Blocking medicine bottle and preparation method thereof

Abstract

The invention relates to the technical field of blocking medicine bottles, and particularly discloses a blocking medicine bottle and a preparation method thereof, aiming at the problems that the upper limit of the blocking performance of the existing blocking medicine bottle is low and the blocking performance is difficult to break through due to the fact that the blocking performance of the existing blocking medicine bottle is mostly realized through structural design. A bottle body of the blocking medicine bottle comprises an inner layer, a secondary inner layer, a middle layer, a secondary outer layer and an outer layer which are sequentially arranged in a covering mode. The inner layer comprises polyethylene; the secondary inner layer comprises an ethylene-methyl acrylate copolymer; the middle layer comprises an ethylene-vinyl alcohol copolymer, cyclic polyolefin and modified montmorillonite; the secondary outer layer comprises an ethylene-methyl acrylate copolymer; the outer layer comprises polyethylene, cyclic polyolefin and modified montmorillonite. The barrier medicine bottle is formed by compositing five layers of materials, the oxygen and water transmittance is low, the barrier property is high, and the barrier medicine bottle has great application value in packaging of medicine or food and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of barrier medicine bottles, and in particular to a barrier medicine bottle and a preparation method thereof. Background Art

[0002] Barrier medicine bottles refer to medicine bottles with good barrier properties to oxygen, carbon dioxide, nitrogen and water vapor, and are mostly achieved through special structural design to prevent drugs from being accidentally ingested or contaminated. At present, the barrier medicine bottles with good barrier effects are mainly made of ethylene-vinyl alcohol copolymer (EVOH) as the main material. Ethylene-vinyl alcohol copolymer can block gases and has good thermal stability. It can maintain product quality and improve product shelf life. It is widely used in food, cosmetics, medicine and other packaging fields.

[0003] For example, the patent with publication number CN112812419A provides a high-barrier pesticide bottle and a preparation method thereof. The high-barrier pesticide bottle includes a barrier layer, an adhesive layer and a PE base layer from the inside to the outside. The barrier layer is made of raw materials containing the following parts by weight: ethylene-vinyl alcohol copolymer: 20 to 30 parts; maleic anhydride grafted polyethylene: 10 to 16 parts. The high-barrier pesticide bottle has excellent barrier effect on oily solvents and has high impact resistance, making it not easy to break.

[0004] However, the barrier function of the existing EVOH barrier medicine bottles such as the above-mentioned ones drops sharply under high humidity conditions, resulting in the barrier performance of the barrier medicine bottles finally prepared being limited, making it difficult to meet the use requirements of high-performance barrier medicine bottles. Summary of the invention

[0005] The purpose of the present invention is to solve the problem that the existing barrier medicine bottles mostly achieve barrier properties through structural design, which results in a low upper limit of the barrier performance and is difficult to break through.

[0006] The present invention is achieved through the following technical solutions:

[0007] The present invention provides a barrier medicine bottle. Along the direction from the inside of the bottle to the outside of the bottle, the bottle body of the barrier medicine bottle includes an inner layer, a sub-inner layer, a middle layer, a sub-outer layer and an outer layer which are covered in sequence; and the inner layer includes polyethylene; the sub-inner layer includes ethylene-methyl acrylate copolymer; the middle layer includes ethylene-vinyl alcohol copolymer, cyclic polyolefin and modified montmorillonite; the sub-outer layer includes ethylene-methyl acrylate copolymer; and the outer layer includes polyethylene, cyclic polyolefin and modified montmorillonite.

[0008] Preferably, the middle layer comprises 75-88 parts by mass of ethylene-vinyl alcohol copolymer, 10-20 parts by mass of cyclic polyolefin and 3-5 parts by mass of modified montmorillonite.

[0009] Preferably, the outer layer comprises, by weight, 75-88 parts by weight of polyethylene, 10-20 parts by weight of cyclic polyolefin and 3-5 parts by weight of modified montmorillonite.

[0010] Preferably, the preparation method of the modified montmorillonite comprises the following steps: first dispersing the montmorillonite in a mixed solvent of ethanol and water, adding a silane coupling agent, heating to 60-80°C, reacting for 1-3h, and then separating and drying the reaction product, and sieving it through 1250-1500 mesh to obtain the modified montmorillonite.

