CN115182202A - Full-biodegradable high-peeling-force paper aluminum composite packaging material and preparation method and application thereof - Google Patents
Full-biodegradable high-peeling-force paper aluminum composite packaging material and preparation method and application thereof Download PDFInfo
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- CN115182202A CN115182202A CN202210520443.8A CN202210520443A CN115182202A CN 115182202 A CN115182202 A CN 115182202A CN 202210520443 A CN202210520443 A CN 202210520443A CN 115182202 A CN115182202 A CN 115182202A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/12—Layered products comprising a layer of metal comprising metal 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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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The invention discloses a full-biodegradable high-peeling-force paper-aluminum composite packaging material and a preparation method and application thereof. The base paper and the aluminum foil synchronously enter a T-shaped laminating die head, the full-biodegradable bonding material is directly melted and extruded from the T-shaped laminating die head, and the laminated film is pressed between the surfaces of the base paper and the aluminum foil through a hot pressing roller, cooled through a cooling roller and rolled to form the full-biodegradable high-peeling-force paper-aluminum composite packaging material with a three-layer structure. The invention has impermeability to light, air, water and other most gases and liquids, and can sterilize at high temperature, make the products not infringed by oxygen, sunlight and bacterium, greatly lengthen the shelf life; the adhesive has good quick adhesion, aging resistance and color tone, and can be used in the industries of adhesives, foods, electronics, medicines, rubber, printing ink, cables and the like; the relative biological decomposition rate is more than or equal to 90 percent.
Description
Technical Field
The invention belongs to the technical field of paper-aluminum composite packaging materials, and relates to a full-biodegradable high-peeling-force paper-aluminum composite packaging material, and a preparation method and application thereof.
Background
The paper-aluminum composite packaging material is divided into a paper base layer, an adhesive layer and an aluminum foil layer. The paper base layer mainly plays roles of beauty, printing, supporting and the like; the aluminum foil layer mainly plays the roles of blocking, shading and the like; and (3) bonding the paper base layer and the aluminum foil layer through an adhesive layer to form the multilayer composite packaging material. The composite material is prepared by laminating a polymer on paper through an extruder and then compounding an aluminum foil with the paper, and is mainly characterized in that the composite material can resist oil and water. The adhesive layer used by the traditional paper-aluminum composite packaging product is made of polyethylene or polyurethane material, and is the source of white pollution. The biodegradable material is a new material, and has good biodegradability and processability.
PLA (polylactic acid) film coated paper developed in the industry can be biologically degraded, has no toxicity, and can achieve the effect of environmental protection, but the application range of the PLA is greatly limited due to the defects of crisp PLA, poor toughness and impact resistance, poor thermal stability and the like. Another biodegradable material, PBS (poly butylene succinate), has low processing temperature, low viscosity and poor melt strength, and in addition, PLA and PBS are crystalline polymers, and products thereof tend to have a certain brittleness, so that the application range of the two in the field of packaging is greatly limited. PBAT is a copolymer of butanediol adipate and butanediol terephthalate, has good ductility and elongation at break, also has good heat resistance and impact resistance, and researches on 'superfine calcium carbonate filled degradable polyester materials' (plastics, 2009, 38 (3): 69-71) of Xiao Yun He and the like show that the blending of PBAT and superfine calcium carbonate can not only realize the complete and rapid degradation of the materials, but also greatly save the cost, but because the physical property of PBAT and the adhesive force of base materials are poor, the PBAT is not firmly bonded with the base materials in the operation process of paper aluminum compounding, the production efficiency is reduced, and the paper-plastic interface is easy to peel off. CN102558797B discloses a biodegradable laminated paper material, which comprises degradable resin and 3-10% of elastomer, and improves the adhesion of the material and paper. The addition of non-biodegradable materials will result in a reduction of the overall material's rate of biodegradation. CN1398766A, discloses a composite paper for packaging, which is made by compounding a PE plastic film and a base paper through an acrylic acid glue layer, the used materials acrylic acid and PE cannot realize biodegradation, and the waste to nature can cause environmental pollution. CN110735360B discloses a process for producing a degradable paper bag, which comprises sequentially spraying a film toughening film and a waterproof film on a paper substrate, blowing hot air by a hot air bag making machine to bond the waterproof film with packaging paper to obtain the waterproof paper bag, wherein the toughening film with bonding effect is non-full biodegradable material such as isocyanate. CN113183495A discloses a process for preparing a biodegradable garbage bag, which comprises the steps of coating a kraft paper with a premix of polylactic acid, polyethylene, etc., and laminating another coated paper layer with an adhesive glue thereon, etc., thereby obtaining a waterproof and moistureproof paper-aluminum composite garbage bag, wherein the premix, the adhesive glue, etc., are made of non-fully biodegradable materials. CN202110690983.6 discloses a full-biodegradable laminated composite paper, which is compounded by a plastic film and paper, has certain permeability to light, air, water and most other gases, and can not meet the product package of high barrier requirement; the used bonding layer materials are PBAT and mineral powder, and the peeling strength is not high when metal materials such as aluminum foil and the like are bonded.
