CN218366846U - High-barrier degradable environment-friendly packaging material and packaging material thereof - Google Patents

High-barrier degradable environment-friendly packaging material and packaging material thereof Download PDF

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CN218366846U
CN218366846U CN202221852408.8U CN202221852408U CN218366846U CN 218366846 U CN218366846 U CN 218366846U CN 202221852408 U CN202221852408 U CN 202221852408U CN 218366846 U CN218366846 U CN 218366846U
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layer
coating
water
packaging material
barrier
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陈明发
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Hainan Yiming Environmental Protection Material Technology Co ltd
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Hainan Yiming Environmental Protection Material Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • 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
    • 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
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/20—Inorganic coating
    • 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
    • B32B2255/24—Organic non-macromolecular coating
    • 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
    • B32B2255/28—Multiple coating on one surface
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • 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
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
    • 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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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

The application provides a high-barrier degradable environment-friendly packaging material and a packaging material thereof, which comprise a paper layer, a coating layer and a barrier coating; the water-based easy-to-strip substrate layer, the coating layer and the water-based porous coating layer form a prefabricated high-resistance layer together, and the prefabricated high-resistance layer is retained and bonded on the front surface of the paper layer. The packaging material and the packaging material thereof can save the energy consumption of the vacuum pump by more than 68 percent, are degradable, are pollution-free and have ultrahigh barrier property.

Description

High-barrier degradable environment-friendly packaging material and packaging material thereof
Technical Field
The application belongs to the technical field of environment-friendly packaging materials, and relates to paper-based packaging materials such as liquid food, solid food, powder food, medicine bubble caps and cigarette lining paper, in particular to a high-barrier degradable environment-friendly packaging material and a packaging material thereof.
Background
The regulations for forbidding disposable non-degradable plastic products in special economic district of Hainan have been promulgated and implemented in 2019, 12 and 31, which is the first forbidden plastic command in China. In 16 days 1 month 2021, the "Chinese scheme" for further enhancing plastics pollution control was published and implemented by the department of ecological environment. China will orderly forbid and limit the production, sale and use of partial plastic products, and actively popularize the recyclable and degradable alternative products which are easy to recycle. In order to control plastic pollution and promote environmental protection development, the inventor of the application carries out extensive and deep theoretical research, experimental test and process and equipment development for more than two years on the current packaging materials such as liquid food packaging boxes, medicine blister packages, cigarette lining paper and the like, and discovers some problems in the prior art.
The invention relates to a barrier film, a laminated packaging material comprising the barrier film and a packaging container made of the barrier film (hereinafter referred to as background art 1), which is a technical scheme of an environment-friendly packaging material with a film coating layer and is advanced in China patent application (CN 111655474A) submitted by the Rileval group of Switzerland and finance limited company. However, a large amount of polyester film substrates which are not naturally degradable are still used in the packaging material of the packaging material, so that the barrier performance of substances such as oxygen, water vapor, chemicals, aroma and the like of the packaging material is improved. That is, the background art 1 still uses a large amount of polyester film substrates that are not naturally degradable, and does not completely solve the environmental problem.
Chinese utility model patent (CN 210116793U) of kangtong tai boyuan scientific and technical materials ltd "a high-barrier paper-based material packaging bag (hereinafter referred to as background art 2)". The invention relates to a single-layer structure barrier heat-seal packaging paper and a preparation method thereof (hereinafter referred to as background technology 3), which is disclosed in the invention patent application (CN 113910733A) filed by Jiangsu Litter Green packaging Ltd. Chinese utility model patent (CN 205171271U) of Nanjing jinling gold foil GmbH is a high-resistance environment-friendly aluminized paper (hereinafter referred to as background art 4), chinese invention patent application (publication No. CN 1789478A) filed by Shanghai gold leaf packaging materials GmbH is a production process of vacuum aluminized paper (hereinafter referred to as background art 5). Chinese patent application CN105463940A "method for producing environment-friendly vacuum aluminized laser paper (hereinafter referred to as background art 6)" filed by sheng li packaging materials ltd in kunshan city. The invention relates to a production process of aluminized paper (hereinafter referred to as background art 7) in Chinese patent application (publication No. CN 109338802A) filed by Jiaxing City Tianyue packaging Co., ltd. Chinese patent CN102966007B of shaoxing gao information technology ltd) "a method for preparing fresnel lens vacuum aluminized paper and its product (hereinafter referred to as background art 8)". A Chinese utility model patent (CN 215243494U) of Yijiang aluminum-sprayed environmental protection materials, inc., anhui, a multi-layer vacuum aluminum-plated laser transfer film composite paper (hereinafter referred to as background technology 9). A chinese utility model patent (CN 211689669U) applied by the company, santa boyuan scientific and technological materials gmbh, "a high temperature resistant vacuum aluminizing laser paper (hereinafter referred to as background art 10)". Chinese utility model patent (CN 2755161Y) vacuum aluminized paper (hereinafter referred to as background art 11) applied by shanghai spinning, printing, and packaging ltd. Chinese patent application No. CN102002894B of boyuan scientific and technical materials (smoke platform) limited "a vacuum aluminizing ground cardboard containing an electron beam curing coating and a production method thereof (hereinafter referred to as background art 12)". The above background art provides some patentable concepts of packaging materials consisting of a heat seal layer, a paper layer, a coating layer (for replacing the current aluminum foil layer), and a barrier coating.
