WO2023226936A1 - 一种针剂包装用复合片材及其制备方法和应用 - Google Patents

一种针剂包装用复合片材及其制备方法和应用 Download PDF

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Publication number
WO2023226936A1
WO2023226936A1 PCT/CN2023/095561 CN2023095561W WO2023226936A1 WO 2023226936 A1 WO2023226936 A1 WO 2023226936A1 CN 2023095561 W CN2023095561 W CN 2023095561W WO 2023226936 A1 WO2023226936 A1 WO 2023226936A1
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layer
composite
composite sheet
density polyethylene
heat sealing
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PCT/CN2023/095561
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English (en)
French (fr)
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WO2023226936A9 (zh
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朱业玲
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上海紫江彩印包装有限公司
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Publication of WO2023226936A1 publication Critical patent/WO2023226936A1/zh
Publication of WO2023226936A9 publication Critical patent/WO2023226936A9/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B32B27/32—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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • 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

Definitions

  • This application belongs to the field of packaging technology, and specifically relates to a composite sheet for injection packaging and its preparation method and application.
  • Pesticides are packaged in various forms depending on the content, such as bottles, boxes, injections and bags. Injection packaging is mostly used in small-weight liquid pesticides.
  • Composite sheet for injection packaging is mainly a packaging material composed of two or more layers of different materials.
  • CN112812419A discloses a high-barrier pesticide bottle and its preparation method.
  • the high-barrier pesticide bottle includes a barrier layer, an adhesive layer and a PE base layer from the inside to the outside.
  • the barrier layer is made of raw materials containing the following parts by weight: ethylene.
  • - Vinyl alcohol copolymer 20 to 30 parts; maleic anhydride grafted polyethylene: 10 to 16 parts; the high-barrier pesticide bottle prepared by this invention has excellent barrier effect on oily solvents and has high impact resistance. , making it less likely to break.
  • CN103434237A discloses an easy-to-tear dry composite sheet, which includes a body.
  • the body is provided with a printing layer, a base layer, and a heat sealing layer from top to bottom.
  • the printing layer is a cast polypropylene film.
  • the base layer It is polyethylene terephthalate (PET), and the heat sealing layer is a polyethylene film; the cast polypropylene film, polyethylene terephthalate, and polyethylene film are combined into a single body.
  • PET polyethylene terephthalate
  • the stretched polypropylene film has good printing and stretch forming properties
  • polyethylene terephthalate has good forming properties
  • the polyethylene film has easy tearing properties, ensuring that the body after production has good printing effects and heat sealability.
  • CN111169131A discloses a blown film forming asymmetric sheet, which includes an inner film layer, a first connecting layer, and an inner film layer arranged sequentially from the inside to the outside.
  • the inner film layer includes a heat sealing layer and a first support layer from the inside to the outside;
  • the outer film layer includes a second support layer and printing from the inside to the outside.
  • the sheet is formed by a one-time upward blowing method, and the entire asymmetric sheet is air-cooled and shaped.
  • the invention provides a one-time blown film forming asymmetric sheet with excellent barrier properties and low preparation cost.
  • the sheets provided in the above-mentioned prior art only have excellent performance in a single aspect, and it is difficult to meet the requirements of barrier properties, mechanical properties and heat sealing strength of composite sheets for injection packaging at the same time. Therefore, the use of composite sheets for injection packaging is limited. Application of composite sheets in liquid pesticide packaging.
  • the purpose of this application is to provide a composite sheet for injection packaging and its preparation method and application.
  • the composite sheet for injection packaging includes a printing layer, an intermediate layer and a heat sealing layer arranged in sequence.
  • the polymer is used as the material of the heat sealing layer, so that the resulting composite sheet for injection packaging has excellent heat sealing strength and peeling strength.
  • the content weight loss rate is low, the pressure bearing capacity is high, and it has a wide range of applications. prospect.
  • the application provides a composite sheet for injection packaging, wherein the composite sheet for injection packaging includes a printing layer, an intermediate layer and a heat sealing layer arranged in sequence;
  • the heat sealing layer is composed of a composite layer, a core layer and an inner layer arranged in sequence;
  • the composite sheet for injection packaging includes a printed layer, an intermediate layer and a heat sealing layer arranged in sequence, and the heat sealing layer is composed of a composite layer, a core layer and an inner layer arranged in sequence; and further limits the composite
  • the material of the layer includes a combination of linear low density polyethylene and low density polyethylene
  • the material of the core layer includes a combination of linear low density polyethylene and a cyclic olefin polymer
  • the material of the inner layer includes metallocene polyethylene; by Choosing polyethylene and cyclic olefin polymers as materials for the heat sealing layer can, on the one hand, improve the peel strength of the heat sealing layer and the middle layer, so that the final composite sheet for injection packaging has strong heat sealing strength and durability after molding.
  • the injection packaging bag obtained after molding the composite sheet for injection packaging has excellent water vapor barrier properties, so that the content weight loss rate of the injection packaging bag is low when used.
  • the innermost layer of the injection packaging bag obtained after molding the composite sheet for injection packaging provided by the present application is a heat sealing layer.
  • the heat sealing layer directly contacts the contents during use, and the heat sealing layer contains
  • the composite layer is in direct contact with the middle layer, and the outermost layer of the composite sheet is the printing layer, which is in direct contact with the air.
  • the material of the inner layer includes a combination of ExxonMobil 1018MB and Dow 1881G, and the mass percentage of Dow 1881G is ⁇ 30%, such as 35%, 40%, 50%, 60%, 70%, 80 % or 90% etc.
  • the thickness ratio of the composite layer and the core layer is 1:(2.5 ⁇ 4), such as 1:2.7, 1:2.9, 1:3.1, 1:3.3, 1:3.5, 1:3.7 or 1:3.9 wait.
