CN1693153B - Multi-layer polymer composite packaging container with nano-layer texture and processing method thereof - Google Patents

Abstract

The invention discloses a multi-layer polymer composite packaging container with nano-layer texture and a processing method thereof. It is processed through processes such as extrusion/co-injection, cooling molding, heat treatment, and thermal stretching. In the container wall, the lamellar c-axis of the base phase polymer layer crosses the lamellar c-axis of the epigenetic phase polymer layer. And the cumulative layer thickness of the base phase polymer layer is 50-99% of the thickness of the packaging container wall, the cumulative layer thickness of the epigenetic phase polymer layer is 1-50%, and the single layer thickness of the epigenetic phase polymer layer is 50-99%. 300 nm. In the present invention, since the nano-layer reinforcement phase of the braided structure is formed in the wall of the packaging container, and the two-phase crystal regions are bridged to each other, the defects in the amorphous region are greatly reduced, and the strength, rigidity and ductility of the composite packaging container are improved. Both have been greatly improved, and endow packaging containers with extremely high barrier properties and corrosion resistance.

Description

Multi-layer polymer composite packaging container with nano-layer texture and processing method thereof

1. Technical field.

The invention belongs to the technical field of polymer material processing, and more specifically relates to a high-strength, high-barrier polymer composite packaging container and a processing method thereof.

2. Background technology

Polymer materials are widely used in the packaging fields of food, beverages, pharmaceuticals, chemical products, mechanical and electronic devices, instruments and meters, and military products. Many foods, beverages and medicines are prone to corruption, taste, color and deterioration under the action of oxygen and other gases, so their packaging containers should have sufficient barrier properties to oxygen and other gases. Different contents have different requirements on the gas barrier properties of packaging containers. Carbonated beverages such as soda are required to keep the internal carbon dioxide gas from escaping as little as possible. For beer packaging containers, higher oxygen and carbon dioxide barrier properties are required. At present, injection-stretch-blow-molded polyethylene terephthalate (PET) containers have been widely used in the packaging of mineral water, fruit juices, carbonated drinks, and canned foods. In the field of application of higher gas barrier properties, the current plastic beer bottles use polyethylene terephthalate/ethylene vinyl alcohol copolymer (PET/EVOH), polyethylene terephthalate/polyamide (PET/ PA) and other multi-layer co-injection-stretch-blow molding, or polyethylene naphthalate (PEN) injection-stretch-blow molding, or in conventional injection-stretch-blow molding PET bottles Internal carbon coating and other methods. However, there are still many problems in the above method. EVOH will lose most of its oxygen barrier properties when the ambient moisture or relative humidity is high. PA needs to be quite thick to have oxygen barrier properties. PEN material is expensive, and the interior of PET bottles is carbon-coated Membrane technology equipment costs are high.

Dry foods, pharmaceutical powders, diluents, chemical raw materials and other highly hygroscopic items are easily affected by moisture and deteriorate during storage and transportation. Electrical components, precision machinery, instruments and meters, etc. are prone to rust or mold erosion when exposed to moisture. Packaging containers are required to have good moisture barrier properties. Generally, polyolefin polymers can be used as moisture barrier packaging materials, but their moisture barrier performance is limited. When the content requires high moisture barrier performance, such as injection drug powder injections, chemical raw materials, etc., glass or aluminum is still mainly used. Obviously, glass containers are fragile, and the manufacturing cost of aluminum containers is high, but polyolefin packaging containers formed according to conventional methods are difficult to meet the requirements of high moisture barrier performance.

3. Contents of the invention

The present invention aims at the deficiencies of the high molecular polymer packaging containers processed in the prior art, and aims to provide a multi-layer polymer composite packaging container with heterogeneous epigenetic crystal nano-layer texture and its production method to improve plastic packaging The strength and barrier properties of the container.

