the invention adopts the following technical scheme:
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 adopting a casting machine, adding a degradable thermoplastic elastomer, fully mixing, and 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 compatilizer or chain extender; the compatilizer is difunctional compatilizer KT20 or EsunBio5004K, and the chain extender is 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 bonding layer is a solvent-free polyurethane adhesive.
The preparation method of the biodegradable high-barrier paper-plastic packaging composite film comprises the following steps:
1) Preparing 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, adding PBAT and PPC, fully mixing, and extruding into a film through a flat sheet-shaped mouth die to obtain a PLA layer;
4) And bonding the barrier coating with the PLA layer through 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 deionized water at 80-95 ℃ according to mass fraction, and uniformly mixing to prepare PVA solution; removing bubbles from PVA solution, cooling, filtering and extruding to obtain a solution; coating the solution on a paper layer at 40-60 ℃, drying and hot-pressing the paper at 60-100 ℃ to level the paper to obtain a barrier coating, wherein the thickness of a wet film is 300-500 microns; wherein the plasticizer is sorbitol or triethanolamine, and the heat stabilizer is laurate or zinc stearate; the drying time is 1-5 minutes, and the paper is hot pressed 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 to form a film through a flat sheet-shaped die, wherein the film forming temperature is 40-60 ℃.
The specific operation of the bonding in the step 4) is as follows: at room temperature, rolling the component A of the solvent-free polyurethane adhesive on the PLA layer, then spraying the component B at 35-45 ℃, and pressing the barrier coating on the component A at room temperature-60 ℃;
or, the component A and the component B of the solvent-free polyurethane adhesive are mixed at 35-45 ℃ and then are immediately sprayed on the PLA layer, and a barrier coating is pressed on the PLA layer, wherein the pressing temperature is room temperature-60 ℃;
or, rolling or spraying a single-component solvent-free polyurethane adhesive on the PLA layer, and pressing a barrier coating on the PLA layer at the room temperature to 60 ℃.
And 4) after bonding, curing, wherein the curing process conditions are as follows, the temperature is 40-60 ℃ and the time is 30-72 h.
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 the printing ink layer, the paper layer, the barrier coating, the adhesive layer and the PLA layer from the outside to the inside, wherein the PLA layer is modified by the thermoplastic elastomer, and the modified PLA layer can improve the temperature resistance and toughness of the biodegradable high-barrier paper-plastic packaging composite film, ensure the heat sealing performance of the biodegradable high-barrier paper-plastic packaging composite film and meet the packaging requirements of different contents and different weights. The barrier coating can ensure that the final finished product has good barrier property and prolongs the shelf life of the content. 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 a degradable material, can be biodegraded after being used, has no pollution to the environment, accords with the national commitment of new plastic economy, is also expected to be exported to countries and regions where degradable plastic products such as Europe and the like are applied on a large scale besides domestic sales, and has good market prospect.
Further, the PLA layer is modified by the thermoplastic elastomer, and in the PLA modification, the ratio between PLA particles and the thermoplastic elastomer is balanced with the toughness, heat sealing performance and cost of the PLA film after film formation by optimizing parameters, so that 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 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 solvent-free adhesive is selected and the technological parameters are controlled, so that the compounded material has good compounding fastness, surface flatness and stiffness.
According to the preparation method of the biodegradable high-barrier paper-plastic packaging composite film, provided by the invention, based on the characteristic that paper and polylactic acid (PLA) are degradable in natural environment, a solvent-free composite process is adopted to compound the PLA film and the paper through pretreatment of materials, adjustment of material proportion, control of technological parameters and the like, and the problems of insufficient temperature resistance, flexibility, barrier property and the like are finally solved through modification of the PLA film and preparation of a barrier coating. The preparation process of the invention does not use organic solvent and solvent type printing ink, the whole preparation process uses green printing technology, and has better prevention and control means before and after production, thereby effectively reducing the generation of organic waste gas, having no pollution in the production process and meeting the environmental protection requirement. The key technology of the invention is PLA modification treatment technology, based on the traditional blending mode, an extrusion casting forming process is adopted, PLA particles are heated to a certain temperature by using a casting machine, and degradable thermoplastic elastomer is added, and the PLA particles are fully mixed and extruded into a film by a flat sheet-shaped mouth die. The method has the advantages that the prepared PLA film has higher thickness precision and better transparency, the toughness and the heat sealing performance are obviously improved while the mechanical property of the PLA is ensured, the production efficiency is high, the cost is reduced, the economy is good, and the method is beneficial to mass production. Compared with the traditional copolymerization and blending, the method has obvious advantages.