  • the thickness ratio of the composite layer and the inner layer is 1:(0.5 ⁇ 1.5), such as 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2 , 1:1.3 or 1:1.4, etc.
  • the printing layer is an amorphous PET film.
  • the thickness of the printing layer is 10-30 ⁇ m, such as 12 ⁇ m, 14 ⁇ m, 16 ⁇ m, 18 ⁇ m, 20 ⁇ m, 22 ⁇ m, 24 ⁇ m, 26 ⁇ m or 28 ⁇ m, etc.
  • the middle layer is an amorphous PET film.
  • the thickness of the intermediate layer is 200-300 ⁇ m, such as 210 ⁇ m, 220 ⁇ m, 230 ⁇ m, 240 ⁇ m, 250 ⁇ m, 260 ⁇ m, 270 ⁇ m, 280 ⁇ m or 290 ⁇ m, etc.
  • the thickness of the heat sealing layer is 150-200 ⁇ m, such as 155 ⁇ m, 160 ⁇ m, 165 ⁇ m, 170 ⁇ m, 175 ⁇ m, 180 ⁇ m, 185 ⁇ m, 190 ⁇ m or 195 ⁇ m, etc.
  • the mass percentage of linear low-density polyethylene in the material of the composite layer is 80 to 89%, such as 81%, 82%, 83%, 84%, 85%, 86%, 87% or 88% wait.
  • the mass percentage of low-density polyethylene in the material of the composite layer is 10 to 15%, such as 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14% or 14.5% etc.
  • the material of the composite layer further includes a processing aid.
  • the mass percentage of linear low-density polyethylene in the material of the core layer is 50 to 70%, such as 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66% Or 68% etc.
  • the mass percentage of cyclic olefin polymer in the material of the core layer is 30 to 50%, such as 32%, 35%, 34%, 36%, 38%, 40%, 42%, 44%, 46% % or 48% etc.
  • the mass percentage of metallocene polyethylene in the material of the inner layer is 95-99%, for example 95.5%, 96%, 96.5%, 97%, 97.5%, 98% or 98.5% etc.
  • the material of the inner layer further includes a processing aid.
  • the mass percentage of the processing aid in the material of the inner layer is 1 to 5%, such as 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%.
  • the melt index of the linear low-density polyethylene in the composite layer and the linear low-density polyethylene in the middle layer are each independently 1 to 4g/10min, such as 1.5g/10min, 2g/10min, 2.5g/ 10min, 3g/10min or 3.5g/10min, etc.
  • the densities of the linear low-density polyethylene in the composite layer and the linear low-density polyethylene in the intermediate layer are each independently 0.92 to 0.94g/cm 3 , such as 0.922g/cm 3 and 0.924g/cm 3 , 0.926g/cm 3 , 0.928g/cm 3 , 0.93g/cm 3 , 0.932g/cm 3 , 0.934g/cm 3 , 0.936g/cm 3 or 0.938g/cm 3 etc.
  • the melt index of the low-density polyethylene is 1 to 4g/10min, such as 1.5g/10min, 2g/10min, 2.5g/10min, 3g/10min or 3.5g/10min, etc.
  • the density of the low-density polyethylene is 0.92-0.94g/cm 3 , such as 0.922g/cm 3 , 0.924g/cm 3 , 0.926g/cm 3 , 0.928g/cm 3 , 0.93g/cm 3 , 0.932g/cm 3 , 0.934g/cm 3 , 0.936g/cm 3 or 0.938g/cm 3 etc.
  • the density of the metallocene polyethylene is 0.90-0.92g/cm 3 , such as 0.902g/cm 3 , 0.906g/cm 3 , 0.912g/cm 3 , 0.914g/cm 3 , 0.915g/cm 3 , 0.916g/cm 3 , 0.917g/cm 3 , 0.918g/cm 3 or 0.919g/cm 3 etc.
  • test conditions for the melt index of the materials provided in this application are all 2.16kg. 190°C.
  • the processing aid in the composite layer and the processing aid in the inner layer each independently include PPA and/or opening agent.
  • the heat sealing layer is prepared by subjecting the composite layer material, the core layer material and the inner layer material to three layers of co-extrusion and corona treatment to obtain the heat sealing layer.
  • the three-layer co-extrusion is performed in blown film equipment.
  • the temperature of the three-layer co-extrusion is 160-250°C, such as 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 210°C, 220°C, 230°C Or 240°C, etc.
  • a first adhesive layer is further provided between the printing layer and the intermediate layer.
  • the raw materials for preparing the first adhesive layer include solvent-based polyurethane glue or solvent-free polyurethane glue.
  • a second adhesive layer is further provided between the intermediate layer and the heat sealing layer.
  • the raw material for preparing the second adhesive layer includes solvent-based polyurethane glue.
  • this application provides a method for preparing a composite sheet for injection packaging as described in the first aspect.
  • the preparation method includes: using the material of the first adhesive layer and the material of the second adhesive layer to print the The layers, the middle layer and the heat sealing layer are connected in sequence and cured to obtain the composite sheet for injection packaging.
  • the temperature of the aging treatment is 50-60°C, such as 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C or 59°C.
  • this application provides an application of the composite sheet for injection packaging as described in the first aspect in liquid pesticide packaging.
  • the composite sheet for injection packaging includes a printed layer, an intermediate layer and a Heat sealing layer, the heat sealing layer is composed of a composite layer, a core layer and an inner layer arranged in sequence; the material of the composite layer includes a combination of linear low density polyethylene and low density polyethylene, and the material of the core layer includes A combination of linear low density polyethylene and cyclic olefin polymers, the material of the inner layer includes metallocene polyethylene; the material of the heat sealing layer includes polyethylene and cyclic olefin polymers; by selecting polyethylene and cyclic olefin polymers The combination is used as the main material of the heat sealing layer, so that the obtained composite sheet for injection packaging has high peel strength and heat sealing strength, and also has excellent moisture barrier properties, which can ensure that the injection packaging bag obtained after its molding is in use It has lower water vapor transmission rate and content weight loss rate, and also has excellent pressure-bearing capacity, and has broad application prospects.
