WO2021189600A1 - 一种复合包装材料及其制作方法 - Google Patents

一种复合包装材料及其制作方法 Download PDF

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Publication number
WO2021189600A1
WO2021189600A1 PCT/CN2020/088440 CN2020088440W WO2021189600A1 WO 2021189600 A1 WO2021189600 A1 WO 2021189600A1 CN 2020088440 W CN2020088440 W CN 2020088440W WO 2021189600 A1 WO2021189600 A1 WO 2021189600A1
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WO
WIPO (PCT)
Prior art keywords
layer
light
barrier layer
adhesive
packaging material
Prior art date
Application number
PCT/CN2020/088440
Other languages
English (en)
French (fr)
Inventor
董亚强
刘华文
吕晓军
Original Assignee
乐美包装（昆山）有限公司
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Publication date
Application filed by 乐美包装（昆山）有限公司 filed Critical 乐美包装（昆山）有限公司
Priority to EP20927207.9A priority Critical patent/EP4137316A4/en
Publication of WO2021189600A1 publication Critical patent/WO2021189600A1/zh

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    • 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
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    • 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
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
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    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/30—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length incorporating preformed parts or layers, e.g. moulding around inserts or for coating articles
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Definitions

  • This application relates to the field of packaging technology, in particular to a composite packaging material and a manufacturing method thereof.
  • the shelf life of the existing aseptic liquid composite packaging materials can reach about six months. This is because the composite packaging materials contain aluminum foil, which has a better barrier effect on oxygen and light. However, since the composite packaging material also contains plastic, it is difficult to separate the aluminum foil and the plastic, which greatly reduces the recycling efficiency of the existing composite packaging material containing aluminum foil.
  • the main technical problem solved by this application is to provide a composite packaging material and a manufacturing method thereof, which can replace the existing composite packaging material containing aluminum foil and improve its recycling efficiency.
  • a composite packaging material comprising: a barrier layer, a light-shielding layer, a core layer, and an outer layer stacked in sequence; wherein the barrier layer and the light-shielding layer are formed of non-metallic materials, and the oxygen gas of the barrier layer is transparent
  • the OTR is less than 1.0cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa)
  • the light-shielding layer is under a light source of 6500K color temperature
  • the light transmittance is less than 0.5% in the wavelength range of 190nm-1100nm
  • the composite packaging material is used For packaging liquid food.
  • a method for manufacturing composite packaging materials including:
  • barrier layer coils and core layer coils wherein the barrier layer coils are produced by a co-extrusion process
  • Forming a light-shielding layer between the barrier layer roll material and the core layer roll material by adopting a coating process, so as to simultaneously form a light-shielding layer and a barrier layer that are sequentially stacked on one side of the core layer;
  • the barrier layer and the light-shielding layer are formed of non-metallic materials, the oxygen transmission rate OTR of the barrier layer is less than 1.0cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa), and the light-shielding layer is at a color temperature of 6500K. Under the light source, the light transmittance is less than 0.5% in the wavelength range of 190nm-1100nm; the composite packaging material is used for packaging liquid food.
  • the composite packaging material provided by the present application includes a barrier layer, a light-shielding layer, a core layer, and an outer layer stacked in sequence; wherein, the barrier layer and the light-shielding layer are made of non-metallic materials.
  • the oxygen transmission rate OTR of the barrier layer is less than 1.0cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa), and the light transmission rate of the light shielding layer is less than 0.5% in the wavelength range of 190nm-1100nm under the light source of 6500K color temperature.
  • the composite packaging material is used for packaging liquid food, and its barrier effect to oxygen and light is equivalent to that of aluminum foil. It can replace the existing composite packaging material containing aluminum foil, and the composite packaging material of the present application does not contain aluminum foil, which is not in the prior art. The problem that aluminum foil and plastic are difficult to separate.
  • Figure 1 is a schematic structural diagram of an embodiment of the composite packaging material of this application.
  • FIG. 2 is a schematic structural diagram of an embodiment of the barrier layer in FIG. 1;
  • Fig. 3 is a schematic structural diagram of another embodiment of the barrier layer in Fig. 1;
  • Fig. 4 is a schematic flow diagram of an embodiment of a method for manufacturing a composite packaging material according to the present application.
  • FIG. 1 is a schematic structural diagram of an embodiment of the composite packaging material of the present application.
  • the composite packaging material 100 includes a barrier layer 11, a light shielding layer 12, a core layer 13, and an outer layer 14 stacked in sequence, wherein the barrier layer 11 And the light shielding layer 12 is formed of a non-metallic material, and the oxygen transmission rate OTR of the barrier layer 11 is less than 1.0cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa), for example, 0.9cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa), 0.8 cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa), 0.7cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa), etc.
  • the light-shielding layer 12 has a light transmittance of 190nm-1100nm under a light source with a color temperature of 6500K Less than 0.5%, such as 0.45%, 0.4%, 0.35%, etc.; the composite packaging material 100 is used for packaging liquid food.
  • the existing composite packaging material contains aluminum foil, which can effectively block oxygen and light. Therefore, the shelf life of the packaged liquid food can reach about 6 months.
  • the composite packaging material also contains plastic, but it is difficult to separate the aluminum foil and the plastic. , Greatly reducing the recycling efficiency of composite packaging materials using aluminum foil.
  • the barrier layer 11 of the composite packaging material 100 of the present application has a good barrier effect on oxygen
  • the light-shielding layer 12 has a good barrier effect on light, which is equivalent to the barrier effect of a composite packaging material containing aluminum foil on oxygen and light. It can replace the existing aluminum foil-containing composite packaging materials, and the barrier layer 11 and the light-shielding layer 12 are both formed of non-metallic materials and do not contain aluminum foil, so there is no problem that aluminum foil and plastic are difficult to separate in the prior art.
  • the oxygen transmission rate OTR test standard in this application refers to the Chinese standard GB/T 19789-2005 or ASTM D 3985, the test condition is 23°C, humidity 50%RH, and the test instrument uses Ametek Mocon's Model 2/ 22 oxygen transmission rate tester.
  • the light transmittance test standard in this application refers to the Chinese standard GB/T 2410-2008 or ASTM D 1003, the test conditions are temperature 23°C, humidity 50%RH, and the test instrument uses PerkinElmer Lambda 950 ultraviolet spectrophotometer.
  • the thickness distribution of each layer of the composite packaging material 100 of the present application is represented by a gram weight range, and the larger the gram weight, the thicker the thickness.
  • the barrier layer is 11 weight range is 20g / m 2 -40g / m 2 , e.g. 20g / m 2, 30g / m 2, 40g / m 2 and the like
  • the light-shielding layer is 12 weight range of 15g / m 2 -30g/m 2 , such as 15g/m 2 , 20g/m 2 , 30g/m 2, etc.
  • the weight range of the outer layer 14 is 10g/m 2 -18g/m 2 , such as 10g/m 2 , 15g/m 2, 18g / m 2 and the like; core layer 13 comprises a stacked layer of paper 131 and the printing layer 132, a printed paper layer 131 is located between the layer 132 and the light shielding layer 12, paper layer 131 g weight range of 170g / m 2 - 330g/m 2 , such as 170g/m 2 , 250g/m 2 , 330g/m 2, etc.
  • the grammage range of the printing layer 132 is 1g/m 2 -3g/m 2 , for example, 1g/m 2 , 2g/m 2 , 3g/m 2 and so on.
  • the composite packaging material 100 formed by the layers distributed in this way meets the requirements of liquid food packaging and has a good barrier effect against oxygen and light.
  • the light-shielding layer 12 includes polyethylene PE and a light-shielding material doped in the polyethylene PE, and the light-shielding material includes at least one of a color masterbatch and a light-shielding agent.
  • Polyethylene PE is the base material of the light-shielding layer, which is mainly used for bonding with the barrier layer 11 of the composite packaging material 100, and the light-shielding material is doped into the polyethylene PE base material to play the role of blocking light.
  • the polyethylene PE includes at least one of low-density polyethylene LDPE, linear low-density polyethylene LLDPE, metallocene linear low-density polyethylene M-LLDPE, and high-density polyethylene HDPE
  • the color masterbatch includes white masterbatch
  • black and white masterbatch or light-shielding agent is selected as the light-shielding material, so that the light-shielding layer 12 has a good function of blocking light.
  • the light source is set to D65 (color temperature 6500K).