The applicant finds three technical difficulties in the implementation according to the assumption: firstly, the packaging material using metal aluminum as a high-barrier coating has low barrier property,the quality guarantee period of the liquid such as fruit juice, milk and the like packaged in the packaging bag is no longer than three months, and compared with the packaging bag using the existing aluminum foil layer packaging material, the quality guarantee period is obviously shortened. Analytical studies have found that the reason for the low barrier properties is: the water content of the paper is high, generally more than 6%, and even if a large amount of heat energy is consumed for vacuum heating dehumidification, absolute removal is difficult. When the paper is directly aluminized, even trace residual moisture is vaporized by heat in the vapor deposition process, the vapor deposition coating can be broken, and few vapor through holes are formed on the coating, so that the air leakage and the barrier property of the coating are greatly reduced. Secondly, use of Si0 2 、AL 2 O 3 The patent assumption of oxides as high-barrier coating packaging materials (background art 2 and 3) cannot be implemented, and thus, the oxides are not practical in a patent sense. The specific reason is that Si0 2 、AL 2 O 3 The oxides can only be evaporated by an electron gun, and the gasification temperature is above 3000 ℃. At the extremely high temperature, on one hand, the paper (with low thermal conductivity coefficient) can not be rapidly cooled and cooled, and the paper surface can be coked, so that the production can not be continued; on the other hand, in the vapor deposition process, the residual moisture in the paper is vaporized by heat and can break through the coating in the vapor deposition process, and few water vapor through holes are formed on the coating, so that the air leakage and the barrier property of the coating are greatly reduced. And thirdly, the vacuum degree is one of indexes which are strictly required during vacuum coating, and the vacuum degree has a direct relation with the qualities of a coated product, such as color, wear resistance, firmness and the like. Paper typically has a water content of 6% or more due to its high water content. Due to the existence of 6% of moisture in the paper, when the vacuum pump is vacuumized, even if the power of the vacuum pump is increased by three times, the vacuum pump cannot reach 10 percent -3 The vacuum requirement of mpa results in high energy consumption, low production rate, low efficiency and high rejection rate. Fourthly, because the plating layer is provided with water vapor through holes and the barrier property is very low, the plating layer can only be used as decorative paper with metallic luster.
In conclusion, how to avoid the perforation of the coating by water vapor, how to avoid the coking of the paper surface and how to reduce the energy consumption of the vacuum pump so as to manufacture the degradable environment-friendly packaging material with high barrier property similar to the performance of the existing aluminum foil is a technical problem in front of researchers of the environment-friendly packaging material.
Disclosure of Invention
One of the objects of the present application: provides a high-barrier degradable environment-friendly packaging material to prevent a coating layer from being perforated by water vapor and manufacture the high-barrier degradable environment-friendly packaging material with the performance similar to that of the existing aluminum foil.
The second objective of the present application is: the high-barrier degradable environment-friendly packaging material is provided to prevent a coating layer from being perforated by water vapor and manufacture the high-barrier degradable environment-friendly packaging material with the performance similar to that of the existing aluminum foil.
To achieve the above objects, in order to facilitate understanding of the technical solution of the present application, a method for preparing a high-barrier degradable environment-friendly packaging material is first described below.
A preparation method of a high-barrier degradable environment-friendly packaging material comprises the steps of laying a film coating layer and a barrier coating layer on a paper layer; the method is characterized by comprising the following process steps:
s1, using a film such as PET or BOPP with high tensile strength, good thermal stability, low thermal shrinkage and flat and smooth surface as a bearing layer, and firstly laying a water-based easy-to-peel liner layer (with the peeling force of 0.1-0.2N/25mm is best) on the back of the bearing layer; then put into the vacuum chamber (the vacuum degree is more than or equal to 10) -3 mpa) vacuum chamber, vapor deposition of Si0 onto an aqueous easy-peel liner layer 2 Or/and AL 2 O 3 Coating the film layer; finally, coating a water-based hole-filling coating on the coating layer; the water-based easily-stripped substrate layer and the film coating layer and other layers jointly form a prefabricated high-resistance (separation) layer which is temporarily coated on the bearing layer for stripping in the subsequent process. The proposal of laying the water-based porous coating is that the coating layer still forms some sand holes caused by various unexpected factors such as dust and the like in the vapor deposition forming process, and the technical measures of coating the water-based porous coating are adopted in order to close the sand holes to improve the barrier property and protect the coating layer to avoid accidental scratches of the roll surface; research shows that the mixed solution prepared by 50 percent of methyl orthosilicate, 30 percent of V-aminopropyl triethoxysilane, 20 percent of zirconium propanol and other three chemical raw materials is coated on a coating layer and heated to 106 ℃ and keptRolling after holding for 5-7 seconds, preserving heat for 7-8 hours in a 65 ℃ heat preservation box after rolling, taking out and naturally cooling after fully curing to form a water-based porous coating with very good performance;
s2, coating a high-resistance water-proof composite glue layer on the prefabricated high-resistance layer, compounding the prefabricated high-resistance layer and the front surface of the paper layer and drying; then stripping off the bearing layer and recovering; the prefabricated high-resistance layer is retained and bonded to the front surface of the paper layer to form the plastic-free high-resistance material;
and S3, preferably coating a water-based barrier coating (capable of being in direct contact with food) on the prefabricated high-resistance layer without the plastic high-resistance material to form the high-barrier degradable environment-friendly packaging material.