The multi-layer polymer composite packaging container with nano-layer texture provided by the present invention includes containers such as boxes, barrels, cans, bottles, bags, bags, boxes, etc., and its technical scheme is as follows:

In the multi-layer polymer composite packaging container with nano-layer texture provided by the present invention, its shell wall is made of an epigenetic phase polymer (represented by A) that can form a non-parallel chain heterogeneous epitaxial crystal cross-braided structure in the orientation The staggered overlapping multi-layer structure formed by epiphytic crystals on the base phase polymer (represented by B), the cumulative thickness of each layer of the oriented base phase polymer is 50-99% of the total thickness of the packaging container wall, preferably the packaging container 75-95% of the total thickness of the wall, the lamellae c-axis of the ordered crystal of the epiphytic phase polymer layer intersects with the c-axis of the base phase polymer lamellae, and the angle of intersection is preferably not less than 30 degrees, and the cumulative thickness of each layer is packaging 1-50% of the total wall thickness of the container, preferably 5-25% of the total wall thickness of the packaging container, and the single layer thickness of the epitaxial phase polymer layer is preferably 50-300 nm.

As mentioned above, the combination pair A/B of the epitaxial phase polymer (represented by A) and the base phase polymer (represented by B) that can form a non-parallel chain heterogeneous epitaxial crystal cross-braided structure can be polyethylene and Polypropylene, polypropylene and polyamide, etc. Said polyethylene can be various types of polyethylene, such as low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene and the like. Said polypropylene can be isotactic polypropylene or syndiotactic polypropylene. Said polyamide can be various types of polyamides, such as polyamide 6, 66, 11, 12 and other models.

The above-mentioned preparation and processing method of the multi-layer polymer composite packaging container with nano-layer texture, the flow chart is shown in Figure 1, mainly including the following process steps:

(1) Melt extrusion: Put the basal phase polymer and the epiphytic phase polymer in the selected polymer combination into different extruders and heat them to a molten state for plasticizing and extruding;

(2) Micro-layer co-extrusion: The two melt streams extruded by the extruder to form the base phase polymer layer and the epiphytic phase polymer layer are simultaneously and quantitatively transported into the layered co-extrusion at a predetermined flow rate ratio Molding, forming a layered composite molten tablet, and then entering the layer multiplier for repeated division-overlap-convergence, so that the number of layers increases and the layer thickness becomes thinner;

(3) Extrusion and calendering of composite film, composite sheet, and composite sheet: the sheet-like material flow out of the layer multiplier enters the flat-slot sheet and die for extrusion to form a multi-layer polymer in a melt state The blanks of composite sheets and plates are rolled and cooled by a series of rollers to form composite films, sheets, and plates;

(4) Reheating treatment: reheat the cooled and shaped composite film, sheet, and plate to make the temperature rise to between the melting point temperature of the epiphytic phase polymer and the melting point temperature of the base phase polymer, or lower than the temperature of the epiphytic phase polymer. The melting point temperature of the phase polymer;

(5) Thermal stretching: Stretch the heat-treated composite film, sheet, and plate to cause stretching deformation and make it reach the designed geometric size and thickness.

(6) Container forming: the composite film, composite sheet, and composite sheet that are stretched and deformed to the designed geometric size and thickness are made into packaging containers of the required shape by thermal welding, thermoforming, and bonding.

The above-mentioned multi-layer polymer composite packaging container with nano-layer texture can also be prepared by the following steps when the container is made of a multi-layer composite film as a base material:

(1) Melt extrusion: Put the basal phase polymer and epiphytic phase polymer in the selected polymer combination into two extruders respectively, heat to a molten state and plasticize and extrude;

(2) Micro-layer co-extrusion: The two melt streams extruded by the extruder to form the base phase polymer layer and the epiphytic phase polymer layer are simultaneously and quantitatively transported into the layered co-extrusion at a predetermined flow rate ratio Molding, forming a layered composite molten tablet, and then entering the layer multiplier for repeated division-overlap-convergence, so that the number of layers increases and the layer thickness becomes thinner;

(3) Composite film extrusion and blow molding: the sheet-like material stream flowing out from the layer multiplier is divided into at least 2 strands, and is extruded through at least 2 feed channels into at least 2-layer co-extruded nozzle dies to form a molten The multi-layer polymer composite tube blank in solid state, after the tube blank leaves the die, it is blown by the compressed air inside to form a tubular bubble film, which is cooled by the wind ring;

(4) Reheating treatment: the cooled composite tubular foam film is cut longitudinally into a flat film, and then heated to make the temperature rise to between the melting point temperature of the epiphytic phase polymer and the melting point temperature of the base phase polymer , or lower than the melting point temperature of the epiphytic phase polymer;

(5) Thermal stretching: Stretch the heat-treated composite film to cause stretching deformation and make it reach the designed geometric size and thickness.