Drawings
FIG. 1 is a schematic structural view of a biodegradable high barrier paper plastic packaging composite film of the present invention;
wherein: 1 is an ink layer, 2 is a paper layer, 3 is an adhesive layer, 4 is a barrier coating, and 5 is a PLA layer.
Detailed Description
The present invention will be 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 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 film formation after modification of a degradable thermoplastic elastomer, wherein the degradable thermoplastic elastomer is PBAT and PPC.
In order to ensure the biodegradation effect, the materials selected by the invention are all green environment-friendly materials, wherein the ink layer 1 adopts degradable water-based ink, such as WPH series degradable water-based ink products of Guangdong good view science and technology Co., ltd, and the products obtain the certification certificate of the biodegradable materials, namely European Union OK composite certification. The paper layer 2 may be kraft paper, wood pulp paper or glassine paper. The selection of paper and 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 double-component adhesive, can be used for bonding and connecting media under the solvent-free condition, is a potential adhesive which is environment-friendly and can be used for food packaging and the like, and can enable the compounded material to have good compounding fastness, surface flatness and stiffness.
PVA film is selected as the barrier coating 3, PVA has unique strong cohesiveness, film flexibility, smoothness, oil resistance, solvent resistance, protective colloid, gas barrier property and wear resistance, is used as a fiber raw material, and is also widely used for producing products such as paint, adhesive, paper processing agent, emulsifying agent, dispersing agent, film and the like, and the application range of the PVA film is wide in textile, food, medicine, building, wood processing, papermaking, printing, packaging, agriculture, steel, high polymer chemical industry and other industries. The PVA aqueous solution has good adhesiveness and film forming property, PVA powder, plasticizer and heat stabilizer are added into deionized water together to prepare the PVA solution for coating, so that the barrier coating 3 is obtained, the final finished product can be ensured to have good barrier property, and the shelf life of the content can be prolonged. In addition, PVA can be decomposed and degraded by specific bacteria in soil, and has the performance of green and environment protection.
PLA has many advantages, but there are also many disadvantages: if the toughness of PLA is relatively poor, the PLA lacks elasticity and flexibility, has hard texture, large brittleness and the like, the thermoplastic elastomer (PBAT and PPC) is selected to modify the PLA, and the specific proportion 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 difunctional compatilizer KT20 or EsunBio5004K, and the chain extender is BASF epoxy chain extender ADR 4468.
PLA (polylactic acid) polylactic acid, also called as 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. The PBAT belongs to thermoplastic biodegradable plastics, is a copolymer of butanediol adipate and polybutylene terephthalate, has the characteristics of PBA and PBT, has good ductility and elongation at break, and has good heat resistance and impact resistance; in addition, the material also has excellent biodegradability, and is one of the best degradable materials which are very active in the research of biodegradable plastics and are applied to the market at present. Poly (propylene carbonate) (PPC), also known as polymethyl ethylene carbonate, is a completely degradable environment-friendly plastic synthesized from carbon dioxide and propylene oxide. PPC, PLA and PBAT all belong to aliphatic resins and are biodegradable materials, and the characteristics of the three raw materials are obvious. The softening point of the PPC is low and only 33-35 ℃, but the toughness is good; PLA softening point 58 deg.C, rigidity is good, but toughness is poor; the two properties are complementary, and the PLA modified by PPC is an ideal material, but the compatibility of the two materials is extremely poor. If the two are blended with PBAT, the complementarity is also very strong, but the compatibility is still a prominent problem.
In the preparation of PLA, PPC and PBAT modified films, poor compatibility can severely affect various properties of the film, such as appearance, physical properties (tensile strength, breaking strength, ductility, processability). Therefore, to improve various properties of the film, a proper compatilizer is added for pretreatment, so that the dispersibility and fluidity of materials and the compatibility with downstream resin are improved. The compatilizer has the following properties that 1. The compatibility in a formula system is enhanced, the particle material is assisted in forming, and the toughness and the strength of the particle material are improved. 2. The toughness, the tensile strength and other mechanical properties of the product are improved, and the glossiness, the light transmittance, the bearing resistance and other properties of the film are improved. 3. By increasing the dispersibility and compatibility of the formula system, the purposes of increasing the filler dosage, reducing the overall cost and improving part of performance are achieved.
Difunctional compatibilizer KT20 (Shenyang plastics technology Co., ltd.) is a high molecular weight ethylene, maleic anhydride, glycidyl ester terpolymer. KT20 can influence the mechanical property, the thermal property, the dynamic rheological property and the micro morphology of the PLA and PBAT blend, 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, the compatibility of PLA and PBAT is improved, the interfacial binding force of a blend two-phase system is improved, and the comprehensive mechanical property of the material can be obviously improved by using a proper amount of KT 20.