Therefore, on one hand, the coating layer is formed on the moisture-free special bearing layer in advance, and the traditional process of feeding paper layers with higher moisture content into a vacuum chamber for evaporation in the background art 2-12 is abandoned, so that vapor perforation does not occur in the vapor deposition forming process; on the other hand, when the bearing layer and the prefabricated high-resistance layer on the bearing layer are compounded with the paper layer, the solidified coating layer with higher strength can not be penetrated even if water vapor exists. Therefore, the process method can successfully prepare the high-barrier degradable environment-friendly packaging material; on the other hand, since there is no moisture in the bearing layer, it is easy to reach 10 when vacuum is pumped -3 Compared with the background technology 2-12, the vacuum requirement of mpa reduces the energy consumption of the vacuum pump by more than 68%, and has high production speed, high efficiency and low rejection rate.
In order to enable the non-plastic high-resistance material and the non-plastic ultrahigh-resistance material prepared by the process method to be used for preparing packages such as milk cartons and the like, the preparation method of the high-resistance degradable environment-friendly packaging material is preferably characterized by comprising the following steps of: and coating a water-based heat sealing adhesive coating on the back surface of the paper layer.
Preferably, the preparation method of the high-barrier degradable environment-friendly packaging material is characterized by comprising the following steps: coating a high-resistance waterproof composite glue layer between the water-based porous coating and the paper layer; wherein, the paper layer adopts breathable moisture absorption paper so as to ensure that the moisture in the water-based composite glue layer can be permeated and evaporated; on the one hand, to retain and bond the preformed high-barrier layer to the paper layer and, on the other hand, to further improve the barrier properties of the packaging material.
In practice, the process method finds that after the bearing layer is stripped, the bearing layer is retained and bonded in the coating layer on the paper layer, and pulling micropores with random positions and quantity inevitably appear, and the pulling micropores can cause air leakage of the coating layer and greatly reduce the barrier property. In order to avoid the generation of the pulling micropores, the applicant invests millions of yuan of research and development cost, repeated experiments are carried out by adopting conventional technical measures of thickening the coating layer, and tests show that the technical measures of thickening the coating layer can not completely avoid the generation of the pulling micropores. Quite unexpectedly, researchers have tried the following innovative process to achieve better results.
Preferably, the preparation method of the high-barrier degradable environment-friendly packaging material is characterized by comprising the following steps: compounding and drying the non-plastic high-resistance material and the prefabricated high-resistance layer on the bearing layer; then stripping off the bearing layer and recovering; the preformed high barrier layer (on the carrier layer) is retained and bonded to the plastic-free high barrier material to form a plastic-free ultra high barrier material having multiple (preferably 2-3) preformed high barrier layers.
Therefore, in the plastic-free ultrahigh-resistance material, the air leakage holes such as the scratch micropores, the sand holes, the water vapor perforation holes and the like on the two adjacent coating layers are staggered with each other in most cases, no superposition exists, and the probability of complete superposition is almost zero. And the air leakage holes are blocked by the adjacent coating layers instead of being compensated by the organic barrier coating. The air leakage path between two nearest air leakage holes of the upper layer and the lower layer is necessarily very long, so that the barrier property can be greatly improved. The comparative experiment shows that compared with the non-plastic high-resistance material with the same thickness, the non-plastic high-resistance material has the advantages that the barrier property is improved by multiple times, for example: the milk and the fruit juice filled into the plastic-free high-resistance material packaging bags with the same thickness have the quality guarantee period of at most 3 months, while the milk and the fruit juice filled into the plastic-free ultrahigh-resistance material packaging bags with the same thickness have the quality guarantee period of more than 12 months, and even do not deteriorate for 3 years.