[0011] Preferably, the melt index of polyethylene is 0.5-2.5 g / 10 min, the melt index of ethylene-vinyl alcohol copolymer is 1-4 g / 10 min, the melt index of cyclic polyolefin is 2-8 g / 10 min, and the melt index of ethylene-methyl acrylate copolymer is 2-4 g / 10 min.

[0012] The present invention also proposes a method for preparing the barrier medicine bottle, comprising the following steps:

[0013] S1: taking ethylene-vinyl alcohol copolymer, cyclic polyolefin and modified montmorillonite, blending and granulating to obtain a middle-layer masterbatch;

[0014] S2: polyethylene, cyclic polyolefin and modified montmorillonite are mixed and pelletized to obtain an outer layer masterbatch;

[0015] S3: High-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, middle layer masterbatch, ethylene-methyl acrylate copolymer masterbatch, and outer layer masterbatch are sequentially put into a five-layer co-extrusion blow molding machine layer by layer to perform five-layer co-extrusion blow molding to obtain the barrier medicine bottle.

[0016] Among them, the five-layer co-extrusion blow molding machine includes a feeding die head, a mold, a trimming mechanism and a conveyor belt. The feeding die head includes five layers of extrusion feeding mechanisms, namely an outer layer extruder, a sub-outer layer extruder, a middle layer extruder, a sub-inner layer extruder and an inner layer extruder stacked in sequence. It can extrude and blow five layers of composite bottle body materials at the same time, with high production efficiency and stable composite effect.

[0017] Preferably, in step S3, when five-layer co-extrusion blow molding is performed, the die head temperature is controlled to be 190-230°C.

[0018] Furthermore, the extrusion temperature of the inner layer is 190-220°C, the extrusion temperature of the sub-inner layer is 180-210°C, the extrusion temperature of the middle layer is 220-240°C, the extrusion temperature of the sub-outer layer is 180-210°C, and the extrusion temperature of the outer layer is 190-220°C.

[0019] Preferably, the total wall thickness of the barrier medicine bottle is 0.9-1.1 mm.

[0020] Furthermore, the thickness of the inner layer is 0.2-0.3 mm, the thickness of the sub-inner layer is 0.1-0.15 mm, the thickness of the middle layer is 0.2-0.3 mm, the thickness of the sub-outer layer is 0.1-0.15 mm, and the thickness of the outer layer is 0.3-0.4 mm.

[0021] The barrier medicine bottle of the present invention is suitable for use in the fields of medicine, food, etc. as packaging equipment, etc.

[0022] The technical solution of the present invention has the following beneficial effects:

[0023] The barrier medicine bottle body of the present invention adopts a composite material and has good barrier properties. Specifically, the inner layer is made of high-density polyethylene, which has good water vapor resistance and is non-hygroscopic, and has stable physical and chemical properties, which can avoid the release of organic components during use and affect the composition effects of medicines or foods; a composite material mainly composed of ethylene-vinyl alcohol copolymer is arranged in the bottle body, and cycloolefin polymer (COP) and montmorillonite are introduced. The molecular structure of COP contains a hard non-polar ring structure, which can give the material an extremely low moisture absorption rate, and montmorillonite has a special lamellar structure, which can effectively improve the barrier properties of the polymer by blending and intercalating with the polymer; the processability of the ethylene polymer and the barrier effect of the vinyl alcohol polymer are combined, which not only shows excellent processing properties, but also presents an excellent blocking effect on gases, odors, solvents, etc., thereby making the middle layer have a good barrier effect; and a secondary outer layer material of ethylene-methyl acrylate copolymer is arranged between the middle layer and the outer layer. By utilizing its good compatibility with polar materials and non-polar materials, the bonding strength between the inner layer and the middle layer and between the middle layer and the outer layer can be significantly improved, so as to improve the composite effect and stability between the multilayer materials.

[0024] The barrier medicine bottle of the present invention is prepared by a five-layer co-extrusion blow molding machine, which can simultaneously extrude and blow five layers of composite bottle materials, has high production efficiency, good composite effect between multi-layer materials, and the oxygen permeability of the prepared barrier medicine bottle is about 0.1-0.3cm 3 / (pkg.24h), the water vapor transmission rate is about 0.0045-0.0085g / (pkg.24h), and the barrier performance is strong. It can fill the gap of the current high-performance barrier medicine bottle and provide great application value for the packaging materials of medicine and food. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic diagram of the hierarchical structure of the barrier medicine bottle in the present invention;

[0026] Figure 2 It is a schematic diagram of the structural flow of the five-layer co-extrusion blow molding machine in the present invention. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. Where specific conditions are not specified in the embodiments, they are carried out under conventional conditions or conditions recommended by the manufacturer; where the manufacturers of the instruments, equipment, reagents and raw materials used are not specified, they are all conventional products that can be purchased commercially.