(6) Container forming: The composite film stretched and deformed to the designed geometric size and thickness is made into a packaging container of the required shape by heat welding, thermoforming, bonding and other methods.

The above-mentioned multi-layer polymer composite packaging containers with nano-layer texture, especially containers with high requirements for dimensional accuracy and surface quality, or containers with a neck diameter smaller than the body, such as composite packaging containers such as cans and bottles, can also be used The following method is prepared, and its specific preparation and processing method flow chart is as shown in Figure 2, mainly comprising the following process steps:

(1) Melt plasticization: put the basal phase polymer and the epiphytic phase polymer in the selected polymer combination into the two barrels of the double barrel injection machine, heat to the molten state and plasticize, and then inject Driven by the components, it is injected into the micro-layer co-injection process through the nozzle of the injection machine;

(2) Microlayer co-injection: The two melt streams that respectively form the basal phase polymer layer and the epiphytic phase polymer layer are injected quantitatively into the layered co-injection mixer at a predetermined flow rate ratio to form layers Composite molten tablets, and then enter the layer multiplier for repeated division-overlap-convergence, so that the number of layers increases and the thickness of the layers becomes thinner;

(3) Container parison injection molding: The material stream flowing out of the layer multiplier is injected into the cavity of the container parison injection molding mold with at least one mold and one cavity, and is cooled and shaped into a multi-layer polymer composite container parison ;

(4) Heat treatment and temperature adjustment of the container parison: the cooled and shaped composite container parison is then heated to make its temperature rise to between the melting point temperature of the epiphytic phase polymer and the melting point temperature of the base phase polymer, or lower than the temperature of the adjacent phase polymer. The melting point temperature of the raw phase polymer;

(5) Stretch blow molding: place the heat-treated container parison into the blow mold, stretch the heat-treated composite container parison through a stretch rod and inject compressed air into the parison to make the mold Billet inflation produces biaxial stretching deformation, the circumferential stretching ratio is controlled at 1.1-4, and the longitudinal stretching ratio is controlled at 1.5-10. After inflating, the container wall adheres to the inner wall of the mold cavity and is cooled to form a bottle, can and other container shapes, reaching the designed geometric size and thickness.

In the above three methods of preparing multilayer polymer composite packaging containers, when the heat treatment temperature in the preparation process step (4) is lower than the melting point temperature of the epiphytic phase polymer, the composite container of stretch blow molding must be re- Heating is carried out once, and the temperature is raised to a temperature higher than the melting point of the epiphytic phase polymer but lower than the melting point of the base phase polymer for a period of heat treatment.

The extruder mentioned above can be a single-screw extruder or a twin-screw extruder, and the injection molding machine can use a double-barrel injection molding machine, or an additional injection device can be installed on the ordinary single-barrel injection molding machine .

In the above-mentioned method of processing a multi-layer polymer composite packaging container with a nano-layer texture by injection-stretching-blow molding, the molding mold of the container parison can be a common injection molding mold or a hot runner type. injection molding mold.

The layered co-extrusion/co-injection mold mentioned above has at least two layers, preferably three layers, and the two polymers forming the base phase and the epigenetic phase are quantitatively transported into the mold by two extruders, or extruded The extruder is combined with the melt pump to quantitatively transport into the mold, or the injection machine is quantitatively transported into the mold, so that the two melt streams of the base phase polymer and the epiphytic phase polymer flowing out of the co-extrusion/co-injection mold follow the predetermined The proportions of the components converge to form a B-A-B three-layer structure melt tablet. Said layer multiplier is a 2-8 stage layer multiplier designed with 2-8 material flow channels, the structure of which is shown in FIG. 3 . The order mentioned here refers to the number of times of splitting-overlapping-merging of the layered structure melt tablet, the second step refers to splitting-overlapping-merging twice, and the eighth step refers to splitting-overlapping-merging eight times. When stretching composite films, sheets, and plates, the longitudinal stretching ratio is controlled at 1.5-30.