  • a composite sheet for injection packaging consisting of a printing layer, a first adhesive layer, an intermediate layer, a second adhesive layer and a heat sealing layer arranged in sequence;
  • the printing layer is an amorphous PET film with a thickness of 20 ⁇ m (the material is PET, Bolian APET-20);
  • the first bonding layer is a solvent-free polyurethane glue layer (Keyi SF7660);
  • the middle layer is an amorphous PET film with a thickness of 250 ⁇ m (material is PET, Sichuan Dongcai PET-250);
  • the second adhesive layer is a solvent-based polyurethane adhesive layer (material is solvent-based polyurethane glue, Henkel UK8640);
  • the thickness of the heat sealing layer is 200 ⁇ m, and it consists of a composite layer, a core layer and an inner layer with a thickness of 1:3.5:1 in sequence.
  • the components in each layer, their contents and sources are shown in Table 1:
  • the preparation method of the heat sealing layer includes: melting at 180°C, plasticizing the materials of the composite layer, core layer and inner layer in the film blowing equipment, extruding through the die, cooling and shaping, and electrically conducting the composite layer. Halo treatment to obtain the heat sealing layer;
  • the middle layer is an amorphous PET film (Sichuan Dongcai PET-250) with a thickness of 250 ⁇ m;
  • the second adhesive layer is a solvent-based polyurethane adhesive layer (Henkel UK8640);
  • the thickness of the heat sealing layer is 200 ⁇ m, and it consists of a composite layer, an intermediate layer and an inner layer with a thickness of 1:3.5:1 in sequence.
  • the components of each layer, their content and sources are shown in Table 2:
  • the preparation method of the heat sealing layer includes: plasticizing the materials of the composite layer, core layer and inner layer in the film blowing equipment under 250°C melting conditions, extruding through the die, cooling and shaping, and corona the composite layer. Process to obtain the heat sealing layer;
  • the preparation method of the composite sheet for injection packaging includes the following steps: using solvent-free polyurethane glue and solvent-based polyurethane glue to sequentially bond the printing layer, the middle layer and the heat-sealing layer, and undergo aging treatment to obtain the above Composite sheet for injection packaging.
  • a composite sheet for injection packaging consisting of a printing layer, a first adhesive layer, an intermediate layer, a second adhesive layer and a heat sealing layer arranged in sequence;
  • the first bonding layer is a solvent-free polyurethane glue layer (Keyi SF7660);
  • the transition layer is an amorphous PET film (Sichuan Dongcai PET-300) with a thickness of 300 ⁇ m;
  • the second adhesive layer is a solvent-based polyurethane adhesive layer (Henkel UK8640);
  • the thickness of the heat sealing layer is 150 ⁇ m and consists of a composite layer, an intermediate layer and an inner layer with a thickness of 1:3.5:1 in sequence; the content and source of the raw materials for each layer are shown in Table 3:
  • the preparation method of the composite sheet for injection packaging includes the following steps: using solvent-free polyurethane glue and solvent-based polyurethane glue to sequentially bond the printing layer, the middle layer and the heat-sealing layer, and undergo aging treatment to obtain the above Composite sheet for injection packaging.
  • a composite sheet for injection packaging consisting of a printing layer, a first adhesive layer, an intermediate layer, a second adhesive layer and a heat sealing layer arranged in sequence;
  • the printing layer is an amorphous PET film (Bolaine APET-23) with a thickness of 23 ⁇ m;
  • the first bonding layer is a solvent-free polyurethane glue layer (Keyi SF7660);
  • the transition layer is an amorphous PET film (Sichuan Dongcai PET-250) with a thickness of 250 ⁇ m;
  • the second adhesive layer is a solvent-based polyurethane adhesive layer (Henkel UK8640);
  • the thickness of the heat sealing layer is 200 ⁇ m and consists of a composite layer, a core layer and an inner layer with a thickness of 1:3.5:1 in sequence; the content and source of the raw materials for each layer are shown in Table 4:
  • the preparation method of the heat sealing layer includes: plasticizing the materials of the composite layer, core layer and inner layer in the film blowing equipment under 190°C melting conditions, extruding through the die, cooling and shaping, and conducting the composite layer Corona treatment to obtain the heat sealing layer;
  • the preparation method of the composite sheet for injection packaging includes the following steps: using solvent-free polyurethane glue and solvent-based polyurethane glue to sequentially bond the printing layer, the middle layer and the heat-sealing layer, and undergo aging treatment to obtain the above Composite sheet for injection packaging.
  • a composite sheet for injection packaging which differs from Example 1 in that the materials of the first adhesive layer and the second adhesive layer are both solvent-based polyurethane glue (Henkel UK8640), and other structures, parameters and preparation methods All are the same as Example 1.
  • a composite sheet for injection packaging which differs from Example 1 in that the mass percentage of linear low-density polyethylene (Dow 2045G) in the material of the composite layer in the heat-sealing layer is 14%, and the low-density polyethylene
  • the mass percentage of ethylene (CSSL 2420H) is 85%, and other structures, parameters and preparation methods are the same as in Example 1.
  • a composite sheet for injection packaging which differs from Example 1 in that the mass percentage of linear low-density polyethylene (Dow 2045G) in the material of the core layer in the heat sealing layer is 85%, and the cyclic olefin polymerization
  • the mass percentage of the compound (TOPAS 8007F-600) is 15%, and other structures, parameters and preparation methods are the same as in Example 1.