One of the main properties of the paper-aluminum composite packaging material is the peel strength between the paper-based material and the aluminum foil material. The paper-based material and the aluminum foil material require sufficient peel strength to withstand bending and peeling during processing and use. Therefore, the adhesive properties of the adhesive resin system are very important. For the application requirements requiring higher peel strength, the fully biodegradable resins such as PBAT, PLA and PBS in the prior art cannot meet the use requirements. Those skilled in the art are keenly required to develop a fully biodegradable composite packaging material to meet the existing application market and performance requirements.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a full-biodegradable high-peeling-force paper-aluminum composite packaging material, wherein a biodegradable bonding material is used for replacing a traditional chemical adhesive and is applied to the compounding of the paper-aluminum composite packaging material so as to reduce the residue of toxic and harmful substances; and the defects of low production efficiency and poor material barrier property of an easily-adhered roller caused by single paper surface film coating resin are overcome by a mode of compounding paper and aluminum foil. The full-biodegradable high-peel-force paper-aluminum composite packaging material adopts a full-biodegradable material, has good overall biodegradability, and can be composted together with organic garbage such as leftovers and the like. Can realize full biodegradation in natural environment after being discarded, and does not pollute the environment. And the paint does not contain VOCs, heavy metals and carcinogenic substances, has no corrosiveness, is pollution-free and is green and friendly. Meets GB/T19277.1 'determination of final required biological decomposition capability of materials under controlled composting conditions', and the relative biological decomposition rate is more than or equal to 90%. The adhesive layer resin material in the packaging material has good quick adhesion, aging resistance and color tone, and excellent adhesive force, cohesion and intermiscibility, is very suitable for the full-biodegradable high-stripping-force paper-aluminum composite packaging material, and can be used for the industries of adhesives, foods, electronics, medicines, rubber, printing ink, cables and the like.
The invention provides a full-biodegradable high-peeling-force paper-aluminum composite packaging material and a production process thereof, which solve the problem that the paper-aluminum composite packaging material in the prior art adopts non-degradable materials (such as EVA, LLDPE, PP, HDPE, POEM and the like) as bonding layers, so that the environment is polluted due to non-degradability, and in order to realize the purpose, the invention provides the following technical scheme:
the invention provides a full-biodegradable high-peeling-force paper-aluminum composite packaging material, which comprises the following components in percentage by weight: a base paper layer 1, an adhesive layer 2 and an aluminum foil layer 3; the base paper layer 1 and the aluminum foil layer 3 are compounded through the bonding layer 2. The bonding layer is formed by extruding and laminating a full-biodegradable bonding material; the full-biodegradable bonding material comprises the following components in percentage by mass: PBAT-1 Polymer: 85-97%; adhesive auxiliary agent: 3 to 15 percent.
In a specific embodiment, the thickness of the base paper layer 1 is 20-400 μm, the thickness of the adhesive layer 2 is 3-15 μm, and the thickness of the aluminum foil layer 3 is 5-50 μm; preferably, the thickness of the base paper layer 1 is 300 μm, the thickness of the adhesive layer 2 is 5 μm, and the thickness of the aluminum foil layer 3 is 6-20 μm.
In the invention, the base paper layer 1 is made of base paper, and can be one or more of kraft paper, coated paper, white cardboard and white board paper; preferably a white cardboard. Preferably, the gram weight of the base paper is 20-300g/m 2 。
In the present invention, the aluminum foil layer 3 is formed of an aluminum foil. Wherein, the aluminum purity of the aluminum foil is more than 99.0 percent, the tensile strength of the aluminum foil is 50-110MPa, and the elongation is 2-15 percent.
In particular embodiments, the aluminum purity can be greater than 99.0%, up to 99.9%, 100%. The thickness of the aluminum foil layer is 5-50um, the aluminum foil layer is subjected to high-vacuum high-temperature annealing softening treatment, the vacuum degree is 0.01-0.02Pa, the annealing temperature is 300-650 ℃, and the annealing time is 4-24 h. Preferably, the aluminum foil layer is subjected to high-vacuum high-temperature annealing softening treatment, the annealing vacuum degree is 0.0133Pa, the annealing temperature is 480-550 ℃, and the annealing time is 8-10h. The thickness of the aluminum foil is 6-20um, the tensile strength is 75-85MPa, and the elongation is 3-8%.