Heterogeneous epitaxial crystallization of polymers is a phenomenon of epitaxial crystallization of one crystalline polymer on an oriented substrate of another crystalline polymer. In the polymer composite packaging container formed by the epitaxial phase polymer layer and the base phase polymer layer, the c-axis of the platelets of the epitaxial phase polymer layer and the c-axis of the platelets of the base phase polymer layer form a large angle At the cross angle, the wall of the polymer composite packaging container is a braided structure with nano-scale layer thickness, so the strength, modulus and ductility of the wall of the polymer composite packaging container in both vertical and horizontal directions are greatly improved. In addition, since the two polymer lamellae become bridges connecting the square crystal region and the amorphous region respectively, and the amorphous region is the weak point of the mechanical properties of the material, the bridging connection of the crystal region can strengthen the weaknesses of both. , resulting in a positive synergistic effect of mechanical properties, which further improves the mechanical properties, barrier properties and corrosion resistance of the polymer composite packaging container wall. The present invention utilizes the principle of heterogeneous epigenetic crystallization of polymers to develop a nano-layer textured multi-layer polymer composite packaging container. In this packaging container, the c-axis of the polymer platelets of the base phase and the c-axis of the polymer platelets of the epiphytic phase intersect at a large angle of 30-60 degrees, as shown in FIG. 4 . In the plastic composite packaging container with this special morphological structure, the crystal orientation of the polymer in the base phase is arranged, and the c-axis of the ordered platelet crystal of the epiphytic phase polymer crosses the c-axis of the polymer platelet in the base phase at a large angle. In the wall of the packaging container, an ordered crystal-reinforced phase cross-woven structure is formed, and the interlayer bonding strength of the two phases is extremely high, which greatly improves the physical and mechanical strength of the packaging container in the longitudinal and transverse directions; at the same time, the mutual frame of the two-phase crystal regions The bridge also greatly reduces the defects in the amorphous region, further improving the longitudinal and transverse strength, rigidity and ductility of the composite packaging container. The crystalline regions of the two-phase polymer bridge each other and are closely connected, so that the crystals of the two close the amorphous regions of each other, which greatly improves the gas (oxygen, carbon dioxide, etc.) barrier and moisture barrier properties of the composite packaging container. wet performance.

The multi-layer polymer composite packaging container with nano-layer texture and its processing method provided by the present invention can form multi-layer polymer composite boxes, barrels, cans, bottles, bags, bags, etc. with nano-layer texture on the production line. Boxes and other packaging containers, the process conditions are simple and easy to control, practical and suitable for large-scale industrial production.

4. Description of drawings

Figure 1. Flow chart of the processing method of multi-layer polymer composite packaging container with nano-layer texture

Fig. 2. Flowchart of processing method for multi-layer polymer composite packaging containers (bottles, cans, etc.) with nano-layer texture

Figure 3. Schematic diagram of the structure of the layer multiplier

Figure 4. Schematic diagram of the morphology and structure of the nanolayer texture of the multilayer polymer composite packaging container

5. Specific implementation

The examples given below are specific descriptions of the present invention. It is necessary to point out that the following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the protection scope of the present invention. Those skilled in the art according to the above-mentioned The content of the present invention The non-essential improvements and adjustments made to the present invention still belong to the protection scope of the present invention.

Example 1:

Preparation of multilayer polymer composite packaging barrels with nanolayer texture.

1. Polymer material: The polymer combination is high-density polyethylene/isotactic polypropylene (HDPE/iPP);

2. Melt extrusion: The polymer (HDPE) forming the epiphytic phase (A) and the polymer (iPP) forming the base phase (B) are respectively melted and plasticized by two twin-screw extruders, wherein the extrusion of HDPE The temperature is: 190°C, and the extrusion temperature of iPP is 220°C. The extruded melt melted and plasticized by the extruder enters the micro-layer co-extrusion process;

3. Micro-layer co-extrusion: The melt of HDPE/iPP is synchronously fed into a design with three-layer co-extrusion mold and 4-channel 5-level multiplier superimposed by two extruders with a flow rate ratio of 10:90. In the micro-layer co-extrusion head, the two melt streams are merged in the co-extrusion die to form a three-layer melt tablet, and the extruded melt tablet enters a 5-level multiplier for 5 divisions-overlap- Convergence increases the number of layers of the melt sheet and reduces the thickness of the layers. The material flow is repeatedly divided and overlapped, and the number of layers reaches 2049 layers in the last stage. The temperature of the micro-layer co-extrusion head is 220°C;

4. Composite sheet calendering: the sheet-like material flowing out of the layer multiplier enters the flat-slit sheet die for extrusion to form a multi-layer polymer composite sheet blank in a melt state, which is calendered and cooled by a series of rollers to form Composite panels;

5. Heating treatment of the composite sheet; the composite sheet goes forward into a tunnel-type infrared heating oven, and the heat treatment temperature is 150°C;

6. Thermal stretching of the composite sheet: Stretch the composite sheet heated to 150°C by adjusting the speed ratio of the traction roller to cause stretching deformation, the longitudinal stretch ratio is 10, and the stretched composite sheet is cooled Roll to room temperature.

