阅读说明：本技术 一种聚烯烃膜、包含其的全塑复合膜及其制备方法和应用 (Polyolefin film, full-plastic composite film containing polyolefin film, and preparation method and application of full-plastic composite film ) 是由 朱兴 马申 于 2020-03-27 设计创作，主要内容包括：本发明提供一种聚烯烃膜、包含其的全塑复合膜及其制备方法和应用。所述聚烯烃膜包括依次层叠的电晕层、中间层和热封层；所述热封层包括质量分数为10-30％的茂金属线性低密度聚乙烯和70-90％的环烯烃共聚物。所述全塑复合膜包括依次层叠的印刷层、阻光层和聚烯烃膜层。通过对聚烯烃膜热封层及其结构的合理改造,所述聚烯烃膜对液体药剂的吸附量较低,利用其制备得到的全塑复合膜体积小,质量轻,能够保障药品的有效性,同时能够达到阻光性等高阻隔性的要求。(The invention provides a polyolefin film, a full-plastic composite film containing the same, and a preparation method and application thereof. The polyolefin film comprises a corona layer, a middle layer and a heat sealing layer which are sequentially laminated; the heat sealing layer comprises 10-30% of metallocene linear low density polyethylene and 70-90% of cyclic olefin copolymer by mass. The all-plastic composite film comprises a printing layer, a light-blocking layer and a polyolefin film layer which are sequentially stacked. Through reasonable transformation of the polyolefin film heat seal layer and the structure thereof, the polyolefin film has low adsorption capacity to liquid medicaments, and the all-plastic composite film prepared by the polyolefin film has small volume and light weight, can ensure the effectiveness of medicaments, and can meet the requirements of high barrier property such as light resistance and the like.)

1. The polyolefin film is characterized by comprising a corona layer, an intermediate layer and a heat sealing layer which are sequentially laminated;

wherein the heat-sealing layer comprises 10-30% of metallocene linear low-density polyethylene and 70-90% of cyclic olefin copolymer by mass percent, based on 100% of the mass of the heat-sealing layer.

2. The polyolefin film according to claim 1, wherein the corona layer of the polyolefin film comprises a mass fraction of 10-30% of low density polyethylene and 70-90% of linear low density polyethylene, based on 100% by mass of the corona layer;

preferably, the intermediate layer comprises 20 to 40 mass% of low density polyethylene and 60 to 80 mass% of metallocene linear low density polyethylene, based on 100 mass% of the intermediate layer.

3. The polyolefin film according to claim 1 or 2, wherein the ratio of the thicknesses of the corona layer, the intermediate layer and the heat-seal layer is (10-50): (10-50);

preferably, the polyolefin film has a thickness of 30 to 150 μm.

4. The polyolefin film of any of claims 1-3, wherein the cyclic olefin copolymer is an amorphous copolymer of ethylene and a cyclic olefin comprising any one or a combination of at least two of cyclopropene, cyclobutene, cyclopentene, cycloheptene, bicycloheptene, or cyclohexene;

preferably, the weight average molecular weight of the cycloolefin copolymer is 10 to 50 ten thousand;

preferably, the metallocene linear low density polyethylene has a weight average molecular weight of 10 to 15 ten thousand;

preferably, the metallocene linear low density polyethylene has a melt mass flow rate of 0.50 to 2.0g/10min and a density of 0.902 to 0.927g/cm³。

5. A method for preparing a polyolefin film according to any of claims 1 to 4, comprising:

and extruding the corona layer, the middle layer and the heat-sealing layer in a melting co-extrusion mode, and then performing blow molding to form the polyolefin film.

6. The method of claim 5, wherein the melt extrusion temperature is: the corona layer is 170-190 ℃, the middle layer is 170-190 ℃, and the heat sealing layer is 170-200 ℃;

preferably, the equipment used for blow molding is a three-layer co-extrusion blow molding machine;

preferably, the screw rotation speed of the three-layer co-extrusion blow molding machine is as follows: 50-130r/min of corona layer, 40-120r/min of middle layer and 60-140r/min of heat sealing layer.