  • the light transmittance of the light shielding layer 12 is measured to be less than 0.5%, while the existing sterile liquid composite packaging materials containing aluminum foil , The light transmittance measured under the same conditions is also less than 0.5%.
  • the composite packaging material 100 of this embodiment can replace the existing aseptic liquid composite packaging material with aluminum foil and other packaging materials.
  • the light transmittance of other packaging materials please refer to Table 1. Among them, the light transmittance is measured at a color temperature of 6500K and a wavelength range of 190nm-1100nm.
  • Packaging Materials type of packaging volume Contents Transmittance Paper-plastic composite Roof packaging (non-transparent) 1000ml Fresh milk 5% PET Bottle (non-transparent) 230g yogurt 1% PS Bottle (non-transparent) 500ml milk 10% HDPE Bottle (translucent) 1000ml milk 50%
  • FIG. 2 is a schematic structural view of an embodiment of the barrier layer in FIG. 1.
  • the barrier layer 11 of the composite packaging material 100 of this embodiment includes a heat seal layer 111, a first adhesive layer 112, The oxygen barrier layer 113, the second adhesive layer 114 and the adhesive layer 115; wherein the adhesive layer 115 is in contact with the light shielding layer 12.
  • the material and thickness of the first adhesive layer 112 and the second adhesive layer 114 are the same, and the material and thickness of the heat-sealing layer 111 and the adhesive layer 115 are the same, that is, the barrier layer 11 of this embodiment With the oxygen barrier layer 113 as the center, a first adhesive layer 112 and a second adhesive layer 114, a heat seal layer 111 and an adhesive layer 115 are sequentially and symmetrically distributed on both sides of the oxygen barrier layer 113.
  • the first adhesive layer 112 is used to bond the oxygen barrier layer 113 and the heat-seal layer 111;
  • the second adhesive layer 114 is used to bond the oxygen barrier layer 113 and the adhesive layer on the other side of the oxygen barrier layer 113.
  • the heat-sealing layer 111 plays a role of hot-sealing when the composite packaging material 100 is processed into a packaging container;
  • the adhesive layer 115 is used for compounding with the light shielding layer 12, and at the same time, it can also protect the oxygen barrier layer 113 from water.
  • the oxygen barrier layer 113 includes ethylene-vinyl alcohol copolymer EVOH, wherein the ethylene content is 24% to 36%, such as 24%, 30%, 36%, etc.
  • the first adhesive layer 112 and the second adhesive Layer 114 includes adhesive resin Adhesive, heat-sealing layer 111 and adhesive layer 115 both include polyethylene PE; wherein, adhesive resin Adhesive includes ethylene-acrylic acid copolymer EAA, ethylene-methacrylic acid copolymer EMAA, maleic anhydride At least one of modified polyethylene MAH-g-PE, polyethylene PE includes at least one of low-density polyethylene LDPE, linear low-density polyethylene LLDPE, metallocene linear low-density polyethylene M-LLDPE, and high-density polyethylene HDPE kind.
  • an appropriate ethylene content is selected to balance the processability and barrier properties.
  • the ethylene-vinyl alcohol copolymer EVOH is a material with excellent oxygen barrier effect, but it is not water resistant. If it encounters water, its oxygen barrier effect will decrease, so it cannot be directly exposed to the air or directly contacted with liquids.
  • this embodiment uses a heat-seal layer 111 formed of a water-blocking material polyethylene PE and an adhesive layer 115 sandwiching the ethylene-vinyl alcohol copolymer EVOH, and the adhesive resin Adhesive is used to increase it and the polyethylene PE material
  • Adhesive is used to increase it and the polyethylene PE material
  • the bonding fastness of the ethylene-vinyl alcohol copolymer EVOH of the oxygen barrier layer 113 has a good water-blocking protection effect.
  • the base material of the light-shielding layer 12 is also polyethylene PE.
  • the same polyethylene PE material is easier to compound, and the light-shielding layer 12 and the barrier layer 11 are common Function, can more effectively maintain the flavor of the packaged liquid food.
  • the thickness distribution of each layer of the barrier layer 11 symmetrically centered on the oxygen barrier layer 113 is as follows: the thickness of the heat-sealing layer 111 or accounts for 25%-40% of the total thickness of the barrier layer 11, such as 25%, 37 %, 40%, etc., the thickness of the first adhesive layer 112 accounts for 5% to 10% of the total thickness of the barrier layer 11, such as 5%, 7%, 10%, etc., and the thickness of the oxygen barrier layer 113 accounts for the total thickness of the barrier layer 11 10% to 25% of the thickness, such as 10%, 17%, 25%, etc., the thickness of the second adhesive layer 114 accounts for 5% to 10% of the total thickness of the barrier layer 11, such as 5%, 7%, 10% The thickness of the adhesive layer 115 accounts for 25%-40% of the total thickness of the barrier layer 11, such as 25%, 37%, 40%, and so on.
  • the barrier layer 11 has a symmetrical structure, the thickness of the first adhesive layer 112 and the second adhesive layer 114 account for the same thickness, and the thickness of the heat-seal layer 111 and the adhesive layer 115 account for the same thickness.
  • the barrier layer 11 can more effectively protect the ethylene-vinyl alcohol copolymer EVOH of the oxygen barrier layer 113, is more conducive to the subsequent processing and production of the composite packaging material of the present application, and can more effectively maintain the flavor of the packaged liquid food.
  • FIG. 3 is a schematic structural view of another embodiment of the barrier layer in FIG. 1.
  • the barrier layer 21 of this embodiment includes a heat seal layer 211 and a first adhesive layer 212 , The oxygen barrier layer 213, the second adhesive layer 214, and the bonding layer 215, and further include a first reinforcement layer 216 and a second reinforcement layer 217, wherein the first reinforcement layer 216 is located between the oxygen barrier layer 213 and the first adhesive layer Between the agent layers 212, the second reinforcement layer 217 is located between the oxygen barrier layer 213 and the second adhesive layer 214.
  • the barrier layer 21 of this embodiment includes a heat-seal layer 211, a first adhesive layer 212, a first reinforcement layer 216, an oxygen barrier layer 213, a second reinforcement layer 217, and a second adhesive layer that are stacked in sequence.
  • the layer 214 and the adhesive layer 215 have a symmetrical structure with the oxygen barrier layer 213 as the center.
  • the first reinforcement layer 216 and the second reinforcement layer 217 have the same material and thickness.
  • the first adhesive layer 212 and the second adhesive layer The material and thickness of the agent layer 214 are the same, and the material and thickness of the heat-sealing layer 211 and the adhesive layer 215 are the same.
  • the oxygen barrier layer 213 includes ethylene-vinyl alcohol copolymer EVOH, wherein the ethylene content is 24% to 36%, such as 24%, 32%, 36%, etc., and the first reinforcement layer 216 and the second reinforcement layer 217 both include Polyamide PA, the first adhesive layer 212 and the second adhesive layer 214 both include adhesive resin Adhesive, the heat-sealing layer 211 and the adhesive layer 215 both include polyethylene PE; wherein the adhesive resin Adhesive includes ethylene- At least one of acrylic copolymer EAA, ethylene-methacrylic acid copolymer EMAA, maleic anhydride modified polyethylene MAH-g-PE, polyethylene PE includes low density polyethylene LDPE, linear low density polyethylene LLDPE, metallocene At least one of linear low-density polyethylene M-LLDPE and high-density polyethylene HDPE; polyamide PA includes polyamide-6, polyamide-66, polyamide-11, polyamide-12, nylon 46, nylon 610, nylon 6
  • an appropriate ethylene content is selected to balance the processability and barrier properties.
  • the ethylene-vinyl alcohol copolymer EVOH is a material with excellent oxygen barrier effect, but it is not water resistant. If it encounters water, its oxygen barrier effect will decrease, so it cannot be directly exposed to the air or directly contacted with liquids.
  • this embodiment first uses polyamide PA to sandwich the ethylene-vinyl alcohol copolymer EVOH, and then uses the heat-seal layer 211 and the adhesive layer 215 formed by the water-blocking material polyethylene PE to be distributed on the two layers of polyamide PA.
  • Adhesive is used to increase the bonding fastness of polyamide PA and polyethylene PE material, which has a good water-blocking protection effect on the ethylene-vinyl alcohol copolymer EVOH of the oxygen barrier layer 213.
  • the light-shielding layer 12 and the barrier layer 11 work together to more effectively maintain the flavor of the liquid food being packaged.