7. Container molding: Cut a piece of material, heat it to 100°C, place it on the thermoforming mold cavity of the barrel, press the periphery tightly, vacuumize the cavity, and vacuum the plate into a barrel of the desired shape.

The multi-layer polymer composite packaging barrel with nano-layer texture produced by the above-mentioned method of processing high-density polyethylene/isotactic polypropylene (HDPE/iPP) by polymer combination, the lamellae of the base phase polymer of the packaging barrel material The c-axis intersects the lamellar c-axis of the epitaxial phase polymer layer, and the intersection angle is 50 degrees. The cumulative thickness of each layer of isotactic polypropylene (iPP) as the base phase polymer layer is 90% of the total thickness of the composite packaging barrel wall , the cumulative thickness of each layer of the high-density polyethylene (HDPE) layer as the epitaxial phase polymer layer is 10% of the total thickness of the composite packaging barrel wall, and the high-density polyethylene (HDPE) layer as the epitaxial phase polymer layer The monolayer thickness is about 100 nm.

For the HDPE/iPP multi-layer composite packaging drum prepared in Example 1, the wall board of the composite packaging drum was cut out for testing. The longitudinal tensile strength along the extrusion direction of the board can reach 260 MPa, the elongation at break can reach 80%, and the transverse tensile strength can reach 260 MPa. The strength can reach 100MPa, and the elongation at break can reach 25%. The barrier and corrosion resistance of the barrel to hydrocarbon solvents are greatly improved.

Example 2:

Preparation of multilayer polymer composite packaging bags with nanolayer texture.

1. Polymer material: The polymer combination is linear low density polyethylene/isotactic polypropylene (LLDPE/iPP);

2. Melt extrusion: The polymer (LLDPE) forming the epiphytic phase (A) and the polymer (iPP) forming the base phase (B) are respectively melted and plasticized by two twin-screw extruders, wherein the extrusion of LLDPE The temperature is: 160°C, and the extrusion temperature of iPP is 200°C. The extruded melt melted and plasticized by the extruder enters the micro-layer co-extrusion process;

3. Micro-layer co-extrusion: two extruders synchronously feed the LLDPE/iPP melt into a three-layer co-extrusion mold with a flow rate ratio of 40:60. In the micro-layer co-extrusion head, the two melt streams are merged in the co-extrusion die to form a three-layer melt tablet, and the extruded melt tablet enters a 4-stage multiplier for 4 divisions-overlap- Convergence increases the number of layers of the melt sheet and reduces the thickness of the layers. The material flow is repeatedly divided and overlapped, and the number of layers reaches 513 layers in the last stage. The temperature of the micro-layer co-extrusion head is 200°C;

4. Composite film extrusion and blow molding: In the last stage of the layer multiplier, the sheet-like material flow is divided into 2 strands, and enters the 2-layer co-extruded nozzle die for extrusion through 2 feed channels to form a multi-layer in a melt state. Polymer composite tube blank, after the blank leaves the die, it is blown by the compressed air inside the mandrel to form a bubble film, which is cooled by the wind ring, and the number of melt layers in the bubble film is 1025;

5. Reheating treatment: the cooled tubular composite foam film is cut longitudinally to become a flat film through a herringbone plate, rubber roller, and cutting knife, and then moves forward under the traction of the traction roller, and enters a tunnel-type infrared heating oven for heat treatment. The temperature is 130°C;

6. Thermal stretching: adjust the speed ratio of the traction roller to stretch the heat-treated composite film to cause longitudinal stretching deformation, the longitudinal stretching ratio is controlled at 5, and the film thickness is 100 microns.

7. Container forming: the composite film is made into a multi-layer composite packaging bag of the required shape by thermal welding.