7. An all-plastic composite film comprising a printed layer, a light-blocking layer and a polyolefin film layer formed of the polyolefin film as claimed in any one of claims 1 to 4, which are laminated in this order.

8. The all-plastic composite film according to claim 7, wherein said print layer comprises a silica or alumina coated PET layer;

preferably, the thickness of the printing layer is 10-30 μm;

preferably, the light-blocking layer is a white PET layer;

preferably, the thickness of the light-blocking layer is 15-50 μm;

preferably, the printing layer, the light-blocking layer and the polyolefin film layer of the all-plastic composite film are connected by adopting aliphatic glue.

9. A method for preparing an all-plastic composite film according to claim 7 or 8, comprising the steps of:

and compounding the printing layer, the light-blocking layer and the polyolefin film layer of the all-plastic composite film in sequence by using an extrusion compounding machine, a dry compounding machine or a solvent-free compounding machine to form the all-plastic composite film.

10. Use of a polyolefin film according to any one of claims 1 to 4 or an all plastic composite film according to claim 7 or 8 for the preparation of a liquid medical flexible packaging material.

Technical Field

The invention belongs to the field of food and medicine packaging materials, and particularly relates to a polyolefin film, an all-plastic composite film containing the polyolefin film, a preparation method and an application of the all-plastic composite film, and particularly relates to the polyolefin film for liquid medicine flexible packaging, the all-plastic composite film containing the polyolefin film, the preparation method and the application of the all-plastic composite film.

Background

The medicine packaging material refers to a packaging material and a container which are in direct contact with medicines, and mainly includes containers such as bottles, bags, inner stoppers and the like made of various materials, and substances such as fillers, liners and the like which are in contact with medicines. Because the medicine packaging material is accompanied with the whole process of production, circulation and use of the medicine, the material composition, the formula, the production process and other factors of the medicine packaging material become potential factors influencing the medicine quality, possibly have certain influence on the health of human bodies, and can also cause serious medical hazard.

At present, materials used for pharmaceutical packaging include glass, ceramics, metals, synthetic polymer materials, and the like. Most of liquid medicine oral liquid products are formed and packaged by glass bottles or PET hard sheets, have large volume and heavy weight, and are not favorable for transportation, carrying and environmental protection. The application range of synthetic polymer materials (such as polyethylene, polypropylene, polyvinyl chloride, polyester, polystyrene, etc.) in the pharmaceutical packaging industry is gradually expanded due to the advantages of light weight, easy processing, low cost, etc. With the rapid development of the pharmaceutical packaging industry, flexible plastic packages have become the leading products in the pharmaceutical packaging field with a great development space, wherein the heat-sealing layer of the flexible packages is mainly composed of polyolefin (such as polyethylene, polypropylene, etc.).

CN110317388A discloses a packaging material directly contacting with a medicine, which is prepared from low-density polyethylene and metallocene polyethylene, wherein the mass ratio of the low-density polyethylene to the metallocene polyethylene is 3: 0.2-2; the density of the low-density polyethylene is 0.925-0.930g/cm³The melt flow rate is 0.29-0.31g/10 min; the density of the metallocene polyethylene is 0.915-0.920g/cm³The melt flow rate is 0.4-1.0g/10min, no other auxiliary agent is needed to be added, and the migration quantity is low. Wherein the low density polyethylene is a common packaging material which is directly contacted with the medicine at present, and is mainly applied to packaging films, composite film inner layer composition materials and eye dropsA bottle and an infusion bottle, but low-density polyethylene has poor barrier properties against water, organic solvents, volatile substances, and the like.