  • polyamide PA is an engineering plastic whose stiffness is greater than that of polyethylene PE, so it is beneficial to the final liquid packaging The completeness of the packaging ensures that the packaging has high mechanical properties.
  • the thickness distribution of each layer of the barrier layer 21 symmetrically centered on the oxygen barrier layer 213 is as follows: the thickness of the heat-sealing layer 211 accounts for 25%-40% of the total thickness of the barrier layer 21, and the first adhesive layer The thickness of 212 accounts for 5% to 10% of the total thickness of the barrier layer 21, the thickness of the first reinforcement layer 216 accounts for 2% to 10% of the total thickness of the barrier layer 21, and the thickness of the oxygen barrier layer 213 accounts for 10% of the total thickness of the barrier layer 21.
  • the thickness of the second reinforcing layer 217 accounts for 2%-10% of the total thickness of the barrier layer 21
  • the thickness of the second adhesive layer 214 accounts for 5%-10% of the total thickness of the barrier layer 21
  • the thickness of 215 accounts for 25%-40% of the total thickness of the barrier layer 21.
  • the symmetrically distributed barrier layer 11 can more effectively protect the ethylene-vinyl alcohol copolymer EVOH of the oxygen barrier layer 113, which is more conducive to the subsequent processing and manufacture of the composite packaging material of the present application, and can more effectively retain the packaged liquid The flavor of the food.
  • the composite packaging material of this application uses the barrier layer 11 or 21 containing ethylene-vinyl alcohol copolymer EVOH, and its oxygen transmission rate OTR ⁇ 1.0cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa), the oxygen transmission rate of the molded package OTR ⁇ 0.2cm 3 /(pkg ⁇ 24h ⁇ 0.1MPa), while the existing sterile liquid composite packaging material containing aluminum foil, its oxygen transmission rate OTR ⁇ 1.0cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa), forming The oxygen transmission rate of the package OTR ⁇ 1.0cm 3 /(pkg ⁇ 24h ⁇ 0.1MPa).
  • the barrier material is aluminum foil, its oxygen transmission rate OTR ⁇ 1.0 cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa); if the barrier material is other non-aluminum foil materials , Its oxygen transmission rate OTR ⁇ 15.0cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa), it can be seen that the composite packaging material of this application not only meets the requirements of the national standard, but also meets the requirements of the national standard for the oxygen transmission rate of aluminum foil as a barrier material.
  • the barrier layer 11 or 21 of the composite packaging material of the present application is formed by a multilayer film
  • the existing aseptic liquid composite packaging material uses aluminum foil to block light and oxygen
  • the advantage of the multilayer film over the aluminum foil is that after folding No cracking occurs, so the oxygen transmission rate OTR of the composite packaging material of the present application is smaller than that of the existing aseptic liquid packaging material containing aluminum foil. Therefore, from the perspective of the OTR of the packaging material, the composite packaging material of this application can replace the existing aseptic liquid composite packaging material containing aluminum foil and other packaging materials.
  • the unit of oxygen transmission rate OTR is cm 3 /(pkg ⁇ 24h ⁇ 0.1MPa).
  • the recycling method of the existing aseptic bag containing aluminum foil is to separate aluminum foil and polyethylene PE.
  • 80% acetic acid must be used for soaking at 50°C during the separation, which will cause serious fragmentation of the recycled aluminum foil and change the value of recycling.
  • the acid solution needs to be diluted or neutralized before being discharged, which increases additional treatment costs and environmental impact.
  • the composite packaging material in this application does not contain aluminum foil, and contains a large amount of polyethylene PE and other oil-soluble or water-soluble non-metallic substances.
  • the acid treatment step can be omitted during recycling, and it can be divided into fiber stream and polyethylene stream only by using water to dissolve it. , Other water-soluble substances dissolve in water, while other oil-soluble substances have very low content and do not affect recovery.
  • ethylene-vinyl alcohol copolymer EVOH in cooperation between Kuraray and nextek (data source: SPE Anaheim 2017), the EVOH polyolefin film containing 5% of the ethylene-vinyl alcohol copolymer can be co-extruded with fresh raw materials after recycling and pelletizing (recycling ratio ⁇ 15%). It is in the food safety and mechanical properties. Acceptable level.
  • the existing recycling system can be used and incorporated into the polyolefin stream without affecting the application of recycled polyolefin.
  • the ethylene-vinyl alcohol copolymer EVOH used in the barrier layer of the composite packaging material of the present application accounts for less than 5% of the total composite packaging material, so the recovery efficiency is higher.
  • liquid foods that can be packaged by the composite packaging material of the present application include at least ultra-high temperature sterilized milk, pasteurized milk, long-term shelf milk, cream, flavor and formula milk products, fermented milk products, concentrated milk, condensed milk, reconstituted milk, fruit juice, and non-productive milk.
  • Carbonated beverages, tea, coconut water, soups, ketchup and sauces can effectively maintain the flavor of the above-mentioned liquid foods and other liquid foods.
  • FIG. 4 is a schematic flowchart of an embodiment of a method for manufacturing a composite packaging material according to the present application. This embodiment includes the following steps:
  • a light-shielding layer is formed between the barrier layer roll material and the core layer roll material by a coating process, so as to simultaneously form a light-shielding layer and a barrier layer that are sequentially stacked on one side of the core layer.
  • the barrier layer and the light shielding layer are formed of non-metallic materials, and the oxygen transmission rate OTR of the barrier layer is less than 1.0cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa), for example, 0.9cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa) , 0.8cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa), 0.7cm 3 /(m 2 ⁇ 24h ⁇ 0.1MPa), etc.
  • the light-shielding layer is transparent under the light source of 6500K color temperature in the wavelength range of 190nm-1100nm The rate is less than 0.5%, such as 0.45%, 0.4%, 0.35%, etc.; composite packaging materials are used for packaging liquid foods.
  • the barrier layer of the composite packaging material prepared in this embodiment has a good barrier effect on oxygen
  • the light-shielding layer has a good barrier effect on light, which is the same as that of existing composite packaging materials containing aluminum foil on oxygen and light.
  • the effect is equivalent and it can replace the existing aluminum foil-containing composite packaging materials, and the barrier layer 11 and the light-shielding layer 12 are both formed of non-metallic materials and do not contain aluminum foil, so there is no problem that aluminum foil and plastic are difficult to separate.
  • the use of the co-extrusion process to produce the barrier layer roll material in step S401 includes: simultaneously forming a heat-seal layer, a first adhesive layer, an oxygen barrier layer, and a second layer that are sequentially stacked by a multi-layer co-extrusion blown film machine.
  • Adhesive layer and bonding layer include: using a multi-layer co-extrusion film blowing machine to simultaneously form the heat-seal layer, the first adhesive layer, the first reinforcement layer, the oxygen barrier layer, the second reinforcement layer, the second adhesive layer, and the adhesive ⁇ The layer.
  • the oxygen barrier layer includes ethylene-vinyl alcohol copolymer EVOH
  • the first reinforcement layer and the second reinforcement layer both include polyamide PA
  • the first adhesive layer and the second adhesive layer both include adhesive resin Adhesive.
  • Both the sealing layer and the adhesive layer include polyethylene PE.
  • Multi-layer co-extrusion blown film machine mainly includes five-layer co-extrusion blown film machine, seven-layer co-extrusion blown film machine, nine-layer co-extrusion blown film machine, eleven-layer co-extrusion blown film machine, etc., such as five-layer co-extrusion blown film
  • the machine can produce multi-layer films with less than or equal to five layers. In the process of making barrier layer coils, the width range is 800mm ⁇ 1600mm.
  • a barrier layer roll material including a heat seal layer, a first adhesive layer, a first reinforcement layer, an oxygen barrier layer, a second reinforcement layer, a second adhesive layer and an adhesive layer as an example, seven-layer co-extrusion
  • the processing temperature setting range of each layer and zone of the film blowing machine is shown in Table 3.
  • PE means heat-sealing layer and adhesive layer
  • Adhesive means first adhesive layer and second adhesive layer
  • PA means first reinforcing layer and The second reinforcement layer
  • EVOH stands for oxygen barrier layer.