The polymer combination is a multi-layer polymer composite packaging bag with a nano-layer texture produced by processing the linear low-density polyethylene/isotactic polypropylene (LLDPE/iPP) by the above method, and the sheet of the base phase polymer of the composite packaging bag material The crystal c-axis crosses the lamellar c-axis of the epiphytic phase polymer layer, and the intersection angle is 50 degrees. The cumulative thickness of each layer of isotactic polypropylene (iPP) as the base phase polymer layer is 60% of the total thickness of the composite packaging bag wall. %, the cumulative thickness of each layer of the linear low-density polyethylene (LLDPE) layer as the epitaxial phase polymer layer is 40% of the total thickness of the bag wall, and the linear low-density polyethylene (LLDPE) as the epitaxial phase polymer layer The monolayer thickness of the layer is about 80 nm.

For the LLDPE/iPP multilayer composite packaging bag prepared in Example 2, the film base material of the composite packaging bag is taken for testing. The longitudinal tensile strength can reach 140MPa, the elongation at break can reach 250%, and the transverse tensile strength can reach more than 80MPa. , The elongation at break can reach 150%. The oxygen transmission rate of the film is 6.5cm ³ /m ² ·24h·0.1MPa, and the water vapor transmission rate is 0.7g/m ² ·24h.

Example 3:

Preparation of multilayer polymer composite packaging bottles with nanolayer texture.

1. Selection of polymer materials: The polymer combination is isotactic polypropylene and polyamide 6 (iPP/PA6);

2. Melt plasticization: using a double-barrel injection molding machine, the polymer isotactic polypropylene (iPP) forming the epiphytic phase (A) and the polymer polyamide 6 (PA6) forming the base phase (B) are respectively injected Melt and plasticize in the two barrels of the machine, where the injection temperature of iPP is 220°C, and the injection temperature of PA6 is 260°C. Driven by the injection screw, it is injected into the subsequent device through the nozzle;

3. Micro-layer co-injection: The melt of iPP/PA6 is plasticized by two barrels respectively, and injected into a three-layer co-injection mixer synchronously with a flow rate ratio of 50:50 to form a three-layer composite molten material slices, and then enter the microlayer co-injection device composed of 5-stage 4-channel and the last stage is 2-channel 1-stage layer multiplier superimposition, repeated division-overlap-convergence, the number of layers in the last stage reaches 4097 layers, and the layer is multiplied The temperature of the device is 260°C;

4. Preform injection molding: The material flow from the layer multiplier enters the preform injection molding mold with one mold and two cavities, and is cooled and shaped into a multi-layer polymer composite preform with 4097 layers in the bottle wall; ;

5. Preform heat treatment and temperature adjustment: Put the cooled and shaped composite preform into a heat treatment oven and heat it to 180°C for heat treatment;

6. Stretch blow molding: put the preform into the blow mold, stretch the heat-treated composite preform longitudinally through the stretch rod, the longitudinal stretch ratio is controlled at 4, and blow compressed air into the preform , so that the preform is blown to produce circumferential stretching deformation, and the circumferential stretching ratio is controlled at 1.5. After inflation, the bottle wall adheres to the inner wall of the mold cavity and is cooled to form a bottle shape with a thickness of 0.4 mm.

Polymer combination isotactic polypropylene and polyamide 6 (iPP/PA6) processed by the above method to produce a multi-layer polymer composite packaging bottle with a nano-layer texture, the base phase polymer crystal platelet of the composite packaging bottle material The c-axis crosses the lamellar c-axis of the ordered crystal of the epiphytic polymer layer, and the intersection angle is 50 degrees. The cumulative thickness of each layer of polyamide 6 (PA6) as the base phase polymer layer is the total thickness of the composite packaging bottle wall. 50% of the total thickness of each layer of isotactic polypropylene (iPP) as the epitaxial phase polymer layer is 50% of the total thickness of the composite packaging bottle wall, and the isotactic polypropylene (iPP) as the epitaxial phase polymer layer ) layer with a single layer thickness of about 100 nm.

For the iPP/PA6 multilayer polymer composite packaging bottle prepared in Example 3, the bottle wall sheet was cut for testing. The longitudinal tensile strength can reach 210MPa, the elongation at break can reach 90%, and the hoop tensile strength can reach 160MPa. The elongation at break can reach 50%. The oxygen transmission rate of the bottle wall sheet is 0.87cm ³ /m ² ·24h·0.1MPa, and the water vapor transmission rate is 0.6g/m ² ·24h.