CN206782377U discloses a high heat-seal prevents outer liquid packaging bag that leaks, including outside protective layer, the supporting layer, leak protection layer and inside heat-seal layer, outside protective layer includes the PET layer, the supporting layer is the aluminium foil layer, leak protection layer uses linear low density polyethylene material to make, inside heat-seal layer uses ethylene-vinyl acetate copolymer material to make, improve the structure of current wrapping bag, the aluminium foil layer uses PET layer centre gripping, prevent that the aluminium foil layer from being corroded, the inlayer uses the EVA material to make, the heat sealability of liquid packaging bag has been improved, effectively prevent to seal the emergence of not firm phenomenon. However, some components in the medicinal liquid, such as camphor oil, menthol, methyl salicylate and other volatile substances, have strong adsorbability and do not meet the requirement of the quality guarantee period of the medicine.

As a packaging material of a direct contact medicine, particularly when the medicine is a liquid preparation or a semi-solid preparation, the quality of the medicine is affected due to high migration volume, so that impurities in the medicine exceed the standard, and the compatibility requirement of the medicine on the packaging material cannot be met.

Therefore, it is an urgent problem to be solved in the art to provide a flexible packaging material with low adsorption capacity to liquid pharmaceutical preparations, small volume and light weight, which can ensure the effectiveness of liquid medicines.

Disclosure of Invention

In view of the problems in the prior art, the invention aims to provide a polyolefin film, an all-plastic composite film comprising the polyolefin film, and a preparation method and application of the all-plastic composite film. The polyolefin film can meet the requirement of light packaging weight, and can ensure the effectiveness of medicaments in the quality guarantee period of contents, and the all-plastic composite film prepared from the polyolefin film is convenient to recycle and more environment-friendly.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a polyolefin film, which comprises a corona layer, an intermediate layer and a heat-sealing layer which are sequentially laminated, wherein the heat-sealing layer comprises 10-30% by mass of metallocene linear low density polyethylene (m LL DPE) and 70-90% by mass of Cyclic Olefin Copolymer (COC) based on 100% by mass of the heat-sealing layer.

The heat-sealing layer of the polyolefin film comprises m LL DPE and COC, wherein m LL DPE and COC play a role in blocking, the adsorption effect of the material on the coated liquid is reduced, the heat-sealing performance of the material and the connection strength of the material and the middle layer can be improved, meanwhile, the heat-sealing layer is matched with the corona layer and the middle layer, the connection strength of all layers of the obtained polyolefin film is good, and the processing is convenient.

In the present invention, the mass fraction of the metallocene linear low density polyethylene in the heat-seal layer is 10 to 30%, and may be, for example, 10%, 12%, 14%, 15%, 16%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, or the like; the mass fraction of the cycloolefin copolymer is 70 to 90%, and may be, for example, 70%, 72%, 74%, 75%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, or the like; in which, if the content of COC exceeds 90%, although the chemical resistance is improved, the heat sealability is lowered, resulting in lower heat sealability than the standard. Therefore, the mass fraction of the metallocene linear low density polyethylene in the heat seal layer is preferably 15 to 25%, and the mass fraction of the cycloolefin copolymer is preferably 75 to 85%.

In a preferred embodiment of the present invention, the corona layer of the polyolefin film comprises 10 to 30 mass% of low density polyethylene (L DPE) and 70 to 90 mass% of linear low density polyethylene (LL DPE) based on 100 mass% of the corona layer, and L DPE and LL DPE are adopted to facilitate processing of the corona layer, LL DPE and L DPE belong to the same density range, but the molecular structure of the two is different, and the melt rheology behavior is different, so the physical basic properties and the molding processing characteristics of the two are different.

In the present invention, the mass fraction of the low-density polyethylene in the corona layer is 10-30%, for example, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, or 30%; the linear low density polyethylene may be 70 to 90% by mass, for example, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90% or the like.

Preferably, the intermediate layer comprises 20-40% by mass of low density polyethylene and 60-80% by mass of metallocene linear low density polyethylene based on 100% by mass of the intermediate layer, the intermediate layer is added with a cycloolefin copolymer such as m LL DPE connected with the heat seal layer, and the effect of strengthening the binding force between the corona layer and the heat seal layer is achieved, and the effect of improving the processability is achieved through L DPE.