Although the multiple prefabricated high-resistance layer compounding method can block the strain micropores to prepare the plastic-free ultrahigh-resistance material, the process is complex and is only suitable for preparing products with longer quality guarantee period (for example, more than 12 months). For products with moderate shelf life requirements (e.g., 6 months), there is little waste. In order to avoid the generation of the pulling micropores as much as possible, the applicant tests and experiments hundreds of formulas of the water-based easily-stripped substrate layer with expensive formulas, so that the generation of the pulling micropores cannot be avoided, and the satisfactory effect cannot be achieved all the time. Surprisingly, researchers have tried innovative processes for stripping the carrier layer by quenching, and better results have been obtained.
Preferably, the preparation method of the high-barrier degradable environment-friendly packaging material is characterized by comprising the following steps: coating the bearing layer and the prefabricated high-resistance layer and the paper layer which come out from the high-temperature oven with the temperature higher than 100 ℃ on a cold roller with the temperature of 4-12 ℃ immediately for rapid cooling; stripping the bearing layer at the low temperature of 4-12 ℃; the time for the back surface of the bearing layer to be tightly attached to the cold roll is preferably 0.5-3 seconds so as to be sufficiently cooled; for sufficient cooling, the bearing layer, the prefabricated high-resistance layer and the paper layer are preferably coated on a plurality of cooling rollers at 4-12 ℃ for multi-stage cooling; then, the non-plastic high-resistance material formed by the prefabricated high-resistance layer and the paper layer is sent into a coating unit and heated to normal temperature, and finally, the water-based easily-peelable substrate layer is coated with a water-based barrier coating to prepare the high-barrier degradable environment-friendly packaging material. Thus, the number of the tension holes is greatly reduced, and statistics show that the number of the tension holes is reduced by at least ten times. Compared with a method for changing the formula of the water-based easily-stripped substrate layer, the method is low in cost and easy to implement. Practice proves that: when the temperature of the prefabricated high-resistance layer and the paper layer is reduced to 4-12 ℃, the film forming property and the toughness of the aqueous easy-to-peel substrate layer are greatly improved, and the aqueous easy-to-peel substrate layer is easy to completely peel from the bearing layer, so that the strain micropores can be reduced. It is emphasized here that: the applicant researches that when the temperature is reduced to 4-12 ℃, the film forming property and toughness of the water-based easily-peelable substrate layer are greatly improved, the water-based easily-peelable substrate layer is easily and completely peeled off from the bearing layer, and the pulling damage micropores are greatly reduced.
Preferably, the preparation method of the high-barrier degradable environment-friendly packaging material is characterized by comprising the following steps: the water-based easy-to-peel liner layer is a water-soluble laminating layer or a film coating layer (but not a coating), and the peeling force between the water-soluble laminating layer or the film coating layer and the bearing layer is set to be 0.1-0.2N/25mm. The water-soluble laminating layer or film coating layer is preferably a polyethylene oxide film. Therefore, because the polyethylene oxide film layer is a film with higher strength and is easy to completely peel off from the bearing layer, the pulling damage of micropores can be avoided, and tests show that the pulling damage of micropores is hardly generated; in contrast, if the aqueous release liner layer is a release agent coating, the micropores are more scratched. Therefore, the water-based easy-to-peel substrate layer adopts the polyethylene oxide film layer, and has remarkable beneficial technical effects. The inventor of the present application has tried to replace PET or BOPP with a water-soluble film such as a polyethylene oxide film as a carrier layer, and experiments have found that the polyethylene oxide film has low tensile strength, poor thermal stability and high thermal shrinkage, so the inventor of the present application has only to coat the polyethylene oxide film on a carrier layer such as PET or BOPP with high tensile strength, good thermal stability, low thermal shrinkage and smooth and clean surface to make up for the performance deficiency. In other words, experiments show that a water-soluble film such as a polyethylene oxide film can not directly replace PET or BOPP as a bearing layer, but can replace the existing release agent coating with excellent performance.
Preferably, the preparation method of the high-barrier degradable environment-friendly packaging material is characterized by comprising the following steps: the coating layer is vapor-deposited 73-75% of Si0 2 And 25-27% of AL 2 O 3 And (6) mixing the coating layer. The study showed that: the barrier property of the mixture ratio is highest, and the milk and the fruit juice in the packaging bag have the shelf life of more than 12 months, even 3 years without deterioration.
Preferably, the preparation method of the high-barrier degradable environment-friendly packaging material is characterized by comprising the following steps: coating a Teflon coating or a silicone oil coating on the surface of the bearing layer to prepare an anti-sticking bearing layer with the stripping force of 0.1-0.2N/25mm; the barrier coating is used as a water-based easy-to-peel liner layer and coated on the Teflon coating or the silicone oil coating of the anti-sticking bearing layer. Thus, the water-based easily-stripped substrate layer is omitted, the material cost is saved, the process of coating the barrier coating is omitted, and the basic fastness of the packaging material is enhanced.