In the invention, the bonding layer 2 is obtained by extruding and laminating a full-biodegradable bonding material, and the base paper layer and the aluminum foil layer are processed by laminating the bonding layer. The full-biodegradable bonding material comprises the following components in percentage by mass: PBAT-1 Polymer: 85 to 97 percent; adhesive auxiliary agent: 3 to 15 percent; preferably, PBAT-1:90 percent; adhesive auxiliary agent: 10 percent.
The adhesive auxiliary agent comprises but is not limited to one or a combination of more of hydrogenated rosin, hydrogenated rosin glyceride, hydrogenated rosin pentaerythritol ester, rosin glyceride and rosin pentaerythritol ester, the acid value is 2-170mgKOH/g, the softening point is 75-100 ℃, the arsenic content is less than or equal to 0.0002%, the ash content is less than or equal to 0.1%, and the Gardner color is 2-10. Preferably, the bonding auxiliary agent is hydrogenated rosin glyceride, the acid value is 3-8mgKOH/g, the softening point is 78-90 ℃, the arsenic content is less than or equal to 0.0002%, the ash content is less than or equal to 0.1%, and the Gardner color is 2-8.
The PBAT-1 is poly terephthalic acid/adipic acid/butylene terephthalate, and the molecular structure is shown as the following formula (1):
wherein, unit B specifically refers to: -O-CH 2 CH 2 CH 2 CH 2 -O-
Unit a specifically refers to:
the T unit specifically refers to:
wherein, in the PBAT-1 polymer, the molar ratio of the repeating unit x containing the B unit and the A unit accounts for 55 to 70 percent of the total sum of the repeating unit x and the repeating unit y; preferably, it is 58%. Wherein the repeating unit y means a repeating unit comprising a B unit and a T unit.
Wherein the melt index of the PBAT-1 is 10-1000g/10min (test method: ISO 1133; test conditions: 2.16kg,190 ℃), and the melting temperature T is m 70-115 ℃, tg of-55 to-20 ℃, tc of-20 to 45 ℃, number average molecular weight Mn of 60000 to 80000 and weight average molecular weight Mw of 130000 to 170000.
The bonding layer is a full-biodegradable bonding material and is prepared by the following steps:
adding the PBAT-1 polymer into a parallel double-screw extruder, and adding the bonding auxiliary agent into the parallel double-screw extruder in a side feeding manner through a high-viscosity polymer metering conveying pump; and melting and blending the PBAT-1 and the bonding auxiliary agent in a parallel double-screw extruder, air cooling, drying and granulating to prepare the fully biodegradable bonding material. The full-biodegradable bonding material comprises 85-97% of PBAT-1 polymer and 3-15% of bonding auxiliary agent by mass percent.
In the steps, the temperatures of the zones 1-7 of the double-screw extruder are respectively 140-180 ℃,150-190 ℃,150-190 ℃,150-190 ℃,150-190 ℃,150-190 ℃,150-190 ℃ and the head temperature is 150-190 ℃; preferably, the temperatures in zones 1-7 are 145 deg.C, 160 deg.C, 170 deg.C, and the head temperature is 170 deg.C, respectively.
In the steps, the high-viscosity polymer metering delivery pump has the delivery temperature of 90-150 ℃ and the delivery pressure of 0.1-2Mpa; preferably, the delivery temperature is 100 ℃ and the delivery pressure is 0.5MPa.
The invention also provides a preparation method of the full-biodegradable high-peeling-force paper-aluminum composite packaging material, which comprises the following steps:
step 2, loading the base paper and the aluminum foil into a compound machine, and conducting paper guide;
and 3, synchronously feeding the base paper and the aluminum foil in the step 2 into a T-shaped laminating die head, directly melting and extruding the full-biodegradable bonding material in the T-shaped laminating die head, laminating the laminated film between the surfaces of the base paper and the aluminum foil through a hot press roll, cooling the laminated film through a cooling roller, and rolling the laminated film to form the full-biodegradable high-peeling-force paper-aluminum composite packaging material with a three-layer structure.
In the step 2, further, the base paper and the aluminum foil may also be aluminum foils which are subjected to corona treatment in advance, that is, the corona treatment is performed on the surfaces to be compounded of the base paper and the aluminum foils, so that the bonding effect of the compounded surfaces can be increased. Wherein the corona setting is 38-50 dynes; preferably 45 dyne.
In the step 3, in the extrusion and film coating process, the thickness of the fully biodegradable bonding material, namely the bonding resin, extruded by the T-shaped extrusion die head is 3-15 μm; preferably 5 μm.