  • Table 3 The processing temperature setting range of each layer and zone of the seven-layer co-extrusion film blowing machine
  • Heating zone Feeding area/°C Second zone/°C The third zone/°C
  • the fourth zone/°C The fifth zone/°C Joint area/°C Die area/°C PE 80-120 95-140 110-160 110-160 110-160 110-160 Adhesive 140-180 165-205 215-255 215-280 215-280 215-280 215-280 PA 170-230 180-240 190-250 200-260 200-260 200-260 EVOH 180-220 190-230 200-240 200-240 200-240 200-240 200-240 200-240 200-240 200-240 200-240 200-240 200-240
  • the adoption of the coating process to form a light-shielding layer between the barrier layer coil and the core layer coil includes: using a high-speed composite laminating machine to compound polyethylene PE and light-shielding material on the adhesive layer and the barrier layer coil.
  • a light-shielding layer is formed in the middle of the core layer roll material, and the barrier layer, the light-shielding layer and the core layer are squeezed together.
  • the light-shielding material includes at least one of a white masterbatch, a black master and a light-shielding agent
  • the light-shielding agent includes at least one of zinc oxide, titanium dioxide, carbon black, and graphene.
  • step S403 using the coating process to form the outer layer on the surface of the core layer away from the light-shielding layer includes: using a high-speed composite laminating machine to compound polyethylene PE on the surface of the core layer away from the light-shielding layer to form the outer layer.
  • the high-speed composite laminating machine includes three extrusion stations: outer layer station, compound station, and inner layer station.
  • the core layer coil is used as the base material to unwind and run.
  • the unwinding operation is carried out on the unwinding device, and the core layer, the light-shielding layer and the barrier layer are compounded at the compounding station, that is, the core layer and the barrier layer are bonded together through the light-shielding layer in the molten state; and then pass directly through the unopened The inner layer station, and finally the outer layer is compounded on the outside of the core layer through the outer layer station.
  • the substrate width range of the high-speed composite laminating machine is 850mm-1650mm
  • the production line speed is 300-800m/min
  • the processing temperature setting range of each station is shown in Table 4.
  • Table 4 The processing temperature setting range of each station of the high-speed composite laminating machine
  • polyethylene PE includes at least one of low-density polyethylene LDPE, linear low-density polyethylene LLDPE, metallocene linear low-density polyethylene M-LLDPE, and high-density polyethylene HDPE.
  • Polyamide PA includes polyamide- 6. At least one of polyamide-66, polyamide-11, polyamide-12, nylon 46, nylon 610, nylon 612, and nylon 1010.
  • the differences include the following:
  • the composite section of the composite packaging material of this application (ie, the high-speed composite laminating machine section) does not need to use an inner station, while the existing aseptic liquid composite packaging material compound section needs to use an inner station.
  • the composite section of the composite packaging material of this application uses an aluminum foil unwinding device to unwind the barrier layer coil, while the existing aseptic liquid composite packaging material composite section uses an aluminum foil unwinding device to unwind the aluminum foil coil.
  • the manufacturing process of the composite packaging material of this application includes two processes: film blowing (multi-layer co-extrusion film blowing machine) and laminating film (high-speed composite laminating machine), while the existing aseptic liquid composite packaging material manufacturing process is only laminating Film, do not blow film.
  • the barrier layer of the composite packaging material of this application is formed by a blown film process. Its advantage is that the tensile strength of the blown film is greater than that of the laminating film.