Preferably, the preparation method of the high-barrier degradable environment-friendly packaging material is characterized by comprising the following steps: and coating a preset high-resistance layer on the front surface or the back surface of the stripped and recovered bearing layer so as to recover and use the bearing layer for multiple times.
In order to achieve one of the above purposes, the technical scheme of the high-barrier degradable environment-friendly packaging material is as follows.
The application relates to a high-barrier degradable environment-friendly packaging material which comprises a paper layer, a coating layer and a barrier coating; the method is characterized in that: the bearing layer is stripped; a prefabricated high-resistance layer which is composed of a water-based easily-stripped substrate layer, a coating layer and a water-based porous coating (and the like) is retained and bonded on the front surface of the paper layer; preferably, a water-based barrier coating is further coated on the prefabricated high-resistance layer.
Therefore, on one hand, the coating layer is formed on the moisture-free bearing layer in advance, so that the coating layer does not have water vapor perforation in the vapor deposition forming process; on the other hand, when the bearing layer is compounded with the paper layer, the solidified coating layer can not be penetrated even if water vapor exists. As such, the present packaging material has high barrier properties and degradability.
In practice, it is found that after the carrier layer is stripped, the carrier layer is adhered and retained on the coating layer on the paper layer, and a plurality of randomly-positioned and-numbered pulling micropores are inevitably generated, and the pulling micropores can cause air leakage of the coating layer and greatly reduce the barrier property. In order to avoid the generation of the pulling micropores, researchers spend nearly one year and over a million yuan of research cost, repeated experiments are carried out by adopting the technical measures of thickening the coating layer, and tests show that the technical measures of thickening the coating layer can not completely avoid the generation of the pulling micropores.
Preferably, the high-barrier degradable environment-friendly packaging material is characterized in that: the formula of the water-based porous coating comprises 50% of methyl orthosilicate, 30% of V-aminopropyl triethoxysilane and 20% of zirconium propanol.
Preferably, the high-barrier degradable environment-friendly packaging material is characterized in that: multiple prefabricated high-resistance layers are retained and bonded on the paper layer; wherein, the strain micropores, the sand holes and the vapor perforations on the upper and the lower coating layers are mutually staggered and do not coincide.
Thus, the non-plastic ultrahigh-resistance material is prepared, dislocation occurs due to the air leakage holes such as the scratch micropores, the sand holes, the water vapor perforation and the like on the upper coating layer and the lower coating layer, the probability of complete coincidence is almost zero, and researches show that the coincidence rate is less than or equal to 10 -7 And (4) finishing. And the material is blocked by another inorganic coating layer instead of being compensated by an organic blocking coating layer, so that the blocking performance of the plastic-free ultrahigh-resistance material can be greatly improved. The contrast experiment shows that compared with the non-plastic high-resistance material with the same thickness, the non-plastic high-resistance material has the barrier property improved by several times, for example: the milk and the fruit juice filled into the plastic-free high-resistance material packaging bags with the same thickness have the shelf life of at most 3 months, while the milk and the fruit juice filled into the plastic-free ultrahigh-resistance material packaging bags with the same thickness have the shelf life of more than 12 months, even 3 years without deterioration.
Preferably, the high-barrier degradable environment-friendly packaging material is characterized in that: a high-resistance water-proof composite glue layer is coated between the water-based porous coating layer (on the prefabricated high-resistance layer) and the paper layer, wherein the paper layer is made of moisture-absorbing and breathable paper (non-breathable non-moisture-absorbing paper such as laminating paper, glassine paper, oil-impregnated paper and the like cannot be used); on the one hand, to retain and adhere the preformed high-barrier layer to the paper layer and, on the other hand, to further improve the barrier properties of the packaging material.
Preferably, the high-barrier degradable environment-friendly packaging material is characterized in that: the water-based easy-to-peel liner layer is a water-soluble laminating layer or a water-soluble laminating layer; the peeling force between the water-based easy-peeling substrate layer and the bearing layer is 0.1-0.2N/25mm.
Preferably, the high-barrier degradable environment-friendly packaging material is characterized in that: the coating layer is vapor-deposited 73-75% of Si0 2 And 25-27% of AL 2 O 3 And (5) mixing the coating layer.
Preferably, the high-barrier degradable environment-friendly packaging material is characterized in that: coating a Teflon coating or a silicone oil coating on the surface of the bearing layer, wherein the stripping force is 0.1-0.2N/25mm; the barrier coating is also used as a water-based easy-stripping substrate layer and is coated on the Teflon coating or the silicone oil coating.
In order to achieve the second purpose, the technical scheme of the high-barrier degradable environment-friendly packaging material is as follows.
The application relates to a high resistant separates degradable environmental protection packing material, its characterized in that: the packaging material is made of any one of the high-barrier degradable environment-friendly packaging materials.