In the step 3, the temperature of the composite hot-pressing roller for melting and extruding the bonding resin is 80-110 ℃, the composite pressure is 0.5-1.0Mpa, and the surface temperature of the cooling roller is 20-40 ℃; preferably, the temperature of the hot-pressing roller is 90-100 ℃, the composite pressure is 0.7MPa, and the surface temperature of the cooling roller is 20 ℃.
In a specific embodiment, the temperatures of the 1-7 areas of the double-screw extruder of the laminating compounding machine are respectively 80-150 ℃,90-190 ℃,100-220 ℃,100-220 ℃,100-220 ℃,100-220 ℃,100-220 ℃ and the head temperature is 100-220 ℃; the melt temperature of the full biodegradable material is 100-220 ℃; preferably, the temperatures in zones 1-7 of the twin-screw extruder are 100 ℃,120 ℃,130 ℃,140 ℃,150 ℃,160 ℃,160 ℃,160 ℃ of the head temperature and 160 ℃ of the melt of the fully biodegradable bonding material.
In a preferred embodiment, the running speed of the laminating compound machine is 20-150m/min, and the gram weight of the laminated film is 3.5-18g/m during laminating 2 (ii) a Preferably, the running speed of the laminating compound machine is 70m/min, and the gram weight of the laminating film is 6.5g/m 2 。
The invention also provides the full-biodegradable high-peeling-force paper-aluminum composite packaging material prepared by the method.
The invention also provides the full-biodegradable high-peeling-force paper aluminum composite packaging material in the aspects of food packaging, such as chocolate, candy packaging, instant food, cooked food packaging, milk powder, liquid milk packaging, tea, coffee, fresh agricultural products, natural food (drink), fruit juice beverage and other beverages, vegetable juice beverage and seasoning; in the industrial aspect, the waterproof and moisture-proof composite board is used for moisture insulation and water proofing, such as desiccant packaging, preservative packaging, sticking on the surface of building materials, blocking moisture from entering the interior of the board and the like; in the aspect of medicine packaging: medical equipment packaging, traditional Chinese medicine packaging and pesticide packaging; in other aspects: the application in the fields of aviation bags, seed bag paper and the like.
The technical breakthroughs and the beneficial effects of the invention comprise: the bonding auxiliary agent adopted by the invention not only reduces the acid value of the PBAT-1 polymer in the bonding layer, has good compatibility, improves thermal stability and better oxidation resistance, but also has the characteristics of water resistance, acid resistance, alkali resistance and the like, so that the fully biodegradable bonding material adopted by the invention, namely the bonding layer material has more polar internal structures, the induction force, the orientation force and the dispersion force of the bonding layer material are improved, and the bonding auxiliary agent is specifically embodied as higher stripping force performance of the bonding layer; the PBAT-1 polymer adopted by the invention forms a very thin viscous layer at a bonding interface through a dispersion phase in the laminating compounding process, the viscous layer can generate viscous flow under the pressure effect of a compounding press roller, the elastic modulus of the PBAT-1 polymer in the bonding layer is further reduced by adding the bonding auxiliary agent, the viscosity of the PBAT-1 polymer in the bonding layer is reduced in the melting processing process by the dissolution of the bonding auxiliary agent, and the bonding strength of the invention is improved.
The invention realizes the full-biodegradable paper-aluminum composite packaging by adopting a paper-aluminum composite structure process and compounding the full-biodegradable bonding material, adopts a three-layer structure of a base paper layer, an adhesive layer and an aluminum foil layer, is a full-biodegradable material, meets GB/T19277.1 'determination of the final required biological decomposition capability of the material under the controlled composting condition', and has a relative biological decomposition rate of more than or equal to 90%. Solves the technical defects and problems of non-degradable compounding realized by polyethylene or polyurethane in the prior art.
The aluminum foil used in the invention is subjected to high-temperature annealing treatment in a high vacuum state, so that the residual lubricating oil on the surface of the aluminum foil is volatilized into gas, the surface cleanliness of the aluminum foil is improved, and the residual oil stains on the surface of the aluminum foil in the rolling manufacturing process are removed. The oil stain removal improves the surface cleanliness of the aluminum foil, so that the composite quality of the composite packaging material is improved.
The fully biodegradable bonding material is prepared by adding a bonding auxiliary agent into a parallel double-screw extruder in a side feeding manner through a high-viscosity polymer metering delivery pump, and carrying out melt blending on the bonding auxiliary agent and a PBAT-1 polymer in the parallel double-screw extruder; the process method is characterized in that the bonding auxiliary agent is stably fed into a screw barrel by a metering delivery pump so as to avoid transesterification side reaction caused by mixing shearing and too long heating time of the bonding auxiliary agent and PBAT-1 in a screw, thereby causing the reduction of the molecular weight and the mechanical property of a product.