In the present invention, the mass fraction of the low-density polyethylene in the intermediate layer is 20 to 40%, and the mass fraction of the metal linear low-density polyethylene such as 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, or 40% may be 60 to 80%, and the mass fraction may be 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, or 80%, for example.

As a preferable technical scheme of the invention, the thickness ratio of the corona layer, the middle layer and the heat sealing layer is (10-50): (10-50); for example, 10:10:10, 10:15:10, 10:20:10, 10:25:10, 10:30:10, 10:35:10, 10:40:10, 10:45:10, 10:50:10, 10:10:15, 10:10:20, 10:10:25, 10:10:30, 10:10:35, 10:10:40, 10:10:45, 10:10:50, 15:10:10, 20:10:10, 25:10:10, 30:10:10, 35:10:10, 40:10:10, 45:10:10, 50:10:10, 20:20:30, or 50:10:50, etc.

Preferably, the polyolefin film has a thickness of 30 to 150. mu.m, and may be, for example, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, or the like.

As a preferred technical scheme of the invention, the cycloolefin copolymer is an amorphous copolymer of ethylene and cycloolefin, and the cycloolefin comprises any one or a combination of at least two of cyclopropene, cyclobutene, cyclopentene, cycloheptene, bicycloheptene or cyclohexene.

Preferably, the weight average molecular weight of the cycloolefin copolymer is 10 to 50 ten thousand, and may be, for example, 10 ten thousand, 12 ten thousand, 15 ten thousand, 20 ten thousand, 22 ten thousand, 25 ten thousand, 28 ten thousand, 30 ten thousand, 32 ten thousand, 35 ten thousand, 38 ten thousand, 40 ten thousand, 42 ten thousand, 45 ten thousand, 48 ten thousand, or 50 ten thousand, or the like.

Preferably, the weight average molecular weight of the metallocene linear low density polyethylene is 10 to 15 ten thousand, for example, 10 ten thousand, 10.2 ten thousand, 10.5 ten thousand, 11 ten thousand, 11.5 ten thousand, 12 ten thousand, 12.5 ten thousand, 13 ten thousand, 13.5 ten thousand, 14 ten thousand, 14.5 ten thousand, or 15 ten thousand, etc.

Preferably, the metallocene linear low density polyethylene melt mass flow rate is 0.50-2.0g/10min, such as 0.5g/10min, 0.8g/10min, 1g/10min, 1.2g/10min, 1.5g/10min, 1.8g/10min or 2.0g/10 min; the density is 0.902-0.927g/cm³For example, it may be 0.902g/cm³、0.905g/cm³、0.908g/cm³、0.910g/cm³、0.912g/cm³、0.915g/cm³、0.920g/cm³、0.922g/cm³、0.925g/cm³Or 0.927g/cm³And the like.

In a second aspect, the present invention provides a production method using the polyolefin film according to the first aspect, the production method comprising:

and extruding the corona layer, the middle layer and the heat-sealing layer in a melting co-extrusion mode, and then performing blow molding to form the polyolefin film.

As a preferred technical solution of the present invention, the melt extrusion temperature is: the corona layer 170 ℃. 190 ℃ may be 170 ℃, 175 ℃, 178 ℃, 180 ℃, 182 ℃, 185 ℃ or 190 ℃ for example; the intermediate layer 170 ℃ 190 ℃ may be, for example, 170 ℃, 175 ℃, 178 ℃, 180 ℃, 182 ℃, 185 ℃, 190 ℃ or the like; the heat-sealing layer 170-200 ℃ may be, for example, 170 ℃, 175 ℃, 178 ℃, 180 ℃, 182 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃.

Preferably, the equipment used for blow molding is a three-layer co-extrusion blow molding machine.