  • the data comparison is shown in Table 5.
  • PA stands for polyamide; and the barrier layer is used instead of aluminum foil. After the packaging is folded and formed, the barrier layer formed by the multilayer film is not easy to be damaged or broken, and will not cause a drop in the oxygen transmission rate OTR.
  • the composite packaging material of this application is to be filled in the aseptic system condition through the filling machine of Tetra Pak at the client.
  • the existing electromagnetic induction sealing method of the filling machine is adapted to the existing aseptic liquid composite packaging materials containing aluminum foil.
  • the filling machine heats the aluminum foil through electromagnetic induction, and then the heated aluminum foil plasticizes the polyethylene PE for sealing.
  • the composite packaging material provided by this application does not contain aluminum foil, it cannot be sealed by electromagnetic induction.
  • the existing electromagnetic induction sealing method needs to be transformed into an ultrasonic sealing method. After the transformation, the polyethylene PE can be directly plasticized for sealing without being restricted by the heat transfer of the aluminum foil.
  • the ultrasonic sealing method can be consistent with the electromagnetic induction sealing method in terms of sealing performance, including: the sealing time is short, the sealing performance is not affected by contaminants, and no cooling is required.
  • the light transmittance of Examples 1-3 and Comparative Example 1 is basically Consistent, the oxygen transmission rate OTR of the composite packaging materials of Examples 1-3 is basically the same as that of Comparative Example 1, while the oxygen transmission rate OTR of the molded package is significantly lower than that of Comparative Example 1. Moreover, the recovery performance of Examples 1-3 is stronger than that of Comparative Example 1, and the sealing method also breaks the limitation of aluminum foil.

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Abstract

一种复合包装材料及其制作方法，所述复合包装材料（100）包括依次层叠设置的阻隔层（11）、遮光层（12）、芯层（13）和外层（14）；其中，阻隔层和遮光层由非金属材料形成，阻隔层的氧气透过率OTR小于1.0cm3/(m2•24h•0.1MPa)，遮光层在6500K色温的光源下，在190nm-1100nm的波长范围内，透光率小于0.5％；复合包装材料用于包装液体食品，对氧气和光照的阻隔效果均与铝箔的效果相当，能够替代现有含铝箔的复合包装材料，而且所述复合包装材料不含有铝箔，没有现有技术中铝箔和塑料难以分离的问题。

Description

一种复合包装材料及其制作方法 技术领域
本申请涉及包装技术领域，特别是涉及一种复合包装材料及其制作方法。
背景技术
现有无菌液体复合包装材料的被包装物的保质期能够达到六个月左右，这是因为复合包装材料中含有铝箔，铝箔对氧气和光照的阻隔效果较好。但是由于复合包装材料还含有塑料，铝箔和塑料很难分离，大大降低了含有铝箔的现有复合包装材料的回收再利用效率。
发明内容
本申请主要解决的技术问题是提供一种复合包装材料及其制作方法，能够替代包含铝箔的现有复合包装材料，并提高其回收再利用效率。
为解决上述技术问题，本申请采用的一个技术方案是：
提供一种复合包装材料，包括：依次层叠设置的阻隔层、遮光层、芯层和外层；其中，所述阻隔层和所述遮光层由非金属材料形成，所述阻隔层的氧气透过率OTR小于1.0cm 3/(m 2·24h·0.1MPa)，所述遮光层在6500K色温的光源下，在190nm-1100nm的波长范围内，透光率小于0.5％，所述复合包装材料用于包装液体食品。
为解决上述技术问题，本申请采用的另一个技术方案是：
提供一种复合包装材料的制作方法，包括：
提供阻隔层卷材和芯层卷材，其中，所述阻隔层卷材采用共挤工艺制作；
采用淋膜工艺在所述阻隔层卷材和所述芯层卷材中间形成遮光层，以同时在所述芯层一侧形成依次层叠设置的遮光层和阻隔层；
采用淋膜工艺在所述芯层远离所述遮光层的一侧表面形成外层；
其中，所述阻隔层和所述遮光层由非金属材料形成，所述阻隔层的氧气透过率OTR小于1.0cm 3/(m 2·24h·0.1MPa)，所述遮光层在6500K色温的光源下，在190nm-1100nm的波长范围内，透光率小于0.5％；所述复合包装材料用于包装液体食品。
本申请的有益效果是：区别于现有技术的情况，本申请提供的复合包装材料包括依次层叠设置的阻隔层、遮光层、芯层和外层；其中，阻隔层和遮光层由 非金属材料形成，阻隔层的氧气透过率OTR小于1.0cm 3/(m 2·24h·0.1MPa)，遮光层在6500K色温的光源下，在190nm-1100nm的波长范围内，透光率小于0.5％，复合包装材料用于包装液体食品，对氧气和光照的阻隔效果均与铝箔的效果相当，能够替代现有含铝箔的复合包装材料，而且本申请的复合包装材料不含有铝箔，没有现有技术中铝箔和塑料难以分离的问题。
【附图说明】
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图，其中：
图1为本申请复合包装材料一实施方式的结构示意图；
图2为图1中阻隔层一实施方式的结构示意图；
图3为图1中阻隔层另一实施方式的结构示意图；
图4为本申请复合包装材料的制作方法一实施方式的流程示意图。
【具体实施方式】
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，均属于本申请保护的范围。
请参阅图1，图1为本申请复合包装材料一实施方式的结构示意图，复合包装材料100包括依次层叠设置的阻隔层11、遮光层12、芯层13和外层14，其中，阻隔层11和遮光层12由非金属材料形成，阻隔层11的氧气透过率OTR小于1.0cm 3/(m 2·24h·0.1MPa)，例如0.9cm 3/(m 2·24h·0.1MPa)、0.8cm 3/(m 2·24h·0.1MPa)、0.7cm 3/(m 2·24h·0.1MPa)等，遮光层12在6500K色温的光源下，在190nm-1100nm的波长范围内，透光率小于0.5％，例如0.45％、0.4％、0.35％等；复合包装材料100用于包装液体食品。现有复合包装材料含有铝箔，能够对氧气和光照起到很好的阻隔作用，因而被包装的液体食品的保质期能够到达6个月左右，复合包装材料还含有塑料，但是铝箔和塑料很难分离，大大降低了使用了铝箔的复合包装材料的回收再利用效率。本申请的复合包装 材料100的阻隔层11具备很好的对氧气的阻隔作用，遮光层12具备很好的对光照的阻隔作用，与含有铝箔的复合包装材料对氧气和光照的阻隔效果相当，能够替代现有含铝箔的复合包装材料，而且阻隔层11和遮光层12均由非金属材料形成，不包含铝箔，没有现有技术中铝箔和塑料难以分离的问题。