[0028] The present invention provides a barrier medicine bottle, which includes an inner layer, a sub-inner layer, a middle layer, a sub-outer layer and an outer layer sequentially covered along the direction from the inside of the bottle to the outside of the bottle; and the total wall thickness of the barrier medicine bottle is 0.9-1.1mm, wherein the inner layer thickness is 0.2-0.3mm, the sub-inner layer thickness is 0.1-0.15mm, the middle layer thickness is 0.2-0.3mm, the sub-outer layer thickness is 0.1-0.15mm, and the outer layer thickness is 0.3-0.4mm. The thickness of the barrier medicine bottle body and its various material layers can be regulated by preparation methods such as extruder frequency and traction speed.

[0029] The inner layer material includes high-density polyethylene, with a density of about 0.95-0.96 g / cm 3 , and the melt index of high-density polyethylene is 0.5-2.5g / 10min;

[0030] The secondary inner layer material includes ethylene-methyl acrylate copolymer;

[0031] The middle layer material comprises a blend of ethylene-vinyl alcohol copolymer, cyclic polyolefin and modified montmorillonite, and comprises 75-88 parts by weight of ethylene-vinyl alcohol copolymer, 10-20 parts by weight of cyclic polyolefin and 3-5 parts by weight of modified montmorillonite, wherein the melt index of the ethylene-vinyl alcohol copolymer is 1-4 g / 10 min, the melt index of the cyclic polyolefin is 2-8 g / 10 min, and the montmorillonite is sieved through 1250-1500 mesh;

[0032] The secondary outer layer material includes ethylene-methyl acrylate copolymer, the melt index of ethylene-methyl acrylate copolymer is 2-4g / 10min, and ethylene-methyl acrylate can provide good compatibility between the middle layer and the outer layer, and between the middle layer and the inner layer;

[0033] The outer layer material comprises a blend of high-density polyethylene, cyclic polyolefin and modified montmorillonite, and comprises 75-88 parts by mass of high-density polyethylene, 10-20 parts by mass of cyclic polyolefin and 3-5 parts by mass of modified montmorillonite.

[0034] In the present invention, the method for preparing the barrier medicine bottle comprises the following steps:

[0035] (1) Dispersing montmorillonite in a mixed solvent of ethanol and water, adding a silane coupling agent, heating to 60-80° C., reacting for 1-3 hours, and then separating and drying the reaction product to obtain modified montmorillonite.

[0036] (2) Ethylene-vinyl alcohol copolymer, cyclic polyolefin and modified montmorillonite are taken in proportions by mass, put into a high-speed mixer for mixing, and then pelletized by a twin-screw extruder to obtain a middle-layer masterbatch.

[0037] (3) According to the mass proportions, high-density polyethylene, cyclic polyolefin and modified montmorillonite are put into a high-speed mixer for mixing, and then pelletized by a twin-screw extruder to obtain outer layer masterbatch.

[0038] (4) High-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, middle layer masterbatch, ethylene-methyl acrylate copolymer masterbatch, and outer layer masterbatch are respectively used as raw materials for the inner layer, sub-inner layer, middle layer, sub-outer layer, and outer layer, and are sequentially put into a five-layer co-extrusion blow molding machine for five-layer co-extrusion blow molding. After extrusion, preform molding, inflation, trimming, cooling and shaping, a barrier medicine bottle is obtained.

[0039] Among them, during five-layer co-extrusion blow molding, the extrusion temperature of each layer is controlled separately, the die head temperature is 190-230℃, the inner layer extrusion temperature is 190-220℃, the sub-inner layer extrusion temperature is 180-210℃, the middle layer extrusion temperature is 220-240℃, the sub-outer layer extrusion temperature is 180-210℃, and the outer layer extrusion temperature is 190-220℃.

[0040] The barrier medicine bottle of the present invention is suitable for use in the fields of medicine, food, etc. as packaging equipment, etc.

