Material for infusion hose and application thereof

Abstract

The invention relates to the technical field of medical instruments, and particularly discloses a material for an infusion hose and application of the material. The material for the infusion hose is composed of an outer layer material, a middle layer material and an inner layer material, and the outer layer material comprises PLLA-PLGA and Bio-PET; the material of the middle layer comprises PHB and Bio-PET; and the material of the inner layer comprises PHB, EVA and Bio-PET. By reasonably designing the formula structure and the material proportion of the multi-layer infusion tube, the invention provides the infusion hose material with the advantages of excellent mechanical property, good biocompatibility, good chemical stability, good environmental protection performance and the like. According to the infusion hose, the compression resistance, the tensile strength and the flexibility of the whole hose are remarkably improved, the controllability of the biodegradation rate is achieved, and the infusion hose is suitable for complex infusion scenes.

Description

Technical Field

[0001] The present invention relates to the technical field of medical devices, and specifically discloses a material for infusion hoses and its applications. Background Art

[0002] The infusion hose is an important channel connecting the infusion bag and the infusion needle in the patient's body, and the infusion hose interface is a key component thereof. Currently, most of the common infusion hoses on the market are made of a single material, and the materials are mostly thermoplastic polymer materials such as polyvinyl chloride (PVC), polyethylene (PE), and polypropylene (PP). PVC hoses were widely used in the infusion system due to their good flexibility and transparency. However, PVC materials usually need to add plasticizers (such as phthalates), and these plasticizers may migrate into the liquid medicine during long-term use, resulting in potential toxicity risks. In addition, PVC produces toxic gases such as hydrogen chloride (HCl) during incineration treatment, causing environmental pollution. To overcome the disadvantages of PVC, many medical device manufacturers have switched to using PE and PP materials. Although these materials have high chemical inertness and good heat resistance, their mechanical properties (such as anti-twisting property, elasticity, and flexibility) are usually not as good as those of PVC, resulting in problems such as hose breakage, deformation, or uneven liquid medicine flow rate during infusion. In addition, the degradability of PE and PP materials is poor and it is difficult to decompose in the natural environment, further exacerbating the difficulty of medical waste treatment.

[0003] With the increasingly strict environmental protection regulations and people's attention to health, the medical device industry has put forward higher requirements for new materials. In addition to meeting the basic mechanical properties and biocompatibility, the environmental protection and degradability of materials have also become new concerns. Especially in the manufacture of infusion hoses and interfaces, the market urgently needs a new material that can simultaneously meet the mechanical properties, biocompatibility, and environmental protection requirements. Summary of the Invention

[0004] Aiming at the deficiencies of traditional infusion hoses and their interfaces in terms of biocompatibility, mechanical properties, and environmental protection, the present invention introduces bio-based polymer materials such as polylactic acid-glycolide copolymer, bio-based polyethylene terephthalate, and ethylene-vinyl acetate copolymer into the infusion hose interface material, which can not only provide excellent physical properties, but also significantly improve the environmental protection of the product and reduce the impact on the environment.

[0005] To achieve the above invention purpose, the present invention adopts the following technical solutions: In the first aspect, the present invention provides a material for infusion hoses, which includes an outer layer material, an intermediate layer material, and an inner layer material; Wherein, the outer layer material includes polylactic acid-glycolide copolymer and bio-based polyethylene terephthalate; The intermediate layer material includes polyhydroxybutyrate and bio-based polyethylene terephthalate; The inner layer material includes polyhydroxybutyrate, ethylene-vinyl acetate copolymer, and bio-based polyethylene terephthalate.

[0006] By reasonably designing the formulation structure and material ratio of the multi-layer infusion tube, the present invention provides an infusion hose material with excellent mechanical properties, good biocompatibility, good chemical stability, and good environmental protection performance. Among them, the outer layer material is composed of polylactic acid-polylactide copolymer (PLLA-PLGA) and bio-based polyethylene terephthalate (Bio-PET), taking into account biodegradability and antioxidant properties; the intermediate layer uses polyhydroxybutyrate (PHB) and bio-based polyethylene terephthalate (Bio-PET) to optimize toughness and strength; the inner layer enhances the resistance to liquid erosion and sealing performance through the ratio of polyhydroxybutyrate (PHB), ethylene-vinyl acetate copolymer (EVA), and bio-based polyethylene terephthalate (Bio-PET).

[0007] Further, based on the total weight of the outer layer material being 100%, the outer layer material includes 25% - 35% by mass of polylactic acid-polylactide copolymer (PLLA-PLGA) and 65% - 75% by mass of polyethylene terephthalate (Bio-PET). Among them, PLLA-PLGA provides rigidity and strength, ensuring that the composite material has sufficient strength and shape retention in medical applications. Bio-PET has excellent heat resistance, mechanical properties, and transparency, and at the same time has excellent biocompatibility and environmental protection performance.