Preferably, the screw rotation speed of the three-layer co-extrusion blow molding machine is as follows: the corona layer is 50-130r/min, such as 50r/min, 60r/min, 70r/min, 80r/min, 90r/min, 100r/min, 110r/min, 120r/min or 130 r/min; the intermediate layer is 40-120r/min, such as 40r/min, 50r/min, 60r/min, 70r/min, 80r/min, 90r/min, 100r/min, 110r/min or 120 r/min; the heat-seal layer is 60 to 140r/min, and may be, for example, 60r/min, 70r/min, 80r/min, 90r/min, 100r/min, 110r/min, 120r/min, 130r/min or 140 r/min.

In a third aspect, the present invention provides an all-plastic composite film, comprising a printing layer, a light-blocking layer and the polyolefin film layer formed by the polyolefin film of the first aspect, which are sequentially stacked.

In a preferred embodiment of the present invention, the printing layer includes a PET (polyethylene terephthalate) layer plated with silicon oxide or aluminum oxide.

Preferably, the thickness of the printed layer is 10-30 μm, and may be, for example, 10 μm, 12 μm, 14 μm, 15 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 26 μm, 28 μm, 30 μm, or the like.

Preferably, the light-blocking layer is a white PET layer.

Preferably, the thickness of the light-blocking layer is 15-50 μm, and may be, for example, 15 μm, 16 μm, 18 μm, 20 μm, 22 μm, 25 μm, 30 μm, 35 μm, 38 μm, 40 μm, 42 μm, 44 μm, 45 μm, or 50 μm, etc.

Preferably, the printing layer, the light-blocking layer and the polyolefin film layer of the all-plastic composite film are connected by adopting aliphatic glue, and compared with glue of aromatic hydrocarbon, the adsorbability of the composite film can be reduced by using the aliphatic glue.

In a fourth aspect, a method for preparing the all-plastic composite film according to the third aspect comprises the following steps: and compounding the printing layer, the light-blocking layer and the polyolefin film layer of the all-plastic composite film in sequence by using an extrusion compounding machine, a dry compounding machine or a solvent-free compounding machine to form the all-plastic composite film.

In a fifth aspect, the present invention further provides a use of the polyolefin film of the first aspect or the all-plastic composite film of the third aspect in the preparation of liquid medical flexible packaging material.

The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.

Compared with the prior art, the invention has at least the following beneficial effects:

(1) the polyolefin film provided by the invention has the advantages that through reasonable modification design of the heat sealing layer, the adsorption capacity of the polyolefin film to liquid medicaments is lower, meanwhile, the composition of each layer of the polyolefin film is adjusted, and the obtained polyolefin film is easy to process and has better connection performance by matching with the corona layer and the middle layer, and can meet the requirements of high barrier property such as light resistance, heat resistance and the like;

(2) the all-plastic composite film prepared by the polyolefin film can be used as a flexible packaging material of liquid medicine, can meet the requirement of light packaging, can ensure the effectiveness of contents, meets the requirement regulations of food and medicine, and has the absorption capacity of 0.11-0.33 mu g of camphor oil when tested at 25 ℃ for 2 weeks; the absorption amount of menthol is 0.14-0.28 μ g; the absorption amount of methyl salicylate is 105-185 mu g; the all-plastic composite film prepared from the polyolefin film has good peel strength and heat seal strength, wherein the peel strength is 2.7-3.6N/15mm, and the heat seal strength is 13.0-44.1N/15mm.

Drawings

Fig. 1 is a schematic cross-sectional structure diagram of the polyolefin film provided in example 1.

Fig. 2 is a schematic cross-sectional structure diagram of an all-plastic composite film provided in application example 1.

Wherein 11 is a corona layer, 12 is an intermediate layer, and 13 is a heat sealing layer; 1 is a polyolefin film layer, 2 is a light-blocking layer, and 3 is a printing layer.

Detailed Description

The technical solutions of the present invention are further described in the following embodiments with reference to the drawings, but the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.

In the following examples, the manufacturers and designations of the materials used are shown in Table 1 below:

TABLE 1