Claims (10)

1. multilayer polymer compound packaging container with nano-layer texture, it is characterized in that the compound packaging container wall constitutes to being overlapping with the gathering compound layer crystal of growing nonparasitically upon another plant by forming the grow nonparasitically upon another plant substrate gathering compound layer of crystallization interlacing structure of non-parallel chain out-phase, wherein the crystal platelet c axle of substrate gathering compound layer is axial along the container wall, its each layer cumulative thickness is the 50-99% of container wall gross thickness, the crystal platelet c axle of the gathering compound layer of growing nonparasitically upon another plant and container wall axle intersect, its each layer cumulative thickness is the 1-50% of container wall gross thickness, and the thickness in monolayer of the gathering compound layer of growing nonparasitically upon another plant is the 50-300 nanometer.

2. the multilayer polymer compound packaging container with nano-layer texture as claimed in claim 1 is characterized in that saidly can forming non-parallel chain out-phase and growing nonparasitically upon another plant the combination of polymers of substrate gathering compound layer and the gathering compound layer of growing nonparasitically upon another plant of crystallization interlacing structure to for polyethylene and polypropylene or polypropylene and polyamide.

3. the multilayer polymer compound packaging container with nano-layer texture as claimed in claim 2, it is characterized in that said polyethylene is selected from low density polyethylene (LDPE), linear low density polyethylene, medium density polyethylene, high density polyethylene (HDPE), polypropylene is selected from isotactic polypropylene and syndiotactic polypropylene, and polyamide is selected from polyamide 6, polyamide 66, polyamide 11, polyamide 12.

4. about the described job operation of claim 1 to 3, it is characterized in that comprising following processing step with multilayer polymer compound packaging container of nano-layer texture:

(1), melt extrudes: the substrate gathering compound and the gathering compound of growing nonparasitically upon another plant of selected combination of polymers centering are inserted different extruders respectively be heated to molten condition and plastify and extrude;

(2), microbedding co-extrusion: two bursts of flow of melt that form substrate gathering compound layer and the gathering compound layer of growing nonparasitically upon another plant respectively of extruding by extruder with predetermined flow rate than quantitatively delivering into the layering co-extrusion touches tool synchronously, form layering composite molten tablet, enter a layer multiplicator again to cut apart repeatedly-overlapping-converge, make the number of plies increase the bed thickness attenuation;

(3), complex film, composite sheet, composite board extrude, calendering formation: the sheet materials flow of being flowed out by layer multiplicator enters flush joint formula sheet, plate mouth mould is extruded, form the multiple layer polymer composite sheet of melt state, the blank of plate, through calendering, cooling formation complex film, sheet, the plate of a series of rollers;

(4), furnace run again: complex film, sheet, the plate of cooling and shaping are carried out furnace run again, its temperature is risen to grow nonparasitically upon another plant between gathering compound melting temperature and the substrate gathering compound melting temperature, perhaps be lower than the melting temperature of the gathering compound of growing nonparasitically upon another plant;

(5), hot-stretch: the complex film after the heat treatment, sheet, plate are stretched, make it produce tensile deformation, and make it reach design-calculated physical dimension and thickness.

(6), container formation: tensile deformation is made the packing container of required shape by thermal welding, Heat forming, method such as bonding to the complex film that designs physical dimension and thickness, composite sheet, composite board.

5. about the described job operation of claim 1 to 3, it is characterized in that comprising following processing step with multilayer polymer compound packaging container of nano-layer texture:

(1), melt extrudes: the substrate gathering compound of selected combination of polymers centering is inserted different extruders respectively with the gathering compound of growing nonparasitically upon another plant, be heated to the molten condition plasticizing and extrude;

(2), microbedding co-extrusion: the two bursts of flow of melt that form substrate gathering compound layer and the gathering compound layer of growing nonparasitically upon another plant respectively that go out by squeeze note machine squeeze note with predetermined flow rate than quantitatively delivering into the layering co-extrusion touches tool synchronously, form layering composite molten tablet, enter a layer multiplicator again to cut apart repeatedly-overlapping-converge, make the number of plies increase the bed thickness attenuation;