Preferably, the flat texture string is embedded in the package, and the texture information file of the flat texture string is stored in the anti-counterfeiting checking system database for the public to check the authenticity. The flat texture string can be referred to Chinese invention patent 'hand-tearing texture anti-counterfeiting method and product and material thereof (CN 109215493B)'.
For convenience, the terms front, back, and the like are used herein in the sense that the front and back are relative, and if one is referred to as the front, the other is necessarily the back, and vice versa.
Compared with the prior art, the application can produce the following beneficial technical effects.
Firstly, the degradable, pollution-free: in the high-barrier degradable environment-friendly packaging material and the packaging material thereof, only the water-based materials such as the paper layer, the water-based porous coating layer and the water-based barrier layer which can be naturally degraded are contained, and Si0 2 Coating layer or/and AL 2 O 3 And harmless inorganic substances such as vapor coating and the like.
Secondly, the composite material has ultrahigh barrier property: the barrier property is close to that of the packaging material and the packaging material which use the aluminum foil layer as the barrier layer currently. Compared with the prior art 2-12, the shelf life of the product in the plastic-free ultrahigh-resistance material can be prolonged to more than one year, and the shelf life of the product in the plastic-free ultrahigh-resistance material with multiple prefabricated high-resistance layers can be prolonged to even three years.
Thirdly, the method is environment-friendly and pollution-free: can be recycled and reused, and can be naturally degraded and broken into harmless inorganic powder even if not recycled. Can not cause pollution to the environment.
Fourthly, energy conservation: because the bearing layer has no moisture, the vacuum degree is easy to reach 10 -3 Compared with the background technology 2-12, the vacuum requirement of mpa reduces the energy consumption of the vacuum pump by more than 68%.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a schematic cross-sectional structure diagram of a carrier layer and a preformed high-resistance layer thereof in this application (embodiment a).
Fig. 2 is a schematic cross-sectional structure diagram of a non-plastic high-resistance material in the present application (example two).
Fig. 3 is a schematic cross-sectional structure diagram of a non-plastic ultra-high-resistance material in the present application (example three).
FIG. 4 is a schematic plan view of the randomly distributed water vapor perforations in the coatings of prior art 2-12.
FIG. 5 is a schematic plan view of randomly distributed scratch micro-holes on a plated film.
Fig. 6 is a schematic diagram of the leakage path of the plastic-free high-resistance material in fig. 2.
Fig. 7 is a schematic diagram of the air leakage path of the plastic-free ultra-high resistance material in fig. 3.
Fig. 8 is a schematic view of a milk package made of a plastic-free ultra-high resistance material according to the present application (example four).
Figure 9 is a schematic view of a blister pack for pharmaceutical products made of a non-plastic ultra-high-resistance material according to the present application (example four).
The reference numbers illustrate: 1-paper layer, 2-water-based composite glue layer, 3-prefabricated high-resistance layer, 301-water-based porous coating layer, 302-film coating layer, 303-water-based easily-stripped substrate layer, 4-bearing layer, 5-water-based barrier coating layer, 6-heat sealing coating layer, 7-water vapor perforation, 8-pulling micropore, 9-air leakage path, 10-milk package and 11-flat texture string.
Detailed Description
The first embodiment.
As shown in fig. 1, fig. 1 is a schematic cross-sectional structure diagram of a carrier layer and a preformed high-resistance layer thereof.
A25-micron PET film is adopted as the bearing layer 4, and a polyethylene oxide film layer with the thickness of 6-12 microns (the peeling force is preferably 0.1-0.2N/25 mm) is firstly laminated on the front surface of the bearing layer 4 by using a laminating machine to be used as the water-based easy-peeling substrate layer 303. Then the vacuum degree is more than or equal to 10 -3 Vapor deposition of Si0 onto an aqueous easy-to-peel liner layer 303 in an mpa vacuum chamber 2 Coating or/and AL 2 O 3 Oxide coatings 302 such as coatings; finally, coating a water-based pore-filling coating 301 such as acrylic emulsion on the coating layer 302 to plug micropores such as sand holes on the coating layer 302; the water-based easy-to-strip substrate layer 303, the film coating layer 302, the water-based porous coating layer 301 and other layers form a prefabricated high-resistance (separation) layer 3 together, and the prefabricated high-resistance (separation) layer is temporarily coated on the bearing layer 4 for later stripping.
In the above steps, the reason why the water-based porous coating 301 is applied is that some sand holes caused by many unexpected factors such as dust are still formed in the vapor deposition process of the film coating 302, and in order to fill the sand holes and improve the barrier property, technical measures for applying the water-based porous coating 301 are taken.
In the above steps, the polyethylene oxide film layer as the aqueous easy-to-peel substrate layer 303 has strong film forming property and degradability, and almost has the same characteristics as a thin film, so that the polyethylene oxide film layer is easy to completely peel off from the carrier layer 4, and therefore, the pulling damage micropores 8 can be reduced, and tests show that the pulling damage micropores 8 are hardly generated. Therefore, the water-based easily-stripped substrate layer 303 adopts a polyethylene oxide film layer, and has a remarkable beneficial technical effect.