  • a composite sheet for injection packaging which differs from Example 1 in that the mass percentage of metallocene polyethylene (Dow 1881G) in the material of the inner layer of the heat sealing layer is 15%, and the metallocene polyethylene The mass percentage of (ExxonMobil 1018MB) is 82%, and other structures, parameters and preparation methods are the same as in Example 1.
  • a composite sheet for injection packaging which differs from Example 1 in that the materials of the first adhesive layer and the second adhesive layer are both solvent-free polyurethane glue (Keyi SF7660), and other structures, parameters and preparation The methods are all the same as in Example 1.
  • a composite sheet for injection packaging The difference from Example 1 is that linear low-density polyethylene (Dow 2045G) is not added to the material of the composite layer in the heat-sealing layer. It is composed of 100% by mass Composed of low-density polyethylene (CSSC 2420H), other structures, parameters and preparation methods are the same as those implemented Same as Example 1.
  • Dow 2045G linear low-density polyethylene
  • CSSC 2420H 100% by mass Composed of low-density polyethylene
  • a composite sheet for injection packaging which differs from Example 1 in that the core layer material in the heat sealing layer does not add cyclic olefin polymer (TOPAS 8007F-600), and is composed of 100% mass percentage It is composed of linear low-density polyethylene (Dow 2045G), and other structures, parameters and preparation methods are the same as in Example 1.
  • TOPAS 8007F-600 cyclic olefin polymer
  • Low 2045G linear low-density polyethylene
  • Example 1 A composite sheet for injection packaging. The difference from Example 1 is that linear low-density polyethylene (Dow 2045G) is not added to the material of the core layer in the heat-sealing layer. It is composed of 100% by mass Cyclic olefin polymer (TOPAS 8007F-600), other structures, parameters and preparation methods are the same as Example 1.
  • Dow 2045G linear low-density polyethylene
  • TOPAS 8007F-600 Cyclic olefin polymer
  • Weight loss rate Make the obtained composite sheet into a packaging bag for packaging liquid pesticides, place it in an oven at 54°C for two weeks, weigh the weight change of the sample before and after, and then calculate the weight loss rate;

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Abstract

本申请提供一种针剂包装用复合片材及其制备方法和应用，所述针剂包装用复合片材包括依次设置的印刷层、中间层和热封层，所述热封层由依次设置的复合层、芯层和内层组成，所述复合层的材料包括线性低密度聚乙烯和低密度聚乙烯的组合，所述芯层的材料包括线性低密度聚乙烯和环烯烃聚合物的组合，所述内层的材料包括茂金属聚乙烯。通过选择聚乙烯和环烯烃聚合物搭配作为热封层的主要材料，使得到的针剂包装用复合片材具有较高的剥离强度和热封强度，还具有优异的阻湿性能，可以保证其成型后得到的针剂包装袋在使用时具有较低的水蒸气透过率和内容物失重率，同时还具有较高的承压能力，具有广泛的应用前景。