PLA/PBAT compatibilizer EsunBio5004K (Shenzhen Guanghua Wenyu Co., ltd.) has the following advantages: 1. is a degradable material, low carbon and environment-friendly; 2. good compatibility with the material matrix; 3. the processing performance is good, the process range is wider, the molding is easy, the water gap is continuous, the cooling and shaping are faster, and the demolding is easy; 4. the surface glossiness of the product is good; 5. the product has low shrinkage, good dimensional stability and strong warp resistance. The compatilizer EsunBio5004K is mainly applied to the compatibilization and modification of PLA and PBAT, not only can improve the interface strength of the PBAT and PLA, but also can be used for adding filler into PLA, adding glass fiber into PLA and the like, improving the interface binding force between the filler and PLA, improving the compatibility, and simultaneously, the material has obvious toughening effect on the PLA and does not influence the degradability of the PLA. Is used for biodegradable film materials, biodegradable injection molding materials and the like.
The BASF epoxy chain extender ADR 4468 (Shanghai Naplastic alloy technology Co., ltd.) is a copolymer containing epoxy functional groups, nine active groups on each molecule are subjected to a linking reaction with reactive groups (hydroxyl, carboxyl, amino and thioether groups) of thermoplastic engineering plastics to form a branched molecular structure, and degraded molecular chains are coupled again in the synthesis, processing, repeated processing and recovery processes, so that the weight average molecular weight is improved, and the mechanical property, the thermal property, the processing property and the optical balance of the material are improved or recovered; the performance of the recycled plastic can be close to that of the original raw material. The following effects will occur after the addition of ADR 4468: 1. chain extension capability-improving molecular weight, increasing melt strength and viscosity, improving mechanical properties of materials, and improving processing stability and mechanical properties of return materials; 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 heat stabilizer laurate into 70 parts of deionized water at 90 ℃ according to mass fraction, and uniformly mixing to prepare PVA solution; removing bubbles from PVA solution, cooling, filtering and extruding to obtain a solution; coating the solution on the paper layer (2) at 40 ℃, drying for 5 minutes at 60 ℃ and hot-pressing the paper by using a flattening roller to obtain a barrier coating (3);
2) Printing degradable water-based ink on the other side of kraft paper by adopting an intaglio printing technology;
3) Adding 55 parts of PLA particles and 1 part of difunctional compatilizer KT20 into a casting machine according to parts by weight, mixing for 20min, heating to 175 ℃ to enable the PLA particles to reach a molten state, cooling to 140 ℃, adding 18 parts of PBAT and 10 parts of PPC, mixing for 2h, extruding into a film through a flat sheet-shaped die, and obtaining a PLA layer 5, wherein the film forming temperature is 50 ℃;
4) The barrier coating is bonded with the PLA layer through a solvent-free polyurethane adhesive, and the specific steps are as follows: at room temperature, rolling the component A of the solvent-free polyurethane adhesive on the PLA layer, then spraying the component B at 45 ℃, and pressing the barrier coating on the component A at 40 ℃; curing treatment is carried out after bonding, wherein the curing temperature is 40 ℃, and the curing time is 72 hours; 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 PVA solution; removing bubbles from PVA solution, cooling, filtering and extruding to obtain a solution; coating the solution on the paper layer (2) at 50 ℃, drying for 1 minute at 100 ℃ to obtain a wet film with the thickness of 400 micrometers, and hot-pressing and leveling the paper by using a leveling roller to obtain a barrier coating (3);
2) Adopting a gravure printing technology, and printing degradable water-based ink on the other side of the wood pulp paper;
3) Adding 58 parts of PLA particles and 2 parts of compatilizer Esuno 5004K into a casting machine, mixing for 30min, heating to 170 ℃ to enable the PLA particles to reach a molten state, cooling to 150 ℃, adding 20 parts of PBAT and 8 parts of PPC, mixing for 1.5h, and extruding to form a film through a flat sheet-shaped die, wherein the film forming temperature is 40 ℃ to obtain a PLA layer 5;
4) The barrier coating is bonded with the PLA layer through a solvent-free polyurethane adhesive, and the specific steps are as follows: the component A and the component B of the solvent-free polyurethane adhesive are mixed at 35 ℃ and then are immediately sprayed on a PLA layer, and a barrier coating is pressed on the PLA layer at room temperature; curing treatment is carried out after bonding, wherein the curing temperature is 50 ℃ and the curing time is 48 hours; 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 PVA solution; removing bubbles from PVA solution, cooling, filtering and extruding to obtain a solution; coating the solution on the paper layer (2) at 60 ℃, drying for 3 minutes at 80 ℃ and hot-pressing the paper by using a flattening roller to obtain a barrier coating (3);