[0041] Example 1

[0042] Step 1: Take montmorillonite, sieve it through 1250 mesh, then disperse it in a mixed solvent of ethanol and water, add KH560 silane coupling agent, heat it to 70±2°C, react for 2h, then separate and dry the reaction product to obtain modified montmorillonite.

[0043] Step 2: Take 80 parts by weight of ethylene-vinyl alcohol copolymer, 17 parts by weight of cyclic polyolefin and 3 parts by weight of modified montmorillonite, the melt index of ethylene-vinyl alcohol copolymer is 1g / 10min, the melt index of cyclic polyolefin is 2g / 10min, put them into a high mixer for mixing, and then use a twin-screw extruder to granulate them to obtain a middle layer masterbatch; take another 80 parts by weight of high-density polyethylene, 17 parts by weight of cyclic polyolefin and 3 parts by weight of modified montmorillonite, the melt index of ethylene-vinyl alcohol copolymer is 2g / 10min, put them into a high mixer for mixing, and then use a twin-screw extruder to granulate them to obtain an outer layer masterbatch.

[0044] Step 3: Take high-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, and ethylene-methyl acrylate copolymer masterbatch, and the high-density polyethylene melt index is 0.8g / 10min, and the ethylene-methyl acrylate copolymer melt index is 2g / 10min; put them into a five-layer co-extrusion blow molding machine in the order of high-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, middle layer masterbatch, ethylene-methyl acrylate copolymer masterbatch, and outer layer masterbatch, and carry out five-layer co-extrusion blow molding, and control the inner layer thickness to 0.2mm, the second inner layer thickness to 0.1mm, the middle layer thickness to 0.3mm, the second outer layer thickness to 0.1mm, the outer layer thickness to 0.4mm, and the total thickness to 1.1mm; then after molding the preform, blowing, trimming, cooling and shaping, a barrier medicine bottle is obtained.

[0045] The oxygen permeability of the barrier medicine bottle prepared in this embodiment is 0.18 cm 3 / (pkg.24h), water vapor permeability is 0.0055g / (pkg.24h).

[0046] Example 2

[0047] Step 1: Take montmorillonite, sieve it through 1250 mesh, then disperse it in a mixed solvent of ethanol and water, add KH560 silane coupling agent, heat it to 70±2°C, react for 2h, then separate and dry the reaction product to obtain modified montmorillonite.

[0048] Step 2: Take 75 parts by mass of ethylene-vinyl alcohol copolymer, 20 parts by mass of cyclic polyolefin and 5 parts by mass of modified montmorillonite, the melt index of ethylene-vinyl alcohol copolymer is 1g / 10min, the melt index of cyclic polyolefin is 2g / 10min, put them into a high mixer for mixing, and then use a twin-screw extruder to granulate to obtain a middle layer masterbatch; take another 75 parts by mass of high-density polyethylene, 20 parts by mass of cyclic polyolefin and 5 parts by mass of modified montmorillonite, the melt index of ethylene-vinyl alcohol copolymer is 2g / 10min, put them into a high mixer for mixing, and then use a twin-screw extruder to granulate to obtain an outer layer masterbatch.

[0049] Step 3: Take high-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, and ethylene-methyl acrylate copolymer masterbatch, and the high-density polyethylene melt index is 0.8g / 10min, and the ethylene-methyl acrylate copolymer melt index is 2g / 10min; put them into a five-layer co-extrusion blow molding machine in the order of high-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, middle layer masterbatch, ethylene-methyl acrylate copolymer masterbatch, and outer layer masterbatch, and carry out five-layer co-extrusion blow molding, and control the inner layer thickness to 0.2mm, the second inner layer thickness to 0.1mm, the middle layer thickness to 0.3mm, the second outer layer thickness to 0.1mm, the outer layer thickness to 0.4mm, and the total thickness to 1.1mm; then after molding the preform, blowing, trimming, cooling and shaping, a barrier medicine bottle is obtained.

[0050] The oxygen permeability of the barrier medicine bottle prepared in this embodiment is 0.16 cm 3 / (pkg.24h), water vapor permeability is 0.0051g / (pkg.24h).

[0051] Example 3

[0052] Step 1: Take montmorillonite, sieve it through 1250 mesh, then disperse it in a mixed solvent of ethanol and water, add KH560 silane coupling agent, heat it to 70±2°C, react for 2h, then separate and dry the reaction product to obtain modified montmorillonite.