Description

一种针剂包装用复合片材及其制备方法和应用 技术领域
本申请属于包装技术领域，具体涉及一种针剂包装用复合片材及其制备方法和应用。
背景技术
农药根据内容物不同有各种形式的包装，如瓶装、盒装、针剂装和袋装等几种形式，其中针剂包装在小重量的液体农药中应用较多。针剂包装用复合片材主要是由两层或多层不同材料复合而成的包装材料。
目前，对于针剂包装用复合片材的研究和报道有很多。CN112812419A公开了一种高阻隔农药瓶及其制备方法，所述高阻隔农药瓶由内向外依次包括阻隔层、粘接层与PE基层，所述阻隔层由包含如下重量份的原料制成：乙烯-乙烯醇共聚物：20～30份；马来酸酐接枝聚乙烯：10～16份；该发明制备得到的高阻隔农药瓶对油性溶剂具有优异的阻隔作用，同时具有较高的抗冲击性能，使其不易破裂。CN103434237A公开了一种易撕型干式复合片材，包括本体，所述本体由上到下依次设有印刷层、基层、热封层，所述印刷层为流延聚丙烯薄膜，所述基层为聚对苯二甲酸乙二醇酯(PET)，所述热封层为聚乙烯薄膜；通过流延聚丙烯薄膜、聚对苯二甲酸乙二醇酯、聚乙烯薄膜复合成本体，因流延聚丙烯薄膜具有印刷且拉伸成型性能好，聚对苯二甲酸乙二醇酯具有成型性能好，聚乙烯薄膜具有易撕性能，保证了生产后的本体具备良好的印刷效果、热封性以及易撕性、成型性，保证了在线加工时成型效果好，成型后印刷图案精美无明显变形，在消费者使用时热封效果好而且可以易撕开。CN111169131A公开了一种吹膜成型非对称片材，包括由内至外依次相排列的内膜层、第一连 接层、阻隔层、第二连接层、外膜层；所述内膜层包括由内至外的热封层和第一支撑层；外膜层包括由内至外的第二支撑层和印刷层；所述内膜层厚度占片材总厚度百分比为15～30％，外膜层厚度占片材总厚度百分比为50～70％，第一连接层、阻隔层和第二连接层厚度之和占片材总厚度百分比0～40％，所述片材总厚度为200～400μm，所述片材经一次上吹法成型，非对称片材整体经过风冷定型。该发明提供一种阻隔性优异，制备成本低的一次吹膜成型非对称片材。
但是，上述现有技术中提供的片材均仅具有单一方面的优异性能，很难同时满足针剂包装用复合片材对阻隔性能、机械性能以及热封强度的要求，因此限制了针剂包装用复合片材在液体农药包装中的应用。
因此，开发一种兼具优异的阻隔性能，同时具有较高的热封强度以及承压能力的针剂包装用复合片材，是本领域急需解决的技术问题。
发明内容
本申请的目的在于提供一种针剂包装用复合片材及其制备方法和应用，所述针剂包装用复合片材包括依次设置的印刷层、中间层和热封层，通过选择聚乙烯和环烯烃聚合物进行搭配作为热封层的材料，使得到的针剂包装用复合片材具有优异的热封强度和剥离强度，成型使用时内容物失重率较低，承压能力较高，具有广泛的应用前景。
第一方面，本申请提供一种针剂包装用复合片材，其中，所述针剂包装用复合片材包括依次设置的印刷层、中间层和热封层；
所述热封层由依次设置的复合层、芯层和内层组成；
所述复合层的材料包括线性低密度聚乙烯和低密度聚乙烯的组合，所述芯层的材料包括线性低密度聚乙烯和环烯烃聚合物的组合，所述内层的材料包括 茂金属聚乙烯。
本申请提供的针剂包装用复合片材包括依次设置的印刷层、中间层和热封层，且所述热封层由依次设置的复合层、芯层和内层组成；且进一步限定所述复合层的材料包括线性低密度聚乙烯和低密度聚乙烯的组合，所述芯层的材料包括线性低密度聚乙烯和环烯烃聚合物的组合，所述内层的材料包括茂金属聚乙烯；通过选择聚乙烯和环烯烃聚合物作为热封层的材料，一方面提高了热封层和中间层的剥离强度，使最终得到的针剂包装用复合片材成型后具有较强的热封强度和承压能力；另一方面还提高了所述针剂包装用复合片材成型后得到的针剂包装袋具有优异的水蒸气阻隔性能，使得所述针剂包装袋在使用时内容物失重率较低。
需要说明的是，本申请提供的针剂包装用复合片材成型后得到的针剂包装袋的最内层为热封层，热封层在使用时直接接触内容物，且所述热封层中的复合层与中间层直接接触，复合片材的最外层为印刷层，直接接触空气。
在本申请中，所述复合层和芯层中的线性低密度聚乙烯牌号均可以选择陶氏2045G；复合层中的低密度聚乙烯可以选择中海壳牌2420H；芯层中的环烯烃聚合物可以选择TOPAS 8007F-600；内层的茂金属聚乙烯牌号可以选择埃克森美孚1018MB和/或陶氏1881G。
优选地，所属内层的材料包括埃克森美孚1018MB和陶氏1881G的组合，且陶氏1881G质量百分含量≥30％，例如35％、40％、50％、60％、70％、80％或90％等。
优选地，所述复合层和芯层的厚度比为1:(2.5～4)，例如1:2.7、1:2.9、1:3.1、1:3.3、1:3.5、1:3.7或1:3.9等。
优选地，所述复合层和内层的厚度比为1:(0.5～1.5)，例如1:0.6、1:0.7、1:0.8、1:0.9、1:1、1:1.1、1:1.2、1:1.3或1:1.4等。
优选地，所述印刷层为无定型PET膜。
优选地，所述印刷层的厚度为10～30μm，例如12μm、14μm、16μm、18μm、20μm、22μm、24μm、26μm或28μm等。
优选地，所述中间层为无定型PET膜。
优选地，所述中间层的厚度为200～300μm，例如210μm、220μm、230μm、240μm、250μm、260μm、270μm、280μm或290μm等。
优选地，所述热封层的厚度为150～200μm，例如155μm、160μm、165μm、170μm、175μm、180μm、185μm、190μm或195μm等。
优选地，所述复合层的材料中线性低密度聚乙烯的质量百分含量为80～89％，例如81％、82％、83％、84％、85％、86％、87％或88％等。
优选地，所述复合层的材料中低密度聚乙烯的质量百分含量为10～15％，例如10.5％、11％、11.5％、12％、12.5％、13％、13.5％、14％或14.5％等。
优选地，所述复合层的材料中还包括加工助剂。