[0008] Based on the total weight of the intermediate layer material being 100%, the intermediate layer material includes 70% - 80% by mass of polyhydroxybutyrate (PHB) and 20% - 30% by mass of bio-based polyethylene terephthalate (Bio-PET). PHB provides structural rigidity and strength, enabling the shape to be maintained during the use of the infusion hose and providing the necessary structural support to prevent the hose from being overly bent or deformed during operation. Bio-PET increases the heat resistance and mechanical properties of the material, making the intermediate layer stable under the sterilization condition of 121°C.

[0009] Based on the total weight of the inner layer material being 100%, the inner layer material includes polyhydroxybutyrate (PHB) with a mass proportion of 45% - 55%, ethylene-vinyl acetate copolymer (EVA) with a mass proportion of 10% - 25%, and bio-based polyethylene terephthalate (Bio-PET) with a mass proportion of 35% - 45%. Among them, at specific ratios, PHB provides rigidity and structural support, EVA provides adhesiveness and flexibility to ensure a firm connection between the joint and the hose, and Bio-PET further enhances the heat resistance of the inner layer material to ensure no deformation or performance degradation during high-temperature sterilization.

[0010] The combination of the three-layer structure not only significantly improves the compressive, tensile strength, and flexibility of the overall pipe, but also realizes the controllability of the biodegradation rate. By optimizing the ratio, the processing performance of the material is significantly improved, the production difficulty and cost are reduced, and the comprehensive performance is enhanced.

[0011] Furthermore, the layer ratio of the outer layer material, the middle layer material, and the inner layer material is 2.5% - 5.5%: 87% - 93%: 4.5% - 7.5%.

[0012] Furthermore, the bio-based polyethylene terephthalate (Bio-PET) is prepared from plant-based ethylene glycol and terephthalic acid, and its bio-based carbon content is 30% - 50%.

[0013] The ratio of L-lactic acid to lactide in poly(lactic acid - poly(lactide) copolymer) (PLLA-PLGA) is 70:30, the weight-average molecular weight is 150000 g / mol - 250000 g / mol, the polydispersity index is 1.5 - 1.8, and its crystallinity is 30% - 40%; Polyhydroxybutyrate (PHB) is poly(3-hydroxybutyrate), the weight-average molecular weight is 200000 g / mol - 300000 g / mol, and the polydispersity index is 1.3 - 1.7; Ethylene-vinyl acetate copolymer (EVA) is EVA with a vinyl acetate (VA) content of 28%, the weight-average molecular weight is from 120000 g / mol to 250000 g / mol, and the polydispersity index is 2.5 - 3.8.

[0014] In the second aspect, the present invention provides the application of the above-mentioned material for infusion hoses in the preparation of infusion hoses.

[0015] In the third aspect, the present invention provides an infusion hose. The structural schematic diagram of the infusion hose is as Figure 1 shown, where 1 is the outer layer material, 2 is the middle layer material, and 3 is the inner layer material, which is co-extruded from the outer layer material, the middle layer material, and the inner layer material described in the material for infusion hoses provided by the first aspect.

[0016] The infusion hose provided by the present invention is obtained by co-extrusion of an outer layer material, an intermediate layer material, and an inner layer material. The multi-layer co-extrusion process enables different materials to fully exert their respective characteristics and simultaneously form a tightly combined composite structure. The inner layer is responsible for biocompatibility and chemical stability, the intermediate layer provides mechanical support, and the outer layer protects the internal structure and provides impact resistance. The complementary and enhanced material properties are achieved, making the hose interface have higher comprehensive performance and being suitable for complex infusion scenarios.

[0017] Further, the thickness of the outer layer material is 25μm - 55μm; the thickness of the intermediate layer material is 870μm - 930μm; the thickness of the inner layer material is 45μm - 75μm.

[0018] Further, the thickness of the outer layer material is 45μm - 55μm; the thickness of the intermediate layer material is 900μm - 920μm; the thickness of the inner layer material is 45μm - 55μm.

[0019] Fourthly, the present invention provides an infusion soft bag, in which the infusion hose as described above is provided. Brief Description of the Drawings

[0020] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the drawings required to be used in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0021] Figure 1 It is a schematic structural diagram of the infusion hose in the present invention, where 1 is the outer layer material, 2 is the intermediate layer material, and 3 is the inner layer material. Detailed Embodiments

[0022] In order to make the objectives, technical solutions, and advantages of the present invention clearer, the following further details the present invention in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0023] To better illustrate what is provided in the embodiments of the present invention, the following further gives examples through embodiments.

[0024] The polylactic acid - lactide copolymer selected in the embodiments of the present invention is purchased from Evonik Industries; The bio-based polyethylene terephthalate is purchased from BASF Corporation; Polyhydroxybutyrate was purchased from Tian'an Biomaterials Co., Ltd.; Ethylene-vinyl acetate copolymer was purchased from Hanwha Group.