(3), complex film extrude, blowing: the sheet materials flow of being flowed out by layer multiplicator is divided at least 2 strands, entering the mouth of pipe mould that is at least 2 layers of co-extrusion via at least 2 feeding-passages extrudes, form the multiple layer polymer composite pipe blank of melt state, after pipe leaves mouthful mould, formed the tubulose vacuolar membrane by the inner pressurized air inflation that feeds, cool off by vane;

(4), furnace run again: the composite tube vacuolar membrane of cooling longitudinally cut becomes flat film, carry out furnace run again, its temperature is risen to grow nonparasitically upon another plant between gathering compound melting temperature and the substrate gathering compound melting temperature, perhaps be lower than the melting temperature of the gathering compound of growing nonparasitically upon another plant;

(5), hot-stretch: the complex film of the speed ratio by adjusting nip rolls after to heat treatment stretches, and makes it produce tensile deformation, and makes it reach design-calculated physical dimension and thickness, and the longitudinal stretching ratio is controlled at 1.5～30.

(6), container formation: tensile deformation to the multilayer complex films that designs physical dimension and thickness is made required shapes of containers by thermal welding, Heat forming, method such as bonding.

6. about the described job operation of claim 1 to 3, it is characterized in that comprising following processing step with multilayer polymer compound packaging container of nano-layer texture:

(1), fusion plastification: the substrate gathering compound and the gathering compound of growing nonparasitically upon another plant of selected combination of polymers centering are inserted respectively in two barrels of double cartridge injector, be heated to the molten condition plasticizing, under the promotion of injection member, be injected into into microbedding through the injector nozzle and annotate operation altogether;

(2), microbedding is injected altogether: two bursts of flow of melt that form substrate gathering compound layer and the gathering compound layer of growing nonparasitically upon another plant respectively enter layering with predetermined flow rate than synchronous calibrated shot and inject blender altogether, form layering composite molten tablet, enter a layer multiplicator again to cut apart repeatedly-overlapping-converge, make the number of plies increase the bed thickness attenuation;

(3), container parison injection moulding: the materials flow injection of being flowed out by layer multiplicator enters in the container parison injecting molding die that is at least a mould one chamber, and the typing that is cooled becomes multiple layer polymer clad vessel parison;

(4), container parison heat treatment temperature adjustment: the clad vessel parison of cooling and shaping is carried out furnace run again, its temperature is risen to grow nonparasitically upon another plant between gathering compound melting temperature and the substrate gathering compound melting temperature, perhaps be lower than the melting temperature of the gathering compound of growing nonparasitically upon another plant;

(5), stretch-blow: the container parison is inserted in the blow mold, carry out longitudinal stretching and make the container preform blowup by the clad vessel parison of stretch after to the inner injecting compressed air of container parison to heat treatment, produce biaxial stretch-formed distortion, the circumferential tension ratio is 1.1～4, the longitudinal stretching ratio is 1.5～10, and to be adjacent to the wall of die cavity cooling forming be needed container shapes to wall of container behind the inflation.

7. as claim 4 or 5 or 6 described job operations with multilayer polymer compound packaging container of nano-layer texture, it is characterized in that being lower than when growing nonparasitically upon another plant gathering compound melting temperature when complex film, sheet material, sheet material furnace run and draft temperature, also complex film, sheet material, the sheet material after stretching must be heated again, its temperature is risen to be higher than the temperature of growing nonparasitically upon another plant gathering compound fusing point and being lower than substrate gathering compound fusing point to be heat-treated.

8. as claim 4 or 5 or 6 described job operations with multilayer polymer compound packaging container of nano-layer texture, the flow rate mode that it is characterized in that two kinds of poly-mer flow of melt is that extruder, the conveying of injector direct quantitative or extruder and Melt Pump coupling are quantitatively carried.

9. as claim 4 or 5 or 6 described job operations with multilayer polymer compound packaging container of nano-layer texture, it is characterized in that the injection mold tool of said layering co-extrusion/altogether is three-layer co-extruded/injection mold tool altogether, in the injection mold tool of co-extrusion/altogether, the substrate gathering compound and the two bursts of flow of melt of gathering compound of growing nonparasitically upon another plant are converged and formed three-decker fusion tablet.

10. the job operation with multilayer polymer compound packaging container of nano-layer texture as claimed in claim 6 is characterized in that the injection molding parison mould of compound packaging container, is selected from normal injection forming mould and hot runner injection molding mould.

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