其中，本申请中氧气透过率OTR的测试标准参照中国标准GB/T 19789-2005或者是ASTM D 3985，测试条件为温度23℃，湿度50％RH，测试仪器采用Ametek Mocon公司的Model 2/22氧气透过率测试仪。
其中，本申请中透光率的测试标准参照中国标准GB/T 2410-2008或者ASTM D 1003，测试条件为温度23℃，湿度50％RH，测试仪器采用PerkinElmer Lambda 950紫外分光光度计。
请继续参阅图1，本申请复合包装材料100各层的厚度分布用克重范围来表示，克重越大，表示厚度越厚。具体地，阻隔层11的克重范围为20g/m 2-40g/m 2，例如20g/m 2、30g/m 2、40g/m 2等，遮光层12的克重范围为15g/m 2-30g/m 2，例如15g/m 2、20g/m 2、30g/m 2等，外层14的克重范围为10g/m 2-18g/m 2，例如10g/m 2、15g/m 2、18g/m 2等；芯层13包括层叠设置的原纸层131和印刷层132，原纸层131位于印刷层132与遮光层12之间，原纸层131的克重范围为170g/m 2-330g/m 2，例如170g/m 2、250g/m 2、330g/m 2等，印刷层132的克重范围为1g/m 2-3g/m 2，例如1g/m 2、2g/m 2、3g/m 2等。如此分布的各层形成的复合包装材料100满足液体食品包装的需求，且具备对氧气和光照的很好的阻隔效果。
具体地，遮光层12包括聚乙烯PE和掺杂在聚乙烯PE中的遮光材料，遮光材料包括色母粒、遮光剂中至少一种。聚乙烯PE为遮光层的基材，主要用于与复合包装材料100的阻隔层11粘接，遮光材料则掺杂在聚乙烯PE基材中，发挥阻隔光照的作用。其中，聚乙烯PE包括低密度聚乙烯LDPE、线性低密度聚乙烯LLDPE、茂金属线性低密度聚乙烯M-LLDPE、高密度聚乙烯HDPE中至少一种，和/或，色母粒包括白色母、黑色母中至少一种，和/或，遮光剂包括氧化锌、钛白粉、炭黑、石墨烯中至少一种。本实施方式选用黑白色母粒或者遮光剂作为遮光材料，能够使遮光层12具备很好的阻隔光照的作用。依照国标GB/T2410-2008，设置光源为D65(色温6500K)，在190nm-1100nm波长范围内，测得遮光层12的透光率小于0.5％，而现有含有铝箔的无菌液体复合包装材料，在同样条件下测得的透光率也是小于0.5％。可见，从复合包装材料的遮光率方面来看，本实施方式的复合包装材料100可以替代现有有铝箔的无菌液体复合 包装材料和其他包装材料，其他包装材料透光率请参见表1，其中，透光率是在色温6500K，波长范围190nm-1100nm范围内测得。
表1其他包装材料的透光率
包装材料 包装类型 体积 内容物 透光率
纸塑复合 屋顶包装(非透明) 1000ml 鲜奶 5％
PET 瓶子(非透明) 230g 酸奶 1％
PS 瓶子(非透明) 500ml 牛奶 10％
HDPE 瓶子(半透明) 1000ml 牛奶 50％
请参阅图2，图2为图1中阻隔层一实施方式的结构示意图，本实施方式的复合包装材料100的阻隔层11包括依次层叠设置的热封层111、第一粘合剂层112、阻氧层113、第二粘合剂层114和粘接层115；其中，粘接层115与遮光层12接触。
优选地，第一粘合剂层112和第二粘合剂层114的材质和厚度相同，热封层111和粘接层115的材质和厚度相同，也就是说，本实施方式的阻隔层11以阻氧层113为中心，在其两侧依次对称分布有第一粘合剂层112和第二粘合剂层114、热封层111和粘接层115。其中，第一粘合剂层112用于粘结阻氧层113和热封层111；第二粘合剂层114用于在阻氧层113的另一侧将阻氧层113和粘接层115粘结在一起；热封层111一方面在复合包装材料100被加工成包装容器时起到热烫封合的作用，另一方面还对阻氧层113起阻水保护作用；最终形成复合包装材料100时，粘接层115用于与遮光层12复合在一起，同时也能对阻氧层113起阻水保护作用。
具体地，阻氧层113包括乙烯-乙烯醇共聚物EVOH，其中乙烯含量为24％～36％，例如24％、30％、36％等，第一粘合剂层112和第二粘合剂层114均包括粘合树脂Adhesive，热封层111和粘接层115均包括聚乙烯PE；其中，粘合树脂Adhesive包括乙烯-丙烯酸共聚物EAA、乙烯-甲基丙烯酸共聚物EMAA、马来酸酐改性聚乙烯MAH-g-PE中至少一种，聚乙烯PE包括低密度聚乙烯LDPE、线性低密度聚乙烯LLDPE、茂金属线性低密度聚乙烯M-LLDPE、高密度聚乙烯HDPE中至少一种。乙烯-乙烯醇共聚物EVOH的乙烯含量越高，加工性能越好，但阻隔性越差，本实施方式选用合适的乙烯含量，使其加工性能和阻隔性能平衡。而且乙烯-乙烯醇共聚物EVOH是一种对氧气有优秀阻隔效果的材料，但其自身不耐水，如果遇到水，其阻隔氧气的效果会下降，因此不能直接暴露在空气中或者直接接触液体食品，本实施方式用由阻水材料聚乙烯 PE形成的热封层111和粘接层115将乙烯-乙烯醇共聚物EVOH夹在中间，又使用粘合树脂Adhesive来增加其与聚乙烯PE材料的粘结牢度，对阻氧层113的乙烯-乙烯醇共聚物EVOH起到很好的阻水保护作用。而且，遮光层12的基材也是聚乙烯PE，在将阻隔层11的粘接层115与遮光层12复合在一起时，同样的聚乙烯PE材料更容易复合，遮光层12和阻隔层11共同作用，可以更有效地保持被包装的液体食品的风味。
请继续参阅图2，以阻氧层113为中心对称的阻隔层11各层的厚度分布如下：热封层111的厚度或占阻隔层11总厚度的25％～40％，例如25％、37％、40％等，第一粘合剂层112的厚度占阻隔层11总厚度的5％～10％，例如5％、7％、10％等，阻氧层113的厚度占阻隔层11总厚度的10％～25％，例如10％、17％、25％等，第二粘合剂层114的厚度占阻隔层11总厚度的5％～10％，例如5％、7％、10％等，粘接层115的厚度占阻隔层11总厚度的25％～40％，例如25％、37％、40％等。因为阻隔层11具有对称结构，因此第一粘合剂层112和第二粘合剂层114的厚度占比相同，热封层111和粘接层115的厚度占比相同，这种对称分布的阻隔层11可以更有效地保护阻氧层113的乙烯-乙烯醇共聚物EVOH，更有利于本申请复合包装材料的后续加工和制成，能够更有效地保持被包装的液体食品的风味。
请参阅图3，图3为图1中阻隔层另一实施方式的结构示意图，相对图2所示的结构，本实施方式的阻隔层21除了包括热封层211、第一粘合剂层212、阻氧层213、第二粘合剂层214和粘接层215，还包括第一加强层216和第二加强层217，其中，第一加强层216位于阻氧层213与第一粘合剂层212之间，第二加强层217位于阻氧层213与第二粘合剂层214之间。
优选地，本实施方式的阻隔层21包括依次层叠设置的热封层211、第一粘合剂层212、第一加强层216、阻氧层213、第二加强层217、第二粘合剂层214和粘接层215，以阻氧层213为中心呈对称结构，其中，第一加强层216和第二加强层217的材质和厚度相同，第一粘合剂层212和第二粘合剂层214的材质和厚度相同，热封层211和粘接层215的材质和厚度相同。
具体地，阻氧层213包括乙烯-乙烯醇共聚物EVOH，其中乙烯含量为24％～36％，例如24％、32％、36％等，第一加强层216和第二加强层217均包括聚酰胺PA，第一粘合剂层212和第二粘合剂层214均包括粘合树脂Adhesive，热封层211和粘接层215均包括聚乙烯PE；其中，粘合树脂Adhesive包括乙烯 -丙烯酸共聚物EAA、乙烯-甲基丙烯酸共聚物EMAA、马来酸酐改性聚乙烯MAH-g-PE中至少一种，聚乙烯PE包括低密度聚乙烯LDPE、线性低密度聚乙烯LLDPE、茂金属线性低密度聚乙烯M-LLDPE、高密度聚乙烯HDPE中至少一种；聚酰胺PA包括聚酰胺-6、聚酰胺-66、聚酰胺-11、聚酰胺-12，尼龙46，尼龙610，尼龙612，尼龙1010中至少一种。乙烯-乙烯醇共聚物EVOH的乙烯含量越高，加工性能越好，但阻隔性越差，本实施方式选用合适的乙烯含量，使其加工性能和阻隔性能平衡。而且乙烯-乙烯醇共聚物EVOH是一种对氧气有优秀阻隔效果的材料，但其自身不耐水，如果遇到水，其阻隔氧气的效果会下降，因此不能直接暴露在空气中或者直接接触液体食品，本实施方式首先用聚酰胺PA将乙烯-乙烯醇共聚物EVOH夹在中间，再用由阻水材料聚乙烯PE形成的热封层211和粘接层215分别分布在两层聚酰胺PA的外侧，又使用粘合树脂Adhesive来增加聚酰胺PA与聚乙烯PE材料的粘结牢度，对阻氧层213的乙烯-乙烯醇共聚物EVOH起到很好的阻水保护作用。遮光层12和阻隔层11共同作用，可以更有效地保持被包装的液体食品的风味，同时聚酰胺PA是一种工程塑料，其自身的挺度要大于聚乙烯PE，因此有利于最终液体包装的完整性，保证包装具有较高的力学性能。
请继续参阅图3，以阻氧层213为中心对称的阻隔层21各层的厚度分布如下：热封层211的厚度占阻隔层21总厚度的25％～40％，第一粘合剂层212的厚度占阻隔层21总厚度的5％～10％，第一加强层216的厚度占阻隔层21总厚度的2％～10％，阻氧层213的厚度占阻隔层21总厚度的10％～25％，第二加强层217的厚度占阻隔层21总厚度的2％～10％，第二粘合剂层214的厚度占阻隔层21总厚度的5％～10％，粘接层215的厚度占阻隔层21总厚度的25％～40％。这种对称分布的阻隔层11可以更有效地保护阻氧层113的乙烯-乙烯醇共聚物EVOH，更有利于本申请复合包装材料的后续加工和制成，能够更有效地保持被包装的液体食品的风味。