[0025] Example 1 This example provides an infusion hose and its preparation method, and the specific content is as follows: I. This example provides an infusion hose, which is made of infusion hose material. The infusion hose material is obtained by co-extrusion of an outer layer material, an intermediate layer material and an inner layer material with thicknesses of 50 μm, 900 μm and 50 μm in sequence; among them, the layer ratio of the outer layer material, the intermediate layer material and the inner layer material is 5%:90%:5%.

[0026] Based on the total weight of the outer layer material being 100%, the outer layer material includes 30% by mass of PLLA-PLGA and 70% by mass of Bio-PET; Based on the total weight of the intermediate layer material being 100%, the intermediate layer material includes 75% by mass of PHB and 25% by mass of Bio-PET; Based on the total weight of the inner layer material being 100%, the inner layer material includes 50% by mass of PHB, 10% by mass of EVA and 40% by mass of Bio-PET.

[0027] II. This example also provides a preparation method for the above infusion hose. The preparation method specifically includes the following steps: S1. According to the set ratio, weigh the raw materials of different layers according to the preset ratio, mix and knead them, extrude into strands, cool and cut into pellets, and granulate the raw materials of different layers to obtain outer layer masterbatch, intermediate layer masterbatch and inner layer masterbatch; S2. Using the outer layer masterbatch, intermediate layer masterbatch and inner layer masterbatch as raw materials, each layer of masterbatch is melted and plasticized by an independent extruder, and the rotational speed of the extruder is adjusted according to the set layer thickness ratio to obtain the melts of each layer; The melts of each layer converge through a multi-channel composite die head. The die head is designed with a layered flow channel to ensure that the materials of each layer are stacked in sequence and there is no mixing at the interface. The extruded composite pipe is expanded to the set size by vacuum, passed through a vacuum cooling and shaping tank, and the diameter of the pipe is controlled by traction by a tractor (in this invention, an example of obtaining a diameter of 8.1 cm is used for illustration), and finally wound up to obtain an infusion hose, denoted as infusion hose I.

[0028] Among them, in step S1, mixing, kneading and granulation are carried out using a single-screw extruder, and the process parameters of the extruder are shown in Table 1.

[0029] Table 1 Extruder process conditions

[0030] Among them, the cooling water tank uses the process water obtained by the purified water preparation process, which is obtained after being cooled by closed refrigeration. The water quality requirements are that there should be no impurities and visible foreign matters.

[0031] The rotation speed of the pelletizer is controlled according to the pelletizing effect, and the particle size of the masterbatch is in the range of 3 mm to 5 mm.

[0032] In step S2, the requirements for setting the process parameters of the extruder when preparing the melts of different layers are shown in Table 2. The temperature setting parameters of the extruder when preparing the melts of the outer layer and the inner layer are shown in Table 3, and the temperature setting parameters of the extruder when preparing the melt of the intermediate layer are shown in Table 4.

[0033] Table 2 Requirements for setting the process parameters of the extruder when preparing the melts of different layers

[0034] Table 3 Temperature setting parameters of the extruder when preparing the melts of the outer layer and the inner layer

[0035] Table 4 Temperature setting parameters of the extruder when preparing the melt of the intermediate layer

[0036] Example 2 This example provides an infusion hose, which is made of an infusion hose material. The infusion hose material is co-extruded from an outer layer material, an intermediate layer material and an inner layer material with thicknesses of 30 μm, 900 μm and 70 μm in sequence; among them, the layer ratio of the outer layer material, the intermediate layer material and the inner layer material is 3%: 90%: 7%.

[0037] Based on the total weight of the outer layer material being 100%, the outer layer material includes 25% by mass of PLLA-PLGA and 75% by mass of Bio-PET; Based on the total weight of the intermediate layer material being 100%, the intermediate layer material includes 70% by mass of PHB and 30% by mass of Bio-PET; Based on the total weight of the inner layer material being 100%, the inner layer material includes 45% by mass of PHB, 10% by mass of EVA and 45% by mass of Bio-PET.

[0038] This example also provides a preparation method for the above-mentioned infusion hose. The preparation method is the same as that in Example 1, and the obtained infusion hose is denoted as infusion hose II.

[0039] Example 3 This embodiment provides an infusion hose, which is made of an infusion hose material. The infusion hose material is obtained by co-extrusion of an outer layer material, an intermediate layer material, and an inner layer material with thicknesses of 55 μm, 900 μm, and 45 μm in sequence; wherein, the layer ratio of the outer layer material, the intermediate layer material, and the inner layer material is 5.5%: 90%: 4.5%.

[0040] Based on the total weight of the outer layer material being 100%, the outer layer material includes 35% by mass of PLLA-PLGA and 65% by mass of Bio-PET; Based on the total weight of the intermediate layer material being 100%, the intermediate layer material includes 80% by mass of PHB and 20% by mass of Bio-PET; Based on the total weight of the inner layer material being 100%, the inner layer material includes 55% by mass of PHB, 10% by mass of EVA, and 35% by mass of Bio-PET.

[0041] This embodiment also provides a preparation method of the above infusion hