Packaging material of low-precipitation ultrahigh-barrier film for injection and preparation process of packaging material

Abstract

The invention belongs to the technical field of packaging materials, and particularly relates to a packaging material of a low-precipitation ultrahigh-barrier film for an injection and a preparation process of the packaging material. The packaging material comprises a two-layer structure including an antibacterial polyvinyl chloride (PVC) layer and a polyvinyl alcohol (PVA) modified coating layer. The packaging material of the low-precipitation ultrahigh-barrier film for the injection is light in weight, high in strength, high in water and oxygen barrier property and good in chemical stability, has certain mechanical property, is simple in preparation process, adopts safe and non-toxic raw materials, meets the requirements of commercial low-precipitation ultrahigh-barrier film packaging materials, and can be in direct contact with the injection.

Description

Technical Field

[0001] The invention belongs to the technical field of packaging materials, and in particular relates to a packaging material of a low-precipitation ultra-high barrier film for injection and a preparation process thereof. Background Art

[0002] Ultra-high barrier films can protect products from external water vapor erosion and extend their service life. They are mainly used for food and drug packaging. At present, ultra-high barrier films are only supplied in small quantities by individual manufacturers in the United States and Japan, and have a small scope of application and are expensive. Initially, researchers used oxides and nitrogen oxides of the same name as barrier layers. Although a single layer of inorganic compounds can increase the film thickness and improve the barrier properties, the extent is limited. In recent years, organic / inorganic multilayer composite materials have been increasingly widely used as barrier layers. The introduction of organic matter can provide a flat surface for the deposition of inorganic layers and achieve high water vapor barrier.

[0003] The demand for flexible, transparent and stable ultra-high barrier films in the field of pharmaceutical packaging is increasing. To meet the market demand, barrier films with higher barrier properties are constantly being developed. However, most of the ultra-high barrier films reported so far have the defects of decreased barrier properties under high temperature and humidity, and difficulty in recycling the packaging, which has caused great pressure on the ecological environment. Therefore, it is still necessary to continuously update the production technology of ultra-high barrier films. Summary of the invention

[0004] PVC has low production cost, good transparency, resilience and toughness, and is widely used in the fields of medical care, medical consumables, etc. Therefore, the present invention selects PVC as the base material, and the low precipitation ultra-high barrier film packaging material for injection produced has the function of preventing the mutual penetration of gases, water vapor, liquids and organic substances, etc., and meets the requirements of commercial ultra-high barrier film packaging materials.

[0005] The packaging material of the low-precipitation ultra-high barrier film for injection and the preparation process thereof of the present invention comprise the following steps:

[0006] (1) placing the prepared antibacterial PVC substrate into the gap between the rubber rollers of the corona treatment machine, turning on the power of the corona treatment machine, and using the adjustment knob to adjust the output current to a stable value of 2A, pulling out the substrate at a uniform speed;

[0007] (2) Place the corona-treated substrate flat on a glass plate, absorb the PVA modified coating layer and drop it on the substrate, and then use a wire rod to scrape at a uniform speed;

[0008] (3) Finally, the coated PVC film is placed in a blast dryer and dried at 60° C. to obtain a low precipitation ultra-high barrier film packaging material for injection.

[0009] Preferably, the packaging material of the low-precipitation ultra-high barrier film for injection comprises, from the outside to the inside, an antibacterial polyvinyl chloride (PVC) layer and a polyvinyl alcohol (PVA) modified coating layer.

[0010] Preferably, the preparation method of the antibacterial PVC layer is to heat and melt the dried PVC pellets with a double-roll mill, then add the organosilicon quaternary ammonium salt antibacterial agent AEM-5700 and the heat stabilizer for mixing, and after the mixing is completed, the blend is pressed into a sheet by a flat vulcanizer.

[0011] Further preferably, the antibacterial PVC layer is composed of 80-85 parts of polyvinyl chloride, 3-5 parts of heat stabilizer, and 10-15 parts of organosilicon quaternary ammonium salt antibacterial agent AEM-5700, by weight.