Compared with other full-biodegradable packaging materials, the full-biodegradable high-peeling-force paper aluminum composite packaging material has impermeability to light, air, water and most other gases and liquids, can be sterilized at high temperature, prevents the product from being damaged by oxygen, sunlight and bacteria, and greatly prolongs the shelf life.
The adhesive layer resin material has the advantages of good quick adhesion, aging resistance and color tone, and excellent adhesive force, cohesion and intermiscibility, is very suitable for the full-biodegradation high-stripping-force paper-aluminum composite packaging material, and can be used for the industries of adhesives, foods, electronics, medicines, rubber, printing ink, cables and the like.
The invention has excellent stripping force, good appearance stiffness and good pressure resistance, and can realize high-efficiency continuous production without sticking a roller during compounding. In the composite processing step, the press roller is not contacted with the hot melt, so that the conditions that the common laminating resin hot melt is easy to adhere to the press roller, the laminating layer is adhered by the press roller and is peeled from the paper surface are avoided.
Drawings
FIG. 1 is a schematic structural view of a fully biodegradable high peel force paper aluminum composite packaging material of the present invention.
FIG. 2 is a schematic view of the processing flow of the fully biodegradable high peel force paper aluminum composite packaging material of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1
A full-biodegradable high-peel-force paper aluminum composite packaging material comprises: base paper layer 1, adhesive layer 2, aluminium foil layer 3.
The base paper layer 2 is kraft paper with the gram weight of 80g/m 2 。
The aluminum foil layer 3 is made of aluminum foil and is annealed and softened at high vacuum and high temperature, the annealing vacuum degree is 0.01Pa, the annealing temperature is 480 ℃, the annealing time is 8h, the thickness of the aluminum foil is 7um, the tensile strength is 83MPa, and the elongation is 4%.
The bonding layer 2 is a full-biodegradable bonding material, and the content of the components is PBAT-1:85 percent; hydrogenated rosin glycerol ester: 15%, an acid value of 4mgKOH/g, a softening point of 80 ℃, and a Gardner color of 3.
The PBAT-1 in which the molar proportion of the repeating unit x comprising the A unit is 58% of the sum of the repeating units x and y and the melt index is 45g/10min (test method: ISO 1133; test conditions: 2.16kg,190 ℃ C.), the melting temperature T m 105 ℃, tg of-30 ℃, tc of 25 ℃, number average molecular weight Mn of 60000 and weight average molecular weight Mw of 140000.
The full-biodegradable bonding material is prepared by the following steps:
adding PBAT-1 into a parallel double-screw extruder, and adding the bonding auxiliary agent into the parallel double-screw extruder in a side feeding manner through a high-viscosity polymer metering conveying pump; the PBAT-1 and the bonding auxiliary agent are melted and blended in a parallel double-screw extruder, and are subjected to air cooling, drying and grain cutting to prepare a fully biodegradable bonding material; the temperatures of the zones 1-7 of the double-screw extruder are respectively 140 ℃,165 ℃,165 ℃,165 ℃,165 ℃,165 ℃ and 165 ℃, and the temperature of the machine head is 165 ℃; the high viscosity polymer metering conveying pump has conveying temperature of 100 deg.c and conveying pressure of 0.5MPa.
The preparation method of the full-biodegradable high-peeling-force paper-aluminum composite packaging material comprises the step of carrying out corona treatment on the surfaces to be compounded of the base paper and the aluminum foil before compounding, wherein the corona is set to be 40 dynes.
Pouring the full-biodegradable bonding material into a material box, and gradually sucking the material into a hopper through a material sucking device of a compound machine;
loading base paper and aluminum foil into a machine, and conducting paper;
base paper and aluminum foil synchronizationAnd (3) entering a T-shaped laminating die head, directly melting and extruding the fully biodegradable bonding material at the T-shaped laminating die head, laminating the film between the base paper and the corona surface of the aluminum foil, rolling the film by hot pressing and combining the film with the base paper and the corona surface of the aluminum foil, cooling the film by a cooling roller, and rolling the film to form the fully biodegradable high-peeling-force paper-aluminum composite packaging material with a three-layer structure. In the process of extruding and laminating the film, the thickness of the bonding resin extruded by the T-shaped extrusion die head is 5um. The temperatures in zones 1-7 of the extruder were 100 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, and 160 deg.C, respectively, and the melt temperature of the biodegradable binder was 160 deg.C. The temperature of the composite hot-pressing roller for melt extrusion of the bonding resin is 90 ℃, the composite pressure is 0.7Mpa, and the surface temperature of the cooling roller is 20 ℃. The running speed of the laminating compound machine is 80m/min, and the gram weight of the laminating compound machine is 6.1g/m 2 。
The peel force between the aluminum foil and the base paper of the obtained full-biodegradable high-peel-force paper-aluminum composite packaging material is 5.2N/15mm (test method: GB/T28118), and the relative biological decomposition rate is more than or equal to 90 percent. Can be used in food packaging such as chocolate, candy packaging, instant food, cooked food packaging, milk powder, liquid milk packaging, tea, coffee, fresh agricultural product, natural food (beverage), fruit juice beverage and other beverage, vegetable juice beverage and seasoning.