优选地，所述复合层的材料中加工助剂的质量百分含量为1～5％，例如1.5％、2％、2.5％、3％、3.5％、4％或4.5％等。
优选地，所述芯层的材料中线性低密度聚乙烯的质量百分含量为50～70％，例如52％、54％、56％、58％、60％、62％、64％、66％或68％等。
优选地，所述芯层的材料中环烯烃聚合物的质量百分含量为30～50％，例如32％、35％、34％、36％、38％、40％、42％、44％、46％或48％等。
优选地，所述内层的材料中茂金属聚乙烯的质量百分含量为95～99％，例如 95.5％、96％、96.5％、97％、97.5％、98％或98.5％等。
优选地，所述内层的材料中还包括加工助剂。
优选地，所述内层的材料中加工助剂的质量百分含量为1～5％，例如1.5％、2％、2.5％、3％、3.5％、4％或4.5％等。
优选地，所述复合层中的线性低密度聚乙烯以及中间层中的线性低密度聚乙烯的熔融指数各自独立地为1～4g/10min，例如1.5g/10min、2g/10min、2.5g/10min、3g/10min或3.5g/10min等。
优选地，所述复合层中的线性低密度聚乙烯以及中间层中的线性低密度聚乙烯的密度各自独立地为0.92～0.94g/cm3，例如0.922g/cm3、0.924g/cm3、0.926g/cm3、0.928g/cm3、0.93g/cm3、0.932g/cm3、0.934g/cm3、0.936g/cm3或0.938g/cm3等。
优选地，所述低密度聚乙烯的熔融指数为1～4g/10min，例如1.5g/10min、2g/10min、2.5g/10min、3g/10min或3.5g/10min等。
优选地，所述低密度聚乙烯的密度为0.92～0.94g/cm3，例如0.922g/cm3、0.924g/cm3、0.926g/cm3、0.928g/cm3、0.93g/cm3、0.932g/cm3、0.934g/cm3、0.936g/cm3或0.938g/cm3等。
优选地，所述茂金属聚乙烯的的熔融指数为0.5～8g/10min，例如1g/10min、2g/10min、3g/10min、4g/10min、5g/10min、6g/10min或7g/10min等。
优选地，所述茂金属聚乙烯的密度为0.90～0.92g/cm3，例如0.902g/cm3、0.906g/cm3、0.912g/cm3、0.914g/cm3、0.915g/cm3、0.916g/cm3、0.917g/cm3、0.918g/cm3或0.919g/cm3等。
需要说明的是，本申请所提供的材料的熔融指数的测试条件均为2.16kg， 190℃。
优选地，所述复合层中的加工助剂以及内层中的加工助剂各自独立地包括PPA和/或开口剂。
优选地，所述热封层通过如下方法制备得到：将复合层的材料、芯层的材料以及内层的材料经过三层共挤、电晕处理，得到所述热封层。
优选地，所述三层共挤在吹膜设备中进行。
优选地，所述三层共挤的温度为160～250℃，例如165℃、170℃、175℃、180℃、185℃、190℃、195℃、200℃、210℃、220℃、230℃或240℃等。
优选地，所述印刷层和中间层之间还设置有第一粘合层。
优选地，所述第一粘合层的制备原料包括溶剂型聚氨酯胶水或无溶剂型聚氨酯胶水。
优选地，所述中间层和热封层之间还设置有第二粘结层。
优选地，所述第二粘结层的制备原料包括溶剂型聚氨酯胶水。
第二方面，本申请提供一种如第一方面所述针剂包装用复合片材的制备方法，所述制备方法包括：分别利用第一粘结层的材料以及第二粘结层的材料将印刷层、中间层和热封层依次连接，熟化处理，得到所述针剂包装用复合片材。
优选地，所述熟化处理的温度为50～60℃，例如51℃、52℃、53℃、54℃、55℃、56℃、57℃、58℃或59℃等。
第三方面，本申请提供一种如第一方面所述的针剂包装用复合片材在液体农药包装中的应用。
相对于现有技术，本申请具有以下有益效果：
(1)本申请提供的针剂包装用复合片材包括依次设置的印刷层、中间层和 热封层，所述热封层由依次设置的复合层、芯层和内层组成；所述复合层的材料包括线性低密度聚乙烯和低密度聚乙烯的组合，所述芯层的材料包括线性低密度聚乙烯和环烯烃聚合物的组合，所述内层的材料包括茂金属聚乙烯；所述热封层的材料包括聚乙烯和环烯烃聚合物；通过选择聚乙烯和环烯烃聚合物的组合作为热封层的主要材料，使得到的针剂包装用复合片材具有较高的剥离强度和热封强度，还具有优异的阻湿性能，可以保证其成型后得到的针剂包装袋在使用时具有较低水蒸气透过率和内容物失重率，同时还具有优异的承压能力，具有广泛的应用前景。
(2)本申请还进一步限定了所属热封层的各层中的材料占比，进而使得到的针剂包装用复合片材具有最为优异的综合性能，具体而言，复合片材的水蒸气透过率为0.4～1g/m2.24h(38℃，90％RH)，剥离强度测试显示印刷层和中间层的剥离强度高达10.2～15N/15mm，而中间层和热封层的剥离强度同样高达10.2～11N/15mm，制成针剂包装袋使用时的热封强度为120～160N/15mm，0.08MPa，30min的承压测试显示外观均良好，没有出现泄漏的情况，且失重率仅为1.56～1.98％。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实施例1
一种针剂包装用复合片材，由依次设置的印刷层、第一粘结层、中间层、第二粘结层和热封层组成；
其中，印刷层为厚度为20μm的无定型的PET膜(材料为PET，博莱恩 APET-20)；
第一粘结层为无溶剂型聚氨酯胶水层(科意SF7660)；
中间层为厚度为250μm的无定型的PET膜(材料为PET，四川东材PET-250)；
第二粘结层为溶剂型聚氨酯粘结层(材料为溶剂型聚氨酯胶水，汉高UK8640)；
热封层的厚度为200μm，由依次设置的厚度为1:3.5:1的复合层、芯层和内层组成，各层中各个组分及其含量和来源如表1所示：
表1
所述热封层的制备方法包括：在180℃熔融下，在吹膜设备中将复合层、芯层和内层的材料塑化后经过模头挤出，冷却定型，并对复合层进行电晕处理，得到所述热封层；