[0012] Further preferably, the tablet pressing temperature is 190-200° C., the pressing pressure is 10-12 MPa, the preheating time is 2-5 min, the pressure holding time is 2 min, and the cooling time is 2-8 min.

[0013] Further preferably, the heat stabilizer added to the antibacterial PVC layer is N,N'-diphenylurea

[0014] Preferably, the preparation steps of the PVA modified coating layer include:

[0015] (1) Add PVA to deionized water and heat and stir until the solution becomes clear, then cool to room temperature.

[0016] (2) A nanocellulose sodium gel with a solid content of 2.5 wt% was added into a blender, and then deionized water was added thereto by high-speed shearing ultrasound to prepare a 1.0 wt% nanocellulose suspension.

[0017] (3) The 1.0 wt% nanocellulose suspension prepared in step (2) was mixed with the PVA solution and stirred at room temperature for 1 h to obtain a PVA / CNF hybrid solution.

[0018] (4) Add stearic acid to the ethanol solution, heat and stir to dissolve, and obtain a stearic acid ethanol solution.

[0019] (5) The PVA / CNF hybrid solution was first heated and then blended with stearic acid ethanol solution to obtain the PVA / CNF / SA barrier coating.

[0020] Further preferably, the raw materials of the PVA modified coating layer are composed, by weight, of 75-80 parts of polyvinyl alcohol, 7-10 parts of stearic acid, 5-10 parts of nanocellulose, and 10-15 parts of ethanol.

[0021] Further preferably, in the preparation step (1) of the PVA modified coating layer, the PVA heating and stirring temperature is 85-100°C, in the step (4), the stearic acid heating temperature is 70-90°C, and in the step (5), the hybrid liquid heating and blending temperature is 85°C.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] (1) The cross-linking and increased crystallinity of polymer materials restrict the movement of molecular chains, resulting in a decrease in the free volume of the polymer, making it difficult for small molecules to penetrate and diffuse, thereby increasing the barrier properties of the polymer.

[0024] (2) PVC not only provides good mechanical support, but also has excellent antibacterial properties, heat resistance, chemical stability and moisture and heat resistance. At the same time, adding a PVA modified coating layer increases the oxygen barrier property and organic solvent resistance of the packaging material.

[0025] (3) PVC is formed by free radical polymerization of vinyl chloride monomer. There is an unstable structure in the polymerized PVC chain, so thermal degradation will occur above 100°C. The present invention adds a thermal stabilizer N,N'-diphenylurea during the synthesis of PVC, which has good compatibility with PVC, interrupts the "zipper-like" degradation in PVC, has a good thermal stabilization effect, and reduces precipitation.

[0026] (4) The low precipitation ultra-high barrier film packaging material for injections prepared with PVC as the base material and PVA as the coating layer is light in weight, high in strength, high in water and oxygen barrier performance, good in chemical stability, and also has certain mechanical properties. These properties are well in line with the requirements of injection packaging materials. DETAILED DESCRIPTION

[0027] The following embodiments of the technical solution of the present invention are described in detail in conjunction with the embodiments. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and are therefore only used as examples, and cannot be used to limit the protection scope of the present invention.

[0028] It should be noted that the experimental methods used in the implementation examples are all conventional methods unless otherwise specified; the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial channels.

[0029] In the present invention, unless otherwise specified, all "parts" and percentages (%) refer to percentages by weight.

[0030] In the present invention, unless otherwise specified, the sum of all percentages in all compositions is 100%.

[0031] In the present invention, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between ab, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed in this document, and "0-5" is just an abbreviation of these numerical combinations.

[0032] In the present invention, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution.

[0033] In the present invention, unless otherwise specified, all the steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially; for example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially; for example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0034] Example 1

[0035] (1) 85 parts of dried PVC pellets were heated and melted using a double-roll mill, and then 12 parts of silicone quaternary ammonium salt antibacterial agent AEM-5700 and 3 parts of N,N'-diphenylurea were added for mixing. After the mixing was completed, the mixture was preheated for 2 minutes, and the blend was pressed at 190°C and a pressure of 10 MPa using a flat plate vulcanizer, the pressure was maintained for 2 minutes, and the mixture was cooled for 2 minutes to obtain an antibacterial PVC substrate.