Example 2
The structure and the process flow of the full-biodegradable high-peeling-force paper-aluminum composite packaging material are the same as those of the embodiment 1 of the invention.
The base paper layer 1 is white cardboard with the gram weight of 250g/m 2 。
The aluminum foil layer 3 is made of aluminum foil, the annealing vacuum degree is 0.015Pa, the annealing temperature is 520 ℃, the annealing time is 9 hours, the thickness of the aluminum foil is 9um, the tensile strength is 81MPa, and the elongation is 5%.
The adhesive layer 2 is a full-biodegradable adhesive material, and the content of the components is PBAT-1:88 percent; rosin glycerin ester: 12%, an acid value of 4mgKOH/g, a softening point of 85 ℃, and a Gardner color of 3.
The PBAT-1 in which the molar proportion of the repeating unit x comprising the A unit is 62% of the sum of the repeating units x and y, the melt index is 58g/10min, and the melting temperature T is m At 98 ℃ and Tg of35 ℃ below zero, tc 20 ℃, number average molecular weight Mn 65000 and weight average molecular weight Mw 150000.
The full-biodegradable bonding material is prepared by the following steps:
adding PBAT-1 into a parallel double-screw extruder, and adding the bonding auxiliary agent into the parallel double-screw extruder in a side feeding manner through a high-viscosity polymer metering conveying pump; the PBAT-1 and the bonding auxiliary agent are melted and blended in a parallel double-screw extruder, and are subjected to air cooling, drying and grain cutting to prepare the fully biodegradable bonding material; the temperatures of the zones 1-7 of the double-screw extruder are respectively 145 ℃,170 ℃,170 ℃,170 ℃,170 ℃,170 ℃,170 ℃ and 170 ℃, and the temperature of a machine head is 170 ℃; the high viscosity polymer metering conveying pump has conveying temperature of 105 deg.c and conveying pressure of 0.4MPa.
The preparation method of the full-biodegradable high-peeling-force paper-aluminum composite packaging material comprises the step of carrying out corona treatment on the surfaces to be compounded of the base paper and the aluminum foil before compounding, wherein the corona is set to be 38 dyne.
In the process of extruding and laminating the film, the thickness of the bonding resin extruded by the T-shaped extrusion die head is 7um. The temperatures of the extruder zones 1-7 are 110 ℃,130 ℃,140 ℃,150 ℃,160 ℃,170 ℃,170 ℃, the head temperature is 160 ℃ and the melt temperature of the fully biodegradable bonding material is 160 ℃. The temperature of the composite hot-pressing roller for melting and extruding the bonding resin is 95 ℃, the composite pressure is 0.8Mpa, and the surface temperature of the cooling roller is 20 ℃. The running speed of the laminating compounding machine is 70m/min, and the gram weight of the laminating is 8.5g/m 2 。
The peeling force between the aluminum foil and the base paper of the obtained full-biodegradable high-peeling-force paper-aluminum composite packaging material is 6.9N/15mm, and the relative biological decomposition rate is more than or equal to 90 percent. Can be applied to the aspect of medicine packaging: packaging medical equipment, traditional Chinese medicine and pesticide; in other aspects: the application in the fields of aviation bags, seed bag paper and the like.
Example 3
The structure and the process flow of the full-biodegradable high-peeling-force paper-aluminum composite packaging material are the same as those of the embodiment 1 of the invention.
The base paper layer 1 is white cardboard with a gram weight of 150g/m 2 。
The aluminum foil layer 3 is made of aluminum foil, the annealing vacuum degree is 0.02Pa, the annealing temperature is 550 ℃, the annealing time is 10h, the thickness of the aluminum foil is 12um, the tensile strength is 85MPa, and the elongation is 3%.
The adhesive layer 2 is a full-biodegradable adhesive material, and the content of the components is PBAT-1:90 percent; hydrogenated rosin pentaerythritol ester: 10%, an acid value of 12mgKOH/g, a softening point of 98 ℃, and a Gardner color of 1.