2) Adopting a gravure printing technology, and printing degradable water-based ink on the other surface of the glassine paper;
3) Adding 60 parts of PLA particles and 0.5 part of BASF epoxy chain extender ADR 4468 into a casting machine according to parts by weight, mixing for 25min, heating to 180 ℃ to enable the PLA particles to reach a molten state, cooling to 160 ℃, adding 15 parts of PBAT and 5 parts of PPC, mixing for 1h, and extruding into a film through a flat sheet-shaped mouth die, wherein the film forming temperature is 60 ℃ to obtain a PLA layer 5;
4) The barrier coating is bonded with the PLA layer through a solvent-free polyurethane adhesive, and the specific steps are as follows: rolling or spraying a single-component solvent-free polyurethane adhesive on the PLA layer, and pressing a 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/fat/alcohol resistance; the water vapor permeability at 38 ℃ is 80-90% RH (g/m 2 And/d) an oxygen transmission rate of 0 to 0.02% RH (cm) at 23 DEG C 3 /m 2 /d)。
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent structural transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (4)
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 sequentially arranged from the outside to the inside; the PLA layer (5) is obtained by heating PLA particles by adopting a casting machine, adding a degradable thermoplastic elastomer, fully mixing, and extruding to form a film, wherein the degradable thermoplastic elastomer is PBAT and PPC; 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 compatilizer or chain extender; the compatilizer is a difunctional compatilizer KT20 or EsunBio5004K, and the chain extender is a BASF epoxy chain extender ADR 4468; the ink layer (1) is degradable water-based ink; the paper layer (2) is kraft paper, wood pulp paper or glassine paper; the barrier coating (3) is a PVA film; the bonding layer (4) is solvent-free polyurethane adhesiveAn adhesive; the water vapor transmittance of the biodegradable high-barrier paper-plastic packaging composite film at 38 ℃ is 80-90% RH (g/m) 2 And/d) an oxygen transmission rate of 0 to 0.02% RH (cm) at 23 DEG C 3 /m 2 /d）。
2. The method for preparing the biodegradable high-barrier paper-plastic packaging composite film as claimed in claim 1, which is characterized by comprising the following steps:
1) preparing PVA solution, coating the PVA solution on one surface of the paper layer (2), and drying to obtain a barrier coating (3); the specific operation 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 deionized water at 80-95 ℃ according to mass fraction, and uniformly mixing to prepare PVA solution; removing bubbles from PVA solution, cooling, filtering and extruding to obtain a solution; coating the solution on the paper layer (2) at 40-60 ℃, drying and hot-pressing the paper at 60-100 ℃ to obtain a barrier coating (3), wherein the thickness of the wet film is 300-500 microns; wherein the plasticizer is sorbitol or triethanolamine, and the heat stabilizer is laurate or zinc stearate; the drying time is 1-5 minutes, and a flattening roller is adopted to carry out hot pressing on the paper;
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, adding PBAT and PPC, fully mixing, and extruding into a film through a flat sheet-shaped mouth die to obtain a PLA layer (5); the specific operation 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 into a film through a flat sheet-shaped die, wherein the film forming temperature is 40-60 ℃;
4) And (3) bonding the barrier coating (3) and the PLA layer (5) through a solvent-free polyurethane adhesive to obtain the biodegradable high-barrier paper-plastic packaging composite film.
3. The method for preparing the biodegradable high-barrier paper-plastic packaging composite film according to claim 2, which is characterized in that: the specific operation of the bonding in the step 4) is as follows: at room temperature, rolling an A component of the solvent-free polyurethane adhesive on the PLA layer (5), then spraying a B component at 35-45 ℃, and pressing the barrier coating (3) on the component, wherein the pressing temperature is room temperature to 60 ℃;
or, the component A and the component B of the solvent-free polyurethane adhesive are mixed at 35-45 ℃ and then immediately sprayed on the PLA layer (5), and the barrier coating (3) is pressed on the PLA layer, wherein the pressing temperature is room temperature-60 ℃;
or, rolling or spraying a single-component solvent-free polyurethane adhesive on the PLA layer (5), and pressing the barrier coating (3) on the PLA layer at the room temperature to 60 ℃.
4. The method for preparing the biodegradable high-barrier paper-plastic packaging composite film according to claim 2, which is characterized in that: and 4) after bonding, curing, wherein the curing process conditions are as follows, the temperature is 40-60 ℃, and the time is 30-72 h.
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| 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 |
| 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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