[0036] (2) Add 80 parts of PVA to deionized water and heat and stir at 95°C until the solution is clear, then cool to room temperature, then add 7 parts of sodium nanocellulose gel with a solid content of 2.5wt% into a blender, add deionized water and high-speed shear ultrasound to obtain a 1.0wt% nanocellulose suspension. Then mix with the PVA solution and stir at room temperature for 1h to obtain a PVA / CNF hybrid solution for use. Add 8 parts of stearic acid to an ethanol solution and stir and dissolve at 85°C to obtain a stearic acid ethanol solution. After the PVA / CNF hybrid solution is heated to 85°C, it is blended with the stearic acid ethanol solution to obtain a PVA / CNF / SA barrier coating.

[0037] (3) The prepared antibacterial PVC substrate was placed in the gap between the rubber rollers of the corona treatment machine, the power of the corona treatment machine was turned on, and the output current was adjusted using the adjustment knob to stabilize at 2A, and the substrate was pulled out at a uniform speed.

[0038] (4) Place the corona-treated substrate flat on a glass plate, drip the PVA modified coating layer prepared in step (2) onto the substrate, and then use a wire rod to scrape at a uniform speed.

[0039] (5) Finally, the coated PVC film is placed in a blast dryer and dried at 60° C. to obtain a low precipitation ultra-high barrier film packaging material for injection.

[0040] Example 2

[0041] (1) 85 parts of dried PVC pellets were heated and melted using a double-roll mill, and then 12 parts of silicone quaternary ammonium salt antibacterial agent AEM-5700 and 3 parts of N,N'-diphenylurea were added for mixing. After mixing, the mixture was preheated for 2 minutes, and the blend was pressed at 200°C and a pressure of 12 MPa using a flat plate vulcanizer, maintained at a pressure of 2 minutes, and cooled for 2 minutes to obtain an antibacterial PVC substrate.

[0042] (2) Add 80 parts of PVA to deionized water and heat and stir at 100°C until the solution is clear, then cool to room temperature, then add 7 parts of sodium nanocellulose gel with a solid content of 2.5wt% to a blender, add deionized water and high-speed shear ultrasound to obtain a 1.0wt% nanocellulose suspension. Then mix with the PVA solution and stir at room temperature for 1h to obtain a PVA / CNF hybrid solution for use. Add 8 parts of stearic acid to the ethanol solution and stir and dissolve at 85°C to obtain a stearic acid ethanol solution. After the PVA / CNF hybrid solution is heated to 85°C, it is blended with the stearic acid ethanol solution to obtain a PVA / CNF / SA barrier coating.

[0043] (3) The prepared antibacterial PVC substrate was placed in the gap between the rubber rollers of the corona treatment machine, the power of the corona treatment machine was turned on, and the output current was adjusted using the adjustment knob to stabilize at 2A, and the substrate was pulled out at a uniform speed.

[0044] (4) Place the corona-treated substrate flat on a glass plate, drip the PVA modified coating layer prepared in step (2) onto the substrate, and then use a wire rod to scrape at a uniform speed.

[0045] (5) Finally, the coated PVC film is placed in a blast dryer and dried at 60° C. to obtain a low precipitation ultra-high barrier film packaging material for injection.

[0046] Example 3

[0047] (1) 80 parts of dried PVC pellets were heated and melted using a double-roll mill, and then 15 parts of silicone quaternary ammonium salt antibacterial agent AEM-5700 and 5 parts of N,N'-diphenylurea were added for mixing. After the mixing was completed, the mixture was preheated for 2 minutes, and the blend was pressed at 200°C and a pressure of 12 MPa using a flat plate vulcanizer, the pressure was maintained for 2 minutes, and the mixture was cooled for 2 minutes to obtain an antibacterial PVC substrate.