[0053] Step 2: Take 75 parts by mass of ethylene-vinyl alcohol copolymer, 20 parts by mass of cyclic polyolefin and 5 parts by mass of modified montmorillonite, the melt index of ethylene-vinyl alcohol copolymer is 1g / 10min, the melt index of cyclic polyolefin is 2g / 10min, put them into a high mixer for mixing, and then use a twin-screw extruder to granulate to obtain a middle layer masterbatch; take another 75 parts by mass of high-density polyethylene, 20 parts by mass of cyclic polyolefin and 5 parts by mass of modified montmorillonite, the melt index of ethylene-vinyl alcohol copolymer is 2g / 10min, put them into a high mixer for mixing, and then use a twin-screw extruder to granulate to obtain an outer layer masterbatch.

[0054] Step 3: Take high-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, and ethylene-methyl acrylate copolymer masterbatch, and the high-density polyethylene melt index is 0.8g / 10min, and the ethylene-methyl acrylate copolymer melt index is 2g / 10min; put them into a five-layer co-extrusion blow molding machine in the order of high-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, middle layer masterbatch, ethylene-methyl acrylate copolymer masterbatch, and outer layer masterbatch, and carry out five-layer co-extrusion blow molding, and control the inner layer thickness to 0.2mm, the second inner layer thickness to 0.1mm, the middle layer thickness to 0.4mm, the second outer layer thickness to 0.1mm, the outer layer thickness to 0.3mm, and the total thickness to 1.1mm; then after molding the preform, blowing, trimming, cooling and shaping, a barrier medicine bottle is obtained.

[0055] The oxygen permeability of the barrier medicine bottle prepared in this embodiment is 0.18 cm 3 / (pkg.24h), water vapor permeability is 0.0051g / (pkg.24h).

[0056] Example 4

[0057] Step 1: Take montmorillonite, sieve it through 1250 mesh, then disperse it in a mixed solvent of ethanol and water, add KH560 silane coupling agent, heat it to 70±2°C, react for 2h, then separate and dry the reaction product to obtain modified montmorillonite.

[0058] Step 2: Take 86 parts by mass of ethylene-vinyl alcohol copolymer, 10 parts by mass of cyclic polyolefin and 4 parts by mass of modified montmorillonite, the melt index of ethylene-vinyl alcohol copolymer is 1g / 10min, the melt index of cyclic polyolefin is 2g / 10min, put them into a high mixer for mixing, and then use a twin-screw extruder to granulate to obtain a middle layer masterbatch; take another 86 parts by mass of high-density polyethylene, 10 parts by mass of cyclic polyolefin and 4 parts by mass of modified montmorillonite, the melt index of ethylene-vinyl alcohol copolymer is 2g / 10min, put them into a high mixer for mixing, and then use a twin-screw extruder to granulate to obtain an outer layer masterbatch.

[0059] Step 3: Take high-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, and ethylene-methyl acrylate copolymer masterbatch, and the high-density polyethylene melt index is 0.8g / 10min, and the ethylene-methyl acrylate copolymer melt index is 2g / 10min; put them into a five-layer co-extrusion blow molding machine in the order of high-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, middle layer masterbatch, ethylene-methyl acrylate copolymer masterbatch, and outer layer masterbatch, and carry out five-layer co-extrusion blow molding, and control the inner layer thickness to 0.2mm, the second inner layer thickness to 0.1mm, the middle layer thickness to 0.3mm, the second outer layer thickness to 0.1mm, the outer layer thickness to 0.4mm, and the total thickness to 1.1mm; then after molding the preform, blowing, trimming, cooling and shaping, a barrier medicine bottle is obtained.

[0060] The oxygen permeability of the barrier medicine bottle prepared in this embodiment is 0.23 cm 3 / (pkg.24h), water vapor permeability is 0.0074g / (pkg.24h).

[0061] Example 5

[0062] Step 1: Take montmorillonite, sieve it through 1250 mesh, then disperse it in a mixed solvent of ethanol and water, add KH560 silane coupling agent, heat it to 70±2°C, react for 2h, then separate and dry the reaction product to obtain modified montmorillonite.