本申请复合包装材料通过使用含有乙烯-乙烯醇共聚物EVOH的阻隔层11或者21，其氧气透过率OTR＜1.0cm 3/(m 2·24h·0.1MPa)，成型包装的氧气透过率OTR＜0.2cm 3/(pkg·24h·0.1MPa)，而现有含有铝箔的无菌液体复合包装材料，其氧气透过率OTR＜1.0cm 3/(m 2·24h·0.1MPa)，成型包装的氧气透过率OTR＜1.0cm 3/(pkg·24h·0.1MPa)。依照无菌液体包装材料的国家标准GB/T18192-2008，如果阻隔材料为铝箔，其氧气透过率OTR＜1.0 cm 3/(m 2·24h·0.1MPa)；如果阻隔材料为其他非铝箔材料，其氧气透过率OTR＜15.0cm 3/(m 2·24h·0.1MPa)，可见本申请复合包装材料不仅满足国标规定，还达到了国标中对于铝箔为阻隔材料的氧气透过率要求。而且，由于本申请复合包装材料的阻隔层11或者21是由多层薄膜形成，而现有无菌液体复合包装材料是使用铝箔来阻隔光照和氧气，多层薄膜比起铝箔的优势在于折叠后不发生开裂，所以本申请复合包装材料成型包装的氧气透过率OTR要小于现有含有铝箔的无菌液体包装材料成型包装的氧气透过率OTR。因此，从包装材料的氧气透过率OTR方面来看，本申请复合包装材料可以替代现有包含铝箔的无菌液体复合包装材料和其他包装材料，其他包装材料的氧气透过率OTR请参见表2，其中，氧气透过率OTR的单位是cm 3/(pkg·24h·0.1MPa)。
表2其他包装材料的氧气透过率OTR
包装材料 包装类型 体积 内容物 OTR
PET 瓶子(透明) 600ml 可乐 1.0
PET 瓶子(非透明) 230g 酸奶 0.6
多层膜 百丽袋(非透明) 200g 牛奶 0.8
多层膜 爱克林(非透明) 200g 牛奶 1.0
PS 瓶子(非透明) 500ml 牛奶 3.0
HDPE 瓶子(非透明) 1000ml 牛奶 5.0
含有铝箔的现有无菌包的回收方法是进行铝箔和聚乙烯PE的分离，分离时需要使用80％的乙酸在50℃下浸泡，这会导致回收后的铝箔严重碎片化，致使回收价值变低，并且可能产生氢气，影响环境，且聚乙烯PE仍会有少量铝箔残留，影响回收PE的纯净度。另外酸液在排放前需要进行稀释或中和处理，增加了额外的处理成本及环境影响。本申请复合包装材料不包含铝箔，含有大量的聚乙烯PE和其他油溶性或者水溶性的非金属物质，回收时可以省去酸处理的步骤，仅使用水溶解便可分成纤维流以及聚乙烯流，水溶的其他物质溶解在水中，油溶性的其他则物质含量很低，不影响回收。根据已知的一份Kuraray与nextek合作的乙烯-乙烯醇共聚物EVOH回收研究报告(数据源：SPE
Figure PCTCN2020088440-appb-000001
Anaheim2017)，含有5％的乙烯-乙烯醇共聚物EVOH聚烯烃膜经过回收造粒后可再与新鲜的原料共挤(回收料比例≤15％)，在食品安全和机械性能等各方面都处于可接受水平。换句话说，EVOH的含量如果不超过5％，完全可以使用现有的回收系统并纳入聚烯烃流而不会影响回收聚烯烃的应用。本申请复合包装材料的阻隔层使用的乙烯-乙烯醇共聚物EVOH含量占复合包装材料总量的比例低于5％， 所以回收效率更高。
另外，本申请复合包装材料可以包装的液体食品至少包括超高温灭菌牛奶、巴氏杀菌奶、长期货架奶、奶油、风味和配方乳品、发酵乳品、浓缩奶、炼乳、复原乳、果汁、非碳酸饮料、茶、椰子水、汤料、番茄酱和酱料，能够有效地保持上述液体食品及其他液体食品的风味。
请参阅图4，图4为本申请复合包装材料的制作方法一实施方式的流程示意图，本实施方式包括如下步骤：
S401，提供阻隔层卷材和芯层卷材，其中，阻隔层卷材采用共挤工艺制作。
S402，采用淋膜工艺在阻隔层卷材和芯层卷材中间形成遮光层，以同时在芯层一侧形成依次层叠设置的遮光层和阻隔层。
S403，采用淋膜工艺在芯层远离遮光层的一侧表面形成外层。
其中，阻隔层和遮光层由非金属材料形成，阻隔层的氧气透过率OTR小于1.0cm 3/(m 2·24h·0.1MPa)，例如0.9cm 3/(m 2·24h·0.1MPa)、0.8cm 3/(m 2·24h·0.1MPa)、0.7cm 3/(m 2·24h·0.1MPa)等，遮光层在6500K色温的光源下，在190nm-1100nm的波长范围内，透光率小于0.5％，例如0.45％、0.4％、0.35％等；复合包装材料用于包装液体食品。本实施方式所制得的复合包装材料的阻隔层具备很好的对氧气的阻隔作用，遮光层具备很好的对光照的阻隔作用，与现有含有铝箔的复合包装材料对氧气和光照的阻隔效果相当，能够替代现有含铝箔复合包装材料，而且阻隔层11和遮光层12均由非金属材料形成，不包含铝箔，也就没有铝箔和塑料难以分离的问题。
具体地，步骤S401所述的采用共挤工艺制作阻隔层卷材包括：利用多层共挤吹膜机同时形成依次层叠设置的热封层、第一粘合剂层、阻氧层、第二粘合剂层和粘接层。或者包括：利用多层共挤吹膜机同时形成依次层叠设置的热封层、第一粘合剂层、第一加强层、阻氧层、第二加强层、第二粘合剂层和粘接层。其中，阻氧层包括乙烯-乙烯醇共聚物EVOH，第一加强层和第二加强层均包括聚酰胺PA，第一粘合剂层和第二粘合剂层均包括粘合树脂Adhesive，热封层和粘接层均包括聚乙烯PE。多层共挤吹膜机主要包括五层共挤吹膜机、七层共挤吹膜机、九层共挤吹膜机、十一层共挤吹膜机等，比如五层共挤吹膜机可以制作小于等于五层的多层薄膜，制作阻隔层卷材过程中，幅宽范围为800mm～1600mm，所制得阻隔层卷材的氧气透过率OTR＜1.0cm 3/(m 2·24h·0.1MPa)，水蒸气透过率＜10.0cm 3/(m 2·24h·0.1MPa)。以制作 包括热封层、第一粘合剂层、第一加强层、阻氧层、第二加强层、第二粘合剂层和粘接层的阻隔层卷材为例，七层共挤吹膜机各层各区加工温度设定范围见表3，其中，PE表示热封层和粘接层，Adhesive表示第一粘合剂层和第二粘合剂层，PA表示第一加强层和第二加强层，EVOH表示阻氧层。
表3七层共挤吹膜机各层各区加工温度设定范围
加热区 喂料区/℃ 第二区/℃ 第三区/℃ 第四区/℃ 第五区/℃ 接头区/℃ 模头区/℃
PE 80-120 95-140 110-160 110-160 110-160 110-160 110-160
Adhesive 140-180 165-205 215-255 215-280 215-280 215-280 215-280
PA 170-230 180-240 190-250 200-260 200-260 200-260 200-260
EVOH 180-220 190-230 200-240 200-240 200-240 200-240 200-240
步骤S402所述的采用淋膜工艺在阻隔层卷材和芯层卷材中间形成遮光层，包括：利用高速复合淋膜机将聚乙烯PE和遮光材料复合在阻隔层卷材的粘接层和芯层卷材中间形成遮光层，并将阻隔层、遮光层和芯层三者挤压在一起。其中，遮光材料包括白色母、黑色母和遮光剂中至少一种，遮光剂包括氧化锌、钛白粉、炭黑、石墨烯中至少一种。
步骤S403所述的采用淋膜工艺在芯层远离遮光层的一侧表面形成外层，包括：利用高速复合淋膜机将聚乙烯PE复合在芯层远离遮光层的一侧表面形成外层。
高速复合淋膜机包括外层站、复合站、内层站三个挤出站，复合过程中，芯层卷材作为基材放卷运行，先通过复合站，同时将阻隔层卷材从铝箔放卷装置上进行放卷运行，在复合站将芯层、遮光层和阻隔层进行复合，也就是将芯层和阻隔层通过熔融状态下的遮光层粘合在一起；然后直接通过未开启的内层站，最后通过外层站将外层复合在芯层外侧。高速复合淋膜机的基材幅宽范围为850mm～1650mm，生产线速度为300～800m/min，各站加工温度设定范围见表4。
表4高速复合淋膜机各站加工温度设定范围
加热区 复合站 外层站
加热一区 210-250℃ 200-240℃
加热二区 240-280℃ 230-270℃
加热三区 270-310℃ 260-300℃
加热四区 300-340℃ 285-325℃
加热五区 300-340℃ 285-325℃
加热六区 300-340℃ 285-325℃
加热七区 300-340℃ 285-325℃
加热八区 300-340℃ 285-325℃
加热九区 300-340℃ 285-325℃
加热十区 300-340℃ 285-325℃
模头 300-340℃ 285-325℃
本实施方式中，聚乙烯PE包括低密度聚乙烯LDPE、线性低密度聚乙烯LLDPE、茂金属线性低密度聚乙烯M-LLDPE、高密度聚乙烯HDPE中至少一种，聚酰胺PA包括聚酰胺-6、聚酰胺-66、聚酰胺-11、聚酰胺-12，尼龙46，尼龙610，尼龙612，尼龙1010中至少一种。
本申请复合包装材料与现有含铝箔无菌液体复合包装材料的制作工艺相比，其差异包括如下内容：
①本申请复合包装材料的复合工段(即高速复合淋膜机工段)不需要使用内层站，而现有无菌液体复合包装材料的复合工段需要使用内层站。
②本申请复合包装材料的复合工段通过铝箔放卷装置进行阻隔层卷材的放卷，而现有无菌液体复合包装材料的复合工段通过铝箔放卷装置进行铝箔卷材的放卷。
③本申请复合包装材料的制作工艺包含吹膜(多层共挤吹膜机)和淋膜(高速复合淋膜机)两种工艺，而现有无菌液体复合包装材料的制作工艺仅为淋膜，不进行吹膜。
④本申请复合包装材料的阻隔层是通过吹膜工艺形成，其优势在于，吹膜的拉伸强度要大于淋膜，数据对比见表5，PA表示聚酰胺；而且用阻隔层替代铝箔，在包装折叠成型后由多层薄膜形成的阻隔层不易发生破损或断裂，不会引起氧气透过率OTR的下降。