The PBAT-1 in which the molar proportion of the repeating unit x comprising the A unit is 65% of the sum of the repeating units x and y, the melt index is 73g/10min, and the melting temperature T is m 98 ℃, tg of-45 ℃, tc of 5 ℃, number average molecular weight Mn of 70000 and weight average molecular weight Mw of 160000.
The full-biodegradable bonding material is prepared by the following steps:
adding PBAT-1 into a parallel double-screw extruder, and adding the bonding auxiliary agent into the parallel double-screw extruder in a side feeding manner through a high-viscosity polymer metering conveying pump; the PBAT-1 and the bonding auxiliary agent are melted and blended in a parallel double-screw extruder, and are subjected to air cooling, drying and grain cutting to prepare the fully biodegradable bonding material; the temperatures of zones 1-7 of the double-screw extruder are respectively 140 ℃,160 ℃,160 ℃,160 ℃,160 ℃,160 ℃ and 160 ℃, and the temperature of a machine head is 150 ℃; the high-viscosity polymer metering delivery pump has the delivery temperature of 100 ℃ and the delivery pressure of 0.3Mpa.
The preparation method of the full-biodegradable high-peeling-force paper-aluminum composite packaging material comprises the step of carrying out corona treatment on the surfaces to be compounded of the base paper and the aluminum foil before compounding, wherein the corona is set to be 42 dyne.
In the process of extruding and laminating the film, the thickness of the bonding resin extruded by the T-shaped extrusion die head is 10um. The temperatures in zones 1-7 of the extruder were 110 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 160 deg.C, and 160 deg.C, respectively, and the melt temperature of the biodegradable binder was 160 deg.C. The temperature of the composite hot-pressing roller for melt extrusion of the bonding resin is 100 ℃, the composite pressure is 0.6Mpa, and the surface temperature of the cooling roller is 20 ℃. The running speed of the laminating compounding machine is 90m/min, and the gram weight of the laminating is 12.0g/m 2 。
The peeling force between the aluminum foil and the base paper of the obtained full-biodegradable high-peeling-force paper-aluminum composite packaging material is 8.3N/15mm, and the relative biological decomposition rate is more than or equal to 90 percent. Can be applied to the industrial aspect for moisture insulation and water resistance, such as desiccant packaging, preservative packaging, pasting on the surface of building materials, blocking moisture from entering the interior of plates, and the like.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, which is set forth in the following claims.
Claims (13)
1. The full-biodegradable high-peeling-force paper-aluminum composite packaging material is characterized by comprising a base paper layer (1), an adhesive layer (2) and an aluminum foil layer (3); the base paper layer (1) and the aluminum foil layer (3) are compounded through the bonding layer (2); the bonding layer (2) is formed by extruding and laminating a full-biodegradable bonding material; the full-biodegradable bonding material comprises the following components in percentage by mass: PBAT-1 Polymer: 85 to 97 percent; adhesive auxiliary agent: 3 to 15 percent.
2. The fully biodegradable high peel force paper aluminum composite packaging material according to claim 1, wherein the PBAT-1 polymer is poly (terephthalic acid)/adipic acid/butylene terephthalate, and the molecular structure thereof is shown as the following formula (1):
wherein, the unit B is: -O-CH 2 CH 2 CH 2 CH 2 -O-; the unit A is:
the unit T is:
in the PBAT-1 polymer, the molar ratio of a repeating unit x comprising a B unit and an A unit accounts for 55-70% of the sum of the repeating unit x and the repeating unit y; the PBAT-1 polymer has a melt index of 10-1000g/10min and a melting temperature T m 70-115 ℃, tg of-55 to-20 ℃, tc of-20 to 45 ℃, number average molecular weight Mn of 60000-80000 and weight average molecular weight Mw of 130000-170000.
3. The fully biodegradable high-peel-force paper aluminum composite packaging material according to claim 1, wherein the bonding auxiliary agent is one or a combination of hydrogenated rosin, hydrogenated rosin glyceride, hydrogenated rosin pentaerythritol ester, rosin glyceride and rosin pentaerythritol ester; the acid value is 2-170mgKOH/g, the softening point is 75-100 ℃, the arsenic content is less than or equal to 0.0002%, the ash content is less than or equal to 0.1%, and the Gardner color is 2-10.
4. The fully biodegradable high peel force paper aluminum composite packaging material according to claim 1, wherein the fully biodegradable bonding material is prepared by the following steps:
adding the PBAT-1 polymer into a parallel double-screw extruder, and adding the bonding auxiliary agent into the parallel double-screw extruder in a side feeding manner through a high-viscosity polymer metering conveying pump; and melting and blending the PBAT-1 and the bonding auxiliary agent in a parallel double-screw extruder, air cooling, drying and granulating to prepare the fully biodegradable bonding material.