本实施例提供的针剂包装用复合片材的制备方法包括如下步骤：分别用无溶剂型聚氨酯胶水和溶剂型聚氨酯胶水将印刷层、中间层和热封层依次粘结，55℃下熟化处理，冷却和分切，得到所述针剂包装用复合片材。
实施例2
一种针剂包装用复合片材，由依次设置的印刷层、第一粘结层、中间层、第二粘结层和热封层组成；
其中，印刷层为厚度为10μm的无定型的PET膜(博莱恩APET-10)；
第一粘结层为无溶剂型聚氨酯胶水层(科意SF7660)；
中间层为厚度为250μm的无定型的PET膜(四川东材PET-250)；
第二粘结层为溶剂型聚氨酯粘结层(汉高UK8640)；
热封层的厚度为200μm，由依次设置的厚度为1:3.5:1的复合层、中间层和内层组成，各层的组分及其的含量和来源如表2所示：
表2

所述热封层的制备方法包括：250℃熔融条件下，在吹膜设备将复合层、芯层和内层的材料塑化后经过模头挤出，冷却定型，并对复合层进行电晕处理，得到所述热封层；
本实施例提供的针剂包装用复合片材的制备方法包括如下步骤：分别用无溶剂型聚氨酯胶水和溶剂型聚氨酯胶水将印刷层、中间层和热封层依次粘结，熟化处理，得到所述针剂包装用复合片材。
实施例3
一种针剂包装用复合片材，由依次设置的印刷层、第一粘结层、中间层、第二粘结层和热封层组成；
其中，印刷层为厚度为30μm的无定型的PET膜(博莱恩APET-30)；
第一粘结层为无溶剂型聚氨酯胶水层(科意SF7660)；
过渡层为厚度为300μm的无定型的PET膜(四川东材PET-300)；
第二粘结层为溶剂型聚氨酯粘结层(汉高UK8640)；
热封层的厚度为150μm，由依次设置的厚度为1:3.5:1的复合层、中间层和内层组成；各层制备原料的含量和来源如表3所示：
表3

所述热封层的制备方法包括：在160℃熔融条件下，在吹膜设备中将复合层、芯层和内层的材料塑化后经过模头挤出，冷却定型，并对复合层进行电晕处理，得到所述热封层；
本实施例提供的针剂包装用复合片材的制备方法包括如下步骤：分别用无溶剂型聚氨酯胶水和溶剂型聚氨酯胶水将印刷层、中间层和热封层依次粘结，熟化处理，得到所述针剂包装用复合片材。
实施例4
一种针剂包装用复合片材，由依次设置的印刷层、第一粘结层、中间层、第二粘结层和热封层组成；
其中，印刷层为厚度为23μm的无定型的PET膜(博莱恩APET-23)；
第一粘结层为无溶剂型聚氨酯胶水层(科意SF7660)；
过渡层为厚度为250μm的无定型的PET膜(四川东材PET-250)；
第二粘结层为溶剂型聚氨酯粘结层(汉高UK8640)；
热封层的厚度为200μm，由依次设置的厚度为1:3.5:1的复合层、芯层和内层组成；各层制备原料的含量和来源如表4所示：
表4
所述热封层的制备方法包括：在190℃熔融条件下，在吹膜设备中将复合层、芯层和内层的材料塑化后经过模头挤出，冷却定型，并对复合层进行电晕处理，得到所述热封层；
本实施例提供的针剂包装用复合片材的制备方法包括如下步骤：分别用无溶剂型聚氨酯胶水和溶剂型聚氨酯胶水将印刷层、中间层和热封层依次粘结，熟化处理，得到所述针剂包装用复合片材。
实施例5
一种针剂包装用复合片材，其与实施例1的区别在于，第一粘结层和第二粘结层的材料均为溶剂型聚氨酯胶水(汉高UK8640)，其他结构、参数和制备方法均与实施例1相同。
实施例6
一种针剂包装用复合片材，其与实施例1的区别在于，热封层中的复合层的材料中线性低密度聚乙烯(陶氏2045G)的质量百分含量为14％，低密度聚乙烯(中海壳牌2420H)的质量百分含量为85％，其他结构、参数和制备方法均与实施例1相同。
实施例7
一种针剂包装用复合片材，其与实施例1的区别在于，热封层中的芯层的材料中线性低密度聚乙烯(陶氏2045G)的质量百分含量为85％，环烯烃聚合物(TOPAS 8007F-600)的质量百分含量为15％，其他结构、参数和制备方法均与实施例1相同。
实施例8
一种针剂包装用复合片材，其与实施例1的区别在于，热封层中的内层的材料中茂金属聚乙烯(陶氏1881G)的质量百分含量为15％，茂金属聚乙烯(埃克森美孚1018MB)的质量百分含量为82％，其他结构、参数和制备方法均与实施例1相同。
实施例9
一种针剂包装用复合片材，其与实施例1的区别在于，第一粘结层和第二粘结层的材料均为无溶剂型聚氨酯胶水(科意SF7660)，其他结构、参数和制备方法均与实施例1相同。
对比例1
一种针剂包装用复合片材，其与实施例1的区别在于，热封层中的复合层的材料中不添加线性低密度聚乙烯(陶氏2045G)，由质量百分含量为100％的低密度聚乙烯(中海壳牌2420H)组成，其他结构、参数和制备方法均与实施 例1相同。
对比例2
一种针剂包装用复合片材，其与实施例1的区别在于，热封层中的芯层的材料中不添加环烯烃聚合物(TOPAS 8007F-600)，由质量百分含量为100％的线性低密度聚乙烯(陶氏2045G)组成，其他结构、参数和制备方法均与实施例1相同。
对比例3
一种针剂包装用复合片材，其与实施例1的区别在于，热封层中的芯层的材料中不添加线性低密度聚乙烯(陶氏2045G)，由质量百分含量为100％的环烯烃聚合物(TOPAS 8007F-600)组成，其他结构、参数和制备方法均与实施例1相同。
性能测试：
(1)水蒸气透过率：按照标准GB/T 26253-2010提供的测试方法进行测试，测试条件为38℃，90％RH；
(2)失重率：将得到的复合片材制成包装袋包装液体农药，在54℃的烘箱里放置二周时间，称量前后样品前后重量变化，然后计算失重率；
(3)剥离强度：按照GB/T 8808-1988的规定进行检测；
(4)热封强度：按照标准QB/T 2358-1998提供的测试方法进行测试；
(5)承压能力：将得到的复合片材制成包装袋包装液体农药，然后在承受0.08MPa下保持30min，观察有无泄漏。
按照上述测试方法对实施例1～9和对比例1～3提供的针剂包装用复合片材进行测试，测试结果如表5所示：
表5

根据表5数据可以看出：