表5不同工艺下阻隔层膜的拉伸强度
Figure PCTCN2020088440-appb-000002
本申请复合包装材料在客户端是要通过利乐公司的灌装机在无菌系统条件下进行灌装。灌装机现有的电磁感应封合方式为适应现有含铝箔的无菌液体复合包装材料，灌装机通过电磁感应将铝箔加热，然后受热的铝箔将聚乙烯PE塑化从而进行封合。但因为本申请提供的复合包装材料不包含铝箔，所以无法通 过电磁感应的方式进行封合，为适应本申请复合包装材料，需将现有电磁感应的封合方式改造为超声波的封合方式，改造之后，可以直接将聚乙烯PE塑化进行封合，不需要受到铝箔传热的限制。而且，超声波的封合方式在封合性能上可以和电磁感应的封合方式保持一致，包括：封合时间短，封合性能不受污染物的影响，无需冷却。
下面结合具体的实施例来描述本申请复合包装材料与现有含铝箔无菌液体复合包装材料的生产工艺和性能对比，请参见表6，其中，复合包装材料的氧气透过率OTR的单位是cm 3/(m 2·24h·0.1MPa)，成型包的氧气透过率OTR的单位是cm 3/(pkg·24h·0.1MPa)，从表中数据可见，对比例1的铝箔同时发挥阻隔光照和氧气的作用，实施例1-3使用含遮光材料的遮光层来阻隔光照，使用由多层膜薄膜形成的阻隔层来阻隔氧气，实施例1-3和对比例1的透光率基本一致，实施例1-3复合包装材料的氧气透过率OTR和对比例1基本一致，而成型包的氧气透过率OTR明显要低于对比例1。而且，实施例1-3的回收性能均要强于对比例1，封合方式也打破了铝箔的限制。
表6复合包装材料与含铝箔复合包装材料的生产工艺和性能对比
Figure PCTCN2020088440-appb-000003
Figure PCTCN2020088440-appb-000004
以上所述仅为本申请的实施方式，并非因此限制本申请的专利范围，凡是利用本申请说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本申请的专利保护范围内。

Claims (18)

  1. 一种复合包装材料，其中：
    所述复合包装材料包括依次层叠设置的阻隔层、遮光层、芯层和外层；
    其中，所述阻隔层和所述遮光层由非金属材料形成，所述阻隔层的氧气透过率OTR小于1.0cm 3/(m 2·24h·0.1MPa)，所述遮光层在6500K色温的光源下，在190nm-1100nm的波长范围内，透光率小于0.5％；
    所述复合包装材料用于包装液体食品。
  2. 根据权利要求1所述的复合包装材料，其中，
    所述遮光层包括聚乙烯PE和掺杂在所述聚乙烯PE中的遮光材料；所述遮光材料包括色母粒、遮光剂中至少一种。
  3. 根据权利要求2所述的复合包装材料，其中，
    所述聚乙烯PE包括低密度聚乙烯LDPE、线性低密度聚乙烯LLDPE、茂金属线性低密度聚乙烯M-LLDPE、高密度聚乙烯HDPE中至少一种；和/或，所述色母粒包括白色母、黑色母中至少一种；和/或，所述遮光剂包括氧化锌、钛白粉、炭黑、石墨烯中至少一种。
  4. 根据权利要求1所述的复合包装材料，其中，
    所述阻隔层包括依次层叠设置的热封层、第一粘合剂层、阻氧层、第二粘合剂层和粘接层；
    其中，所述粘接层与所述遮光层接触。
  5. 根据权利要求4所述的复合包装材料，其中，
    所述第一粘合剂层和所述第二粘合剂层的材质和厚度相同，所述热封层和所述粘接层的材质和厚度相同。
  6. 根据权利要求4所述的复合包装材料，其中，
    所述阻氧层包括乙烯-乙烯醇共聚物EVOH，所述第一粘合剂层和所述第二粘合剂层均包括粘合树脂Adhesive，所述热封层和所述粘接层均包括聚乙烯PE；
    其中，所述乙烯-乙烯醇共聚物EVOH的乙烯含量为24％-36％，所述粘合树脂Adhesive包括乙烯-丙烯酸共聚物EAA、乙烯-甲基丙烯酸共聚物EMAA、马来酸酐改性聚乙烯MAH-g-PE中至少一种，所述聚乙烯PE包括低密度聚乙烯LDPE、线性低密度聚乙烯LLDPE、茂金属线性低密度聚乙烯M-LLDPE、高密度聚乙烯HDPE中至少一种。
  7. 根据权利要求4所述的复合包装材料，其中，
    所述热封层的厚度或占所述阻隔层总厚度的25％～40％，所述第一粘合剂层的厚度占所述阻隔层总厚度的5％～10％，所述阻氧层的厚度占所述阻隔层总厚度的10％～25％，所述第二粘合剂层的厚度占所述阻隔层总厚度的5％～10％，所述粘接层的厚度占所述阻隔层总厚度的25％～40％。
  8. 根据权利要求4所述的复合包装材料，其中，
    所述阻隔层还包括第一加强层和第二加强层，所述第一加强层位于所述阻氧层与所述第一粘合剂层之间，所述第二加强层位于所述阻氧层与所述第二粘合剂层之间。
  9. 根据权利要求8所述的复合包装材料，其中，
    所述第一加强层和所述第二加强层的材质和厚度相同，所述第一粘合剂层和所述第二粘合剂层的材质和厚度相同，所述热封层和所述粘接层的材质和厚度相同。
  10. 根据权利要求8所述的复合包装材料，其中，
    所述阻氧层包括乙烯-乙烯醇共聚物EVOH，所述第一加强层和所述第二加强层均包括聚酰胺PA，所述第一粘合剂层和所述第二粘合剂层均包括粘合树脂Adhesive，所述热封层和所述粘接层均包括聚乙烯PE；
    其中，所述乙烯-乙烯醇共聚物EVOH的乙烯含量为24％-36％，所述粘合树脂Adhesive包括乙烯-丙烯酸共聚物EAA、乙烯-甲基丙烯酸共聚物EMAA、马来酸酐改性聚乙烯MAH-g-PE中至少一种，所述聚乙烯PE包括低密度聚乙烯LDPE、线性低密度聚乙烯LLDPE、茂金属线性低密度聚乙烯M-LLDPE、高密度聚乙烯HDPE中至少一种，所述聚酰胺PA包括聚酰胺-6、聚酰胺-66、聚酰胺-11、聚酰胺-12，尼龙46，尼龙610，尼龙612，尼龙1010中至少一种。
  11. 根据权利要求8所述的复合包装材料，其中，
    所述热封层的厚度占所述阻隔层总厚度的25％～40％，所述第一粘合剂层的厚度占所述阻隔层总厚度的5％～10％，所述第一加强层的厚度占所述阻隔层总厚度的2％～10％，所述阻氧层的厚度占所述阻隔层总厚度的10％～25％，所述第二加强层的厚度占所述阻隔层总厚度的2％～10％，所述第二粘合剂层的厚度占所述阻隔层总厚度的5％～10％，所述粘接层的厚度占所述阻隔层总厚度的25％～40％。
  12. 根据权利要求1所述的复合包装材料，其中，
    所述阻隔层的克重范围为20g/m 2-40g/m 2，所述遮光层的克重范围为15g/m 2-30g/m 2，所述外层的克重范围为10g/m 2-18g/m 2；所述芯层包括层叠设置的原纸层和印刷层，所述原纸层位于所述印刷层与所述遮光层之间，所述原纸层的克重范围为170g/m 2-330g/m 2，所述印刷层的克重范围为1g/m 2-3g/m 2。
  13. 根据权利要求1所述的复合包装材料，其中，
    所述液体食品至少包括超高温灭菌牛奶、巴氏杀菌奶、长期货架奶、奶油、风味和配方乳品、发酵乳品、浓缩奶、炼乳、复原乳、果汁、非碳酸饮料、茶、椰子水、汤料、番茄酱和酱料。
  14. 一种复合包装材料的制作方法，其中，所述制作方法包括：
    提供阻隔层卷材和芯层卷材，其中，所述阻隔层卷材采用共挤工艺制作；
    采用淋膜工艺在所述阻隔层卷材和所述芯层卷材中间形成遮光层，以同时在所述芯层一侧形成依次层叠设置的遮光层和阻隔层；
    采用淋膜工艺在所述芯层远离所述遮光层的一侧表面形成外层；
    其中，所述阻隔层和所述遮光层由非金属材料形成，所述阻隔层的氧气透过率OTR小于1.0cm 3/(m 2·24h·0.1MPa)，所述遮光层在6500K色温的光源下，在190nm-1100nm的波长范围内，透光率小于0.5％；
    所述复合包装材料用于包装液体食品。
  15. 根据权利要求14所述的制作方法，其中，所述采用共挤工艺制作所述阻隔层卷材，包括：
    利用多层共挤吹膜机同时形成依次层叠设置的热封层、第一粘合剂层、阻氧层、第二粘合剂层和粘接层；
    其中，所述阻氧层包括乙烯-乙烯醇共聚物EVOH，所述第一粘合剂层和所述第二粘合剂层均包括粘合树脂Adhesive，所述热封层和所述粘接层均包括聚乙烯PE。
  16. 根据权利要求14所述的制作方法，其中，所述采用共挤工艺制作阻隔层卷材，包括：
    利用多层共挤吹膜机同时形成依次层叠设置的热封层、第一粘合剂层、第一加强层、阻氧层、第二加强层、第二粘合剂层和粘接层；
    其中，所述阻氧层包括乙烯-乙烯醇共聚物EVOH，所述第一加强层和所述第二加强层均包括聚酰胺PA，所述第一粘合剂层和所述第二粘合剂层均包括粘合树脂Adhesive，所述热封层和所述粘接层均包括聚乙烯PE。
  17. 根据权利要求15或16所述的制作方法，其中，所述采用淋膜工艺在所述阻隔层卷材和所述芯层卷材中间形成遮光层，包括：
    利用高速复合淋膜机将聚乙烯PE和遮光材料复合在所述阻隔层卷材的所述粘接层和所述芯层卷材中间形成遮光层，并将所述阻隔层、所述遮光层和所述芯层三者挤压在一起；
    其中，所述遮光材料包括白色母、黑色母和遮光剂中至少一种。
  18. 根据权利要求14所述的制作方法，其中，所述采用淋膜工艺在所述芯层远离所述遮光层的一侧表面形成外层，包括：
    利用高速复合淋膜机将聚乙烯PE复合在所述芯层远离所述遮光层的一侧表面形成外层。
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