[0048] (2) Add 85 parts of PVA to deionized water and heat and stir at 95°C until the solution is clear, then cool to room temperature, then add 7 parts of sodium nanocellulose gel with a solid content of 2.5wt% to a blender, add deionized water and high-speed shear ultrasound to obtain a 1.0wt% nanocellulose suspension. Then mix with the PVA solution and stir at room temperature for 1h to obtain a PVA / CNF hybrid solution for use. Add 8 parts of stearic acid to the ethanol solution and stir and dissolve at 85°C to obtain a stearic acid ethanol solution. After the PVA / CNF hybrid solution is heated to 85°C, it is blended with the stearic acid ethanol solution to obtain a PVA / CNF / SA barrier coating.

[0049] (3) The prepared antibacterial PVC substrate was placed in the gap between the rubber rollers of the corona treatment machine, the power of the corona treatment machine was turned on, and the output current was adjusted using the adjustment knob to stabilize at 2A, and the substrate was pulled out at a uniform speed.

[0050] (4) Place the corona-treated substrate flat on a glass plate, drip the PVA modified coating layer prepared in step (2) onto the substrate, and then use a wire rod to scrape at a uniform speed.

[0051] (5) Finally, the coated PVC film is placed in a blast dryer and dried at 60° C. to obtain a low precipitation ultra-high barrier film packaging material for injection.

[0052] The samples obtained in Examples 1-3 were subjected to performance tests, and commercially available PVC films were used as comparative examples.

[0053] Water Permeability Test

[0054] According to GB / T26253-2010, use MOCON 3 / 33 Water Vapor Transmission Rate (WTR) Tester, test the sample thickness, then cut the sample into a circle with a diameter of 20mm and adhere it to the circular hole in the aluminum foil and clamp it, then put the aluminum foil into the cavity of the tester, and test the coated film sample at a temperature of 23±2℃ and a relative humidity of 90%. The results are shown in Table 1.

[0055] Table 1

[0056] Group Example 1 Example 2 Example 3 Comparative Example <![CDATA[Water vapor transmission rate g / (m 2 ·d)]]> 2.2 3.1 1.5 53.2

[0057] Oxygen permeability test

[0058] According to the pressure difference method in GB / T1038-2000, the oxygen transmission rate (OTR) value of the composite film is calculated using MOCON 2 / 21 tester, first test the sample thickness, then cut the sample into a circle with a diameter of 20mm and stick it to the circular hole in the aluminum foil and clamp it, then put the aluminum foil into the cavity of the tester and test it at 23±2℃ and relative humidity of 0%. The results are shown in Table 2.

[0059] Table 2

[0060] Group Example 1 Example 2 Example 3 Comparative Example <![CDATA[Oxygen transmission rate cm 3 / (m 2 ·d)]]> 1.3 4.5 3.2 86.3

[0061] Thermal stability precipitation performance evaluation

[0062] The precipitation rate of the heat stabilizer is determined according to the following method:

[0063] The prepared packaging material was pressed into a 3mm*3mm*2mm square sample and placed in a constant temperature and humidity chamber at 50°C and 50% humidity, and tested every 0.5 days. The comparative example was treated in the same way.

[0064] 1. Wash off the heat stabilizer precipitated on the surface of the sample with methanol, prepare a standard volume of methanol solution, and then use an ultraviolet spectrophotometer to measure its absorbance at a specific ultraviolet wavelength, and then calculate the absolute precipitation amount based on the standard curve.

[0065] 2. Weigh the mass of multiple samples to calculate the average mass, and calculate the heat stabilizer content in each sample based on the proportion of heat stabilizer in the formula.

[0066] 3. The precipitation rate was calculated according to the following formula: P = m / M*100%. The results are shown in Table 3.

[0067] Where P is the precipitation rate, m is the absolute precipitation amount of the heat stabilizer, and M is the total amount of heat stabilizer contained in each sample.

[0068] Table 3

[0069]

[0070] The above results show that the low precipitation ultra-high barrier film packaging material for injection prepared by the present invention has high water and oxygen barrier performance and good chemical stability, meeting the requirements of commercial low precipitation ultra-high barrier film packaging materials.

[0071] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. These modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and specification of the present invention.