[0063] Step 2: Take 86 parts by mass of ethylene-vinyl alcohol copolymer, 10 parts by mass of cyclic polyolefin and 4 parts by mass of modified montmorillonite, the melt index of ethylene-vinyl alcohol copolymer is 1g / 10min, the melt index of cyclic polyolefin is 2g / 10min, put them into a high mixer for mixing, and then use a twin-screw extruder to granulate to obtain a middle layer masterbatch; take another 86 parts by mass of high-density polyethylene, 10 parts by mass of cyclic polyolefin and 4 parts by mass of modified montmorillonite, the melt index of ethylene-vinyl alcohol copolymer is 2g / 10min, put them into a high mixer for mixing, and then use a twin-screw extruder to granulate to obtain an outer layer masterbatch.

[0064] Step 3: Take high-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, and ethylene-methyl acrylate copolymer masterbatch, and the high-density polyethylene melt index is 0.8g / 10min, and the ethylene-methyl acrylate copolymer melt index is 2g / 10min; put them into a five-layer co-extrusion blow molding machine in the order of high-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, middle layer masterbatch, ethylene-methyl acrylate copolymer masterbatch, and outer layer masterbatch, and carry out five-layer co-extrusion blow molding, and control the inner layer thickness to 0.2mm, the second inner layer thickness to 0.1mm, the middle layer thickness to 0.4mm, the second outer layer thickness to 0.1mm, the outer layer thickness to 0.3mm, and the total thickness to 1.1mm; then after molding the preform, blowing, trimming, cooling and shaping, a barrier medicine bottle is obtained.

[0065] The oxygen permeability of the barrier medicine bottle prepared in this embodiment is 0.25 cm 3 / (pkg.24h), water vapor permeability is 0.0075g / (pkg.24h).

[0066] Example 6

[0067] Step 1: Take montmorillonite, sieve it through 1500 mesh, then disperse it in a mixed solvent of ethanol and water, add KH560 silane coupling agent, heat it to 70±2°C, react for 2h, then separate and dry the reaction product to obtain modified montmorillonite.

[0068] Step 2: Take 75 parts by mass of ethylene-vinyl alcohol copolymer, 20 parts by mass of cyclic polyolefin and 5 parts by mass of modified montmorillonite, the melt index of ethylene-vinyl alcohol copolymer is 2g / 10min, the melt index of cyclic polyolefin is 4g / 10min, put them into a high mixer for mixing, and then use a twin-screw extruder to granulate to obtain a middle layer masterbatch; take another 75 parts by mass of high-density polyethylene, 20 parts by mass of cyclic polyolefin and 5 parts by mass of modified montmorillonite, the melt index of ethylene-vinyl alcohol copolymer is 4g / 10min, put them into a high mixer for mixing, and then use a twin-screw extruder to granulate to obtain an outer layer masterbatch.

[0069] Step 3: Take high-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, and ethylene-methyl acrylate copolymer masterbatch, and the high-density polyethylene melt index is 1.2g / 10min, and the ethylene-methyl acrylate copolymer melt index is 2g / 10min; put them into a five-layer co-extrusion blow molding machine in the order of high-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, middle layer masterbatch, ethylene-methyl acrylate copolymer masterbatch, and outer layer masterbatch, and carry out five-layer co-extrusion blow molding, and control the inner layer thickness to 0.2mm, the second inner layer thickness to 0.1mm, the middle layer thickness to 0.4mm, the second outer layer thickness to 0.1mm, the outer layer thickness to 0.3mm, and the total thickness to 1.1mm; then after molding the preform, blowing, trimming, cooling and shaping, a barrier medicine bottle is obtained.

[0070] The oxygen permeability of the barrier medicine bottle prepared in this embodiment is 0.10 cm 3 / (pkg.24h), water vapor permeability is 0.0045g / (pkg.24h).

[0071] Comparative Example 1

[0072] Step 1: Take 75 parts by mass of PE, 16 parts by mass of maleic anhydride grafted POE, 0.5 parts by mass of antioxidant, 1 part by mass of lubricant and 20 parts by mass of sodium bentonite as the PE base layer mixture; take 28 parts by mass of ethylene-vinyl alcohol copolymer, 12 parts by mass of maleic anhydride grafted polyethylene, 6 parts by mass of mesoporous silica and 3 parts by mass of modified chitosan nanofibers as the barrier layer mixture.

[0073] Step 2: Using a twin-screw extruder, the PE base layer mixture is mixed and melted, cooled and granulated to obtain a first masterbatch; the barrier layer mixture is mixed and melted, cooled and granulated to obtain a second masterbatch.