In the above steps, the aqueous easy-to-peel substrate layer 303 may also be prepared by using an aqueous low-viscosity coating, for example, a formula of 1015 parts of mica powder, 58 parts of silicon dioxide, 1522 parts of borax, 38 parts of talcum powder, 1218 parts of graphite emulsion, 1116 parts of an emulsifier, 25 parts of a defoaming agent, 2025 parts of an organic silicon resin, 1624 parts of a polyurethane adhesive, and 712 parts of a hydrophilic chain extender. The aqueous low-viscosity coating with the formula also has good easy-stripping characteristic, and can be used for coating and setting the aqueous easy-stripping substrate layer 303. Of course, one skilled in the art can select a variety of suitable low viscosity waterborne coatings, following a peel force of 0.1-0.2N/25mm.
Preferably, 73-75% Si0 is used 2 And 25-27% of AL 2 O 3 The mixed raw materials are evaporated. The study shows that: the coating layer 302 formed by the formula has the highest barrier property, and the packaging bag made of the coating layer is filled with milk and fruit juice, so that the shelf life is as long as more than 12 months, and even 3 years can not deteriorate. Conversely, less than 72% and more than 75% Si0 in the formulation 2 And less than 25% and more than 27% AL 2 O 3 The formed plating layer 302 has low barrier properties. In other words, the window of the formulation with the highest barrier is narrow, si0 2 Only 75% -72% =3%, AL 2 O 3 Only 27% -25% =2%, and the narrow formula window data is discovered by the inventor of the applicant accidentally, so that the method is not easy to use and has a very obvious technical effect.
The second embodiment.
As shown in fig. 2, fig. 2 is a schematic cross-sectional structure diagram of a plastic-free high-resistance material.
One material of 76g/m is selected and purchased 2 The non-fluorescent white lining paper is used as a paper layer 1, and an acrylic ester emulsion is selected as a water-based composite glue layer 2. Compounding the prefabricated high-resistance layer 3 on the bearing layer 4 facing the front side of the paper layer 1 by adopting a wet compounding process, and drying at a high temperature of more than 100 ℃; then coating the mixture on a plurality of cooling rollers at the temperature of 4-12 ℃ for rapid cooling; stripping and recovering the bearing layer 4 at the low temperature of 4-12 ℃, wherein the back surface of the bearing layer 4 is tightly attached to the cold roll for 0.5-3 seconds to reserve enough time and fully cool; then, the plastic-free high-resistance material formed by the prefabricated high-resistance layer 3 and the paper layer 1 is sent to a coating unit and heated to normal temperature. Finally, a layer of acrylic ester emulsion is coated on the exposed water-based easily-stripped substrate layer 303 after the bearing layer 4 is stripped to serve as a water-based barrier coating 5, and then the non-plastic high-resistance material can be prepared. The plastic-free high resistanceThe material can replace the existing aluminum foil lining paper, for example, the aluminum foil lining paper in the existing cigarette box.
Thus, the number of the pulling micropores 8 is greatly reduced, and statistics show that the number of the pulling micropores 8 is reduced by at least ten times. Compared with the traditional method for changing the formula of the water-based easily-stripped substrate layer 303, the method is low in cost and easy to implement. Practice proves that: when the temperature of the prefabricated high-resistance layer 3 and the paper layer 1 is reduced to 4-12 ℃, the film forming property and the toughness of the water-based easily-stripped substrate layer 303 are greatly improved, and the substrate layer is easily and completely stripped from the bearing layer 4, so that strain micropores 8 can be reduced. It is to be emphasized here that: the applicant researches that when the temperature is reduced to 4-12 ℃, the film forming property and toughness of the water-based easily-peelable substrate layer 303 are greatly improved, so that the water-based easily-peelable substrate layer can be easily and completely peeled off from the bearing layer 4, and the strain micro-holes 8 are greatly reduced.
Example three.
Preferably, as shown in fig. 3, on the non-plastic high-resistance material prepared on the above example, 1-2 layers of the prefabricated high-resistance layer 3 are compounded, dried, retained and bonded to prepare the non-plastic ultrahigh-resistance material.
Thus, the scratch micropores 8, the sand holes and the water vapor through holes 7 on the upper and lower coating layers 4 are necessarily mutually staggered, and the probability of complete superposition is almost zero. And the gas leakage path 9 between two nearest gas leakage holes of the upper layer and the lower layer is inevitably very long because the gas leakage path is completely blocked by the other inorganic coating layer 302 instead of being simply compensated by the water-based barrier coating layer 5, so that the barrier property of the material is greatly improved, in other words, the plastic-free ultrahigh-resistance material can be prepared by adopting the process method of the embodiment.