本申请提供的针剂包装用复合片材具有较高的剥离强度和热封强度，还具有较低的水蒸气透过率，可以保证其成型后得到的针剂包装袋在使用时具有较低的内容物失重率，同时还具有较高的承压能力；且进一步限定热封层的各层中的材料占比，使得到的针剂包装用复合片材具有最为优异的综合性能；具体而言，实施例1～5得到的针剂包装用复合片材的水蒸气透过率为0.4～1g/m2.24h (38℃，90％RH)，剥离强度测试显示，印刷层和中间层的剥离强度高达10.2～15N/15mm，而中间层和复合层的剥离强度同样高达10.2～11N/15mm，制成针剂包装袋使用时的热封强度为120～160N/15mm，0.08MPa，30min的承压测试显示外观均良好，没有出现泄漏的情况，且失重率仅为1.56～1.98％。
比较实施例1和对比例1、3可以发现，复合层的材料中不添加线性低密度聚乙烯(对比例1)以及芯层的材料中不添加线性低密度聚乙烯(对比例3)均会导致得到的复合片材的承压能力下降且使用时内容物失重率较高，甚至测试失重率时产生分层。
比较实施例1和对比例2可以发现，芯层的材料中不添加环烯烃聚合物，会使得到的复合片材的水蒸气透过率大幅度增加，说明其阻隔性能较差。
进一步比较实施例1和实施例6可以发现，复合层的材料中线性低密度聚乙烯以及低密度聚乙烯的质量百分含量不在本申请限定的优选范围内，会导致复合片材的剥离强度和热封强度有所降低，进而还导致制成包装袋使用时失重率有所增加。
再进一步比较实施例1和实施例7可以发现，芯层的材料中线性低密度聚乙烯和环烯烃聚合物的质量百分含量不在本申请限定的优选范围内，会导致得到的复合片材的水蒸气透过率有所增加，进而同样还导致制成包装袋后失重率有所增加。
更进一步比较实施例1和实施例8可以发现，内层的材料中茂金属聚乙烯(陶氏1881G)和茂金属聚乙烯(埃克森美孚1018MB)的质量百分含量不在本申请限定的优选范围内同样会导致复合片材的热封强度有所下降，进而导致失重率有所增加。
最后再比较实施例1和实施例9可以发现，第一粘结层和第二粘结层的材料均为无溶剂型聚氨酯胶水会使得制成包装袋之后测试失重率时容易出现分层。
申请人声明，本申请通过上述实施例来说明一种针剂包装用复合片材及其制备方法和应用，但本申请并不局限于上述工艺步骤，即不意味着本申请必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请所选用原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本申请的保护范围和公开范围。

Claims (10)

  1. 一种针剂包装用复合片材，其中，所述针剂包装用复合片材包括依次设置的印刷层、中间层和热封层；
    所述热封层由依次设置的复合层、芯层和内层组成；
    所述复合层的材料包括线性低密度聚乙烯和低密度聚乙烯的组合，所述芯层的材料包括线性低密度聚乙烯和环烯烃聚合物的组合，所述内层的材料包括茂金属聚乙烯。
  2. 根据权利要求1所属的针剂包装用复合片材，其中，所述复合层和芯层的厚度比为1:(2.5～4)；
    优选地，所述复合层和内层的厚度比为1:(0.5～1.5)。
  3. 根据权利要求1或2所述的针剂包装用复合片材，其中，所述印刷层为无定型PET膜；
    优选地，所述印刷层的厚度为10～30μm；
    优选地，所述中间层为无定型PET膜；
    优选地，所述中间层的厚度为200～300μm；
    优选地，所述热封层的厚度为150～200μm。
  4. 根据权利要求1～3任一项所述的针剂包装用复合片材，其中，所述复合层的材料中线性低密度聚乙烯的质量百分含量为80～89％；
    优选地，所述复合层的材料中低密度聚乙烯的质量百分含量为10～15％；
    优选地，所述复合层的材料中还包括加工助剂；
    优选地，所述复合层的材料中加工助剂的质量百分含量为1～5％；
    优选地，所述芯层的材料中线性低密度聚乙烯的质量百分含量为50～70％；
    优选地，所述芯层的材料中环烯烃聚合物的质量百分含量为30～50％；
    优选地，所述内层的材料中茂金属聚乙烯的质量百分含量为95～99％；
    优选地，所述内层的材料中还包括加工助剂；
    优选地，所述内层的材料中加工助剂的质量百分含量为1～5％。
  5. 根据权利要求1～4任一项所述的针剂包装用复合片材，其中，所述复合层中的线性低密度聚乙烯以及中间层中的线性低密度聚乙烯的熔融指数各自独立地为1～4g/10min；
    优选地，所述复合层中的线性低密度聚乙烯以及中间层中的线性低密度聚乙烯的密度各自独立地为0.92～0.94g/cm3；
    优选地，所述低密度聚乙烯的熔融指数为1～4g/10min；
    优选地，所述低密度聚乙烯的密度为0.92～0.94g/cm3；
    优选地，所述茂金属聚乙烯的熔融指数为0.5～8g/10min；
    优选地，所述茂金属聚乙烯的密度为0.90～0.92g/cm3；
    优选地，所述复合层中的加工助剂以及内层中的加工助剂各自独立地为PPA和/或开口剂。
  6. 根据权利要求1～5任一项所述的针剂包装用复合片材，其中，所述热封层通过如下方法制备得到，所述方法包括：将复合层的材料、芯层的材料以及内层的材料经三层共挤、电晕处理，得到所述热封层；
    优选地，所述三层共挤在吹膜设备中进行；
    优选地，所述三层共挤的温度为160～250℃。
  7. 根据权利要求1～6任一项所述的针剂包装用复合片材，其中，所述印刷层和中间层之间还设置有第一粘合层；
    优选地，所述第一粘合层的制备原料包括无溶剂型聚氨酯胶水或溶剂型聚氨酯胶水；
    优选地，所述中间层和热封层之间还设置有第二粘结层；
    优选地，所述第二粘结层的制备原料为溶剂型聚氨酯胶水。
  8. 一种如权利要求1～7任一项所述针剂包装用复合片材的制备方法，其中，所述制备方法包括：分别用第一粘结层的材料以及第二粘结层的材料将印刷层、中间层和热封层依次粘结，熟化处理，得到所述针剂包装用复合片材。
  9. 根据权利要求8所述的制备方法，其中，所述熟化处理的温度为50～60℃。
  10. 一种如权利要求1～8任一项所述的针剂包装用复合片材在液体农药包装中的应用。
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