[0074] Step three: Use co-extrusion equipment to melt-extrude the first masterbatch to obtain a PE base layer with a thickness of 0.6 mm, then melt-extrude the acrylic hot melt adhesive on the PE base layer to obtain a bonding layer with a thickness of 0.2 mm, and finally melt-extrude the second masterbatch on the bonding layer to obtain a barrier layer with a thickness of 0.1 mm, and obtain a sheet after cooling and molding; use the blister process to make the sheet into a barrier medicine bottle.

[0075] The barrier medicine bottle prepared by this comparative example has an oxygen permeability of 0.67 cm 3 / (pkg.24h), water vapor permeability is 0.0113g / (pkg.24h).

[0076] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A barrier medicine bottle, characterized in that: Along the direction from the inside of the bottle to the outside of the bottle, the bottle body of the barrier medicine bottle includes an inner layer, a sub-inner layer, a middle layer, a sub-outer layer and an outer layer which are sequentially covered; and the inner layer comprises polyethylene; The second inner layer includes ethylene-methyl acrylate copolymer; The middle layer includes ethylene-vinyl alcohol copolymer, cyclic polyolefin and modified montmorillonite; The second outer layer includes ethylene-methyl acrylate copolymer; The outer layer includes polyethylene, cyclic polyolefin and modified montmorillonite.

2. The barrier medicine bottle according to claim 1, characterized in that: In terms of weight parts, the middle layer comprises 75-88 weight parts of ethylene-vinyl alcohol copolymer, 10-20 weight parts of cyclic polyolefin and 3-5 weight parts of modified montmorillonite.

3. The barrier medicine bottle according to claim 1, characterized in that: In terms of weight percentage, the outer layer comprises 75-88 weight percentages of polyethylene, 10-20 weight percentages of cyclic polyolefin and 3-5 weight percentages of modified montmorillonite.

4. The barrier medicine bottle according to any one of claims 1 to 3, characterized in that: The preparation method of the modified montmorillonite comprises the following steps: Firstly, montmorillonite is dispersed in a mixed solvent of ethanol and water, a silane coupling agent is added, the mixture is heated to 60-80°C, and the mixture is reacted for 1-3 hours. Then, the reaction product is separated, dried, and sieved through 1250-1500 meshes to obtain modified montmorillonite.

5. The barrier medicine bottle according to claim 1, characterized in that: The melt index of polyethylene is 0.5-2.5 g / 10 min, the melt index of ethylene-vinyl alcohol copolymer is 1-4 g / 10 min, the melt index of cyclic polyolefin is 2-8 g / 10 min, and the melt index of ethylene-methyl acrylate copolymer is 2-4 g / 10 min.

6. A method for preparing a barrier medicine bottle according to any one of claims 1 to 5, characterized in that: The steps include: S1: taking ethylene-vinyl alcohol copolymer, cyclic polyolefin and modified montmorillonite, blending and granulating to obtain a middle-layer masterbatch; S2: polyethylene, cyclic polyolefin and modified montmorillonite are mixed and pelletized to obtain an outer layer masterbatch; S3: High-density polyethylene masterbatch, ethylene-methyl acrylate copolymer masterbatch, middle layer masterbatch, ethylene-methyl acrylate copolymer masterbatch, and outer layer masterbatch are sequentially put into a five-layer co-extrusion blow molding machine layer by layer to perform five-layer co-extrusion blow molding to obtain the barrier medicine bottle.

7. The method for preparing a barrier medicine bottle according to claim 6, characterized in that: In step S3, when five-layer co-extrusion blow molding is performed, the die head temperature is controlled to be 190-230°C.

8. The method for preparing the barrier medicine bottle according to claim 7, characterized in that: The inner layer extrusion temperature is 190-220°C, the sub-inner layer extrusion temperature is 180-210°C, the middle layer extrusion temperature is 220-240°C, the sub-outer layer extrusion temperature is 180-210°C, and the outer layer extrusion temperature is 190-220°C.

9. The method for preparing a barrier medicine bottle according to claim 6, characterized in that: The total wall thickness of the barrier medicine bottle is 0.9-1.1 mm.

10. The method for preparing a barrier medicine bottle according to claim 9, characterized in that: The thickness of the inner layer is 0.2-0.3mm, the thickness of the sub-inner layer is 0.1-0.15mm, the thickness of the middle layer is 0.2-0.3mm, the thickness of the sub-outer layer is 0.1-0.15mm, and the thickness of the outer layer is 0.3-0.4mm.

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