5. The fully biodegradable high peel force paper aluminum composite packaging material according to claim 1,
the base paper layer (1) is made of base paper and is made of one or more of kraft paper, coated paper, white cardboard and white board paper; the gram weight of the base paper is 20-300g/m 2 ；
The aluminum foil layer (3) is composed of an aluminum foil, the aluminum purity of the aluminum foil is more than 99.0%, and the thickness of the aluminum foil is 5-50 mu m; the tensile strength is 50-110MPa, and the elongation is 2-15%.
6. The fully biodegradable high peel force paper aluminum composite packaging material according to claim 5, wherein the aluminum foil is prepared by the following steps: the untreated aluminum foil is annealed and softened in high vacuum at high temperature, the vacuum degree is 0.01-0.02Pa, the annealing temperature is 300-650 ℃, and the annealing time is 4-24 h.
7. A preparation method of a full-biodegradable high-peeling-force paper aluminum composite packaging material is characterized by comprising the following steps:
step 1, pouring a full-biodegradable bonding material into a material box, and sucking the full-biodegradable bonding material into a hopper through a material sucking device of a compound machine;
step 2, loading the base paper and the aluminum foil into a compound machine, and conducting paper guiding;
and 3, synchronously feeding the base paper and the aluminum foil in the step 2 into a T-shaped laminating die head, directly melting and extruding the full-biodegradable bonding material in the T-shaped laminating die head, laminating the laminated film between the surfaces of the base paper and the aluminum foil through a hot press roll, cooling through a cooling roll, and rolling to form the full-biodegradable high-peeling-force paper-aluminum composite packaging material with the three-layer structure as claimed in claim 1.
8. The method according to claim 7, wherein in the step 3,
in the process of extruding and laminating the film, the thickness of the full-biodegradable bonding material extruded by the T-shaped extrusion die head is 3-15 mu m;
in the process of melt extrusion of the fully biodegradable bonding material, the temperature of the composite hot-pressing roller is 80-110 ℃, the composite pressure is 0.5-1.0Mpa, and the surface temperature of the cooling roller is 20-40 ℃; the temperature of the zones 1-7 of the double-screw extruder is respectively 80-150 ℃,90-190 ℃,100-220 ℃,100-220 ℃,100-220 ℃,100-220 ℃ and the head temperature is 100-220 ℃; the melt temperature of the full biodegradable material is 100-220 ℃; the running speed of the laminating compounding machine is 20-150m/min; the gram weight of the laminated film during laminating is 3.5-18g/m 2 。
9. The method of claim 7,
the aluminum foil is prepared by the following steps: the untreated aluminum foil is annealed and softened in high vacuum at high temperature, the vacuum degree is 0.01-0.02Pa, the annealing temperature is 300-650 ℃, and the annealing time is 4-24 h.
10. The production method according to claim 7,
the full-biodegradable bonding material is prepared by the following steps: feeding the PBAT-1 polymer according to claim 2 into a parallel twin-screw extruder, the adhesion promoter being fed in a side-feed manner into the parallel twin-screw extruder by means of a high-viscosity polymer metering pump; the PBAT-1 and the bonding auxiliary agent are melted and blended in a parallel double-screw extruder, and are subjected to air cooling, drying and grain cutting to prepare the fully biodegradable bonding material;
the bonding auxiliary agent is one or a combination of more of hydrogenated rosin, hydrogenated rosin glyceride, hydrogenated rosin pentaerythritol ester, rosin glyceride and rosin pentaerythritol ester; the acid value is 2-170mgKOH/g, the softening point is 75-100 ℃, the arsenic content is less than or equal to 0.0002%, the ash content is less than or equal to 0.1%, and the Gardner color is 2-10.
11. The method of claim 10,
in the preparation process of the full-biodegradable bonding material, the temperatures of the zones 1-7 of the double-screw extruder are 140-180 ℃,150-190 ℃,150-190 ℃,150-190 ℃,150-190 ℃,150-190 ℃ and the head temperature is 150-190 ℃; the high-viscosity polymer metering delivery pump has the delivery temperature of 90-150 ℃ and the delivery pressure of 0.1-2Mpa.
12. The fully biodegradable high-peel-force paper aluminum composite packaging material prepared by the method according to the claims 7-11.
13. Use of the fully biodegradable high peel force paper aluminium composite packaging material according to any one of claims 1-6, 12 in the fields of food packaging, industry, pharmaceutical packaging.
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