Fig. 6 is a schematic diagram of the leakage path of the plastic-free high-resistance material in fig. 2. Fig. 7 is a schematic view of the leakage path of the plastic-free ultra-high resistance material in fig. 3. Comparing the two figures, it can be seen that the leakage path 9 with the multiple pre-made high resistance layers 3 is the longest, and the leakage path 9 in fig. 7 is lengthened hundreds of times compared with the leakage path 9 in fig. 6, which is the most difficult reason for leakage. In other words, the plastic-free high-resistance material with multiple prefabricated high-resistance layers 3 has ultrahigh resistance.
The back of the paper layer 1 on the non-plastic high-resistance material manufactured by the process is coated with the water-based heat-sealing coating 6, and then the packaging bag for milk and fruit juice can be manufactured by using the packaging bag.
The comparative experiment shows that compared with the non-plastic high-resistance material with the same thickness, the barrier property of the non-plastic high-resistance material is improved by multiple times, for example: the milk and the fruit juice filled into the plastic-free high-resistance material packaging bags with the same thickness have the shelf life of at most 3 months, while the milk and the fruit juice filled into the plastic-free ultrahigh-resistance material packaging bags with the same thickness have the shelf life of more than 12 months, even 3 years without deterioration.
Example four.
Preferably, as shown in fig. 8 and 9, the above examples of the milk package 10 made of plastic-free super-high-resistance material can be made into a tetra pak type, which can replace the tetra pak package made of the existing aluminum foil composite material.
Preferably, the plastic-free super-high-resistance materials prepared in the previous examples are used for medicine blister packages, and can replace the existing aluminum foil. If the flat texture string is embedded in the medicine blister package, the texture information file of the flat texture string is collected and stored in the anti-counterfeiting checking system database, and therefore the public can check the authenticity. The flat texture string can be referred to the Chinese invention patent 'hand-tearing texture anti-counterfeiting method and product and material thereof (CN 109215493B)'.
The technical solutions provided by the present application are described in detail above. The principles and embodiments of the present application are explained herein using specific examples, which are provided only to help understand the method and the core idea of the present application. It should be noted that, for those skilled in the art, without departing from the principle of the present application, several improvements and modifications can be made to the present application, and these improvements and modifications also fall into the protection scope of the present application.

Claims (10)

1. A high-barrier degradable environment-friendly packaging material comprises a paper layer, a coating layer and a barrier coating; the method is characterized in that: the bearing layer is stripped; the prefabricated high-resistance layer is formed by the water-based easy-to-peel substrate layer, the coating layer and the water-based porous coating layer, and is retained and bonded on the front surface of the paper layer.
2. The high-barrier degradable environment-friendly packaging material as claimed in claim 1, wherein: and the prefabricated high-resistance layer is also coated with a water-based barrier coating.
3. The high-barrier degradable environment-friendly packaging material as claimed in claim 1, wherein: and a water-based heat sealing adhesive coating is coated on the back surface of the paper layer.
4. The high-barrier degradable environment-friendly packaging material as claimed in claim 2, wherein: and a water-based heat sealing adhesive coating is coated on the back surface of the paper layer.
5. The high-barrier degradable environment-friendly packaging material as claimed in claim 1, 2, 3 or 4, wherein: multiple prefabricated high-resistance layers are retained and bonded on the paper layer; wherein, the strain micropores, the sand holes and the water vapor perforations on the upper and the lower coating layers are staggered with the coincidence rate less than or equal to 10 -7 。
6. The high-barrier degradable environment-friendly packaging material as claimed in claim 1, 2, 3 or 4, wherein: a high-resistance waterproof composite glue layer is coated between the water-based porous coating and the paper layer; wherein the paper layer is made of breathable moisture absorption paper.
7. The high-barrier degradable environment-friendly packaging material as claimed in claim 1, 2, 3 or 4, wherein: the water-based easy-to-peel liner layer is a water-soluble laminating layer or a water-soluble laminating layer; the peeling force between the water-based easy-peeling substrate layer and the bearing layer is 0.1-0.2N/25mm.
8. The high-barrier degradable environment-friendly packaging material as claimed in claim 1, 2, 3 or 4, wherein: coating a Teflon coating or a silicone oil coating on the surface of the bearing layer, wherein the stripping force is 0.1-0.2N/25mm; the barrier coating is also used as a water-based easy-stripping substrate layer and is coated on the Teflon coating or the silicone oil coating.
9. A high-barrier degradable environment-friendly packaging material is characterized in that: the packaging material is made of the high-barrier degradable environment-friendly packaging material in any one of claims 1-8.
10. The high barrier degradable environment friendly package according to claim 9, wherein: the flat grain string is embedded in the packing material, and the grain information file of the flat grain string is stored in the anti-counterfeiting checking system database for the public to check the authenticity.
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Inventor after: Chen Xueling

Inventor before: Chen Mingfa