Claims

1. A packaging material of a low-precipitation ultra-high barrier film for injection and a preparation process thereof, comprising the following steps: (1) placing the prepared antibacterial PVC substrate into the gap between the rubber rollers of the corona treatment machine, turning on the power of the corona treatment machine, and using the adjustment knob to adjust the output current to a stable value of 2A, pulling out the substrate at a uniform speed; (2) Place the corona-treated substrate flat on a glass plate, absorb the PVA modified coating layer and drop it on the substrate, and then use a wire rod to scrape at a uniform speed; (3) Finally, the coated PVC film is placed in a blast dryer and dried at 60° C. to obtain a low precipitation ultra-high barrier film packaging material for injection.

2. The packaging material of a low-precipitation ultra-high barrier film for injection and its preparation process according to claim 1, characterized in that: The packaging materials of the low-precipitation ultra-high barrier film for injection are, from the outside to the inside, an antibacterial polyvinyl chloride (PVC) layer and a polyvinyl alcohol (PVA) modified coating layer.

3. The packaging material of the low precipitation ultra-high barrier film for injection and the preparation process thereof according to claim 1, characterized in that: The preparation method of the antibacterial PVC layer is to heat and melt the dried PVC pellets with a double-roll mill, then add the silicone quaternary ammonium salt antibacterial agent AEM-5700 and the heat stabilizer for mixing, and after the mixing is completed, the blend is pressed into a sheet through a flat vulcanizer.

4. The packaging material of the low precipitation ultra-high barrier film for injection and the preparation process thereof according to claim 3, characterized in that: In parts by weight, 80-85 parts of polyvinyl chloride, 3-5 parts of heat stabilizer, and 10-15 parts of organosilicon quaternary ammonium salt antibacterial agent AEM-5700 constitute the antibacterial PVC layer.

5. The packaging material of the low precipitation ultra-high barrier film for injection and the preparation process thereof according to claim 3, characterized in that: The tablet pressing temperature is 190-200°C, the pressing pressure is 10-12MPa, the preheating time is 2-5min, the pressure holding time is 2min, and the cooling time is 2-8min.

6. The packaging material of the low precipitation ultra-high barrier film for injection and the preparation process thereof according to claim 4, characterized in that: The heat stabilizer is N,N'-diphenylurea.

7. The packaging material of the low precipitation ultra-high barrier film for injection and the preparation process thereof according to claim 1, characterized in that: The preparation steps of the PVA modified coating layer include: (1) Add PVA to deionized water and heat and stir until the solution becomes clear, then cool to room temperature. (2) A nanocellulose sodium gel with a solid content of 2.5 wt% was added into a blender, and then deionized water was added thereto by high-speed shearing ultrasound to prepare a 1.0 wt% nanocellulose suspension. (3) The 1.0 wt% nanocellulose suspension prepared in step (2) was mixed with the PVA solution and stirred at room temperature for 1 h to obtain a PVA / CNF hybrid solution. (4) Add stearic acid to the ethanol solution, heat and stir to dissolve, and obtain a stearic acid ethanol solution. (5) The PVA / CNF hybrid solution was first heated and then blended with stearic acid ethanol solution to obtain the PVA / CNF / SA barrier coating.

8. The low precipitation ultra-high barrier film packaging material for injection and the preparation process thereof according to claim 7, characterized in that: The raw materials of the PVA modified coating layer are composed, by weight, of 75-80 parts of polyvinyl alcohol, 7-10 parts of stearic acid, 5-10 parts of nanocellulose and 10-15 parts of ethanol.

9. The packaging material of the low precipitation ultra-high barrier film for injection and the preparation process thereof according to claim 7, characterized in that: In step (1), the heating and stirring temperature of PVA is 85-100° C., in step (4), the heating temperature of stearic acid is 70-90° C., and in step (5), the heating and blending temperature of the hybrid liquid is 85° C.

10. Packaging material of low precipitation ultra-high barrier film for injection and its preparation process, characterized in that: The low-precipitation ultra-high barrier film packaging material for injection is prepared by the method described in any one of claims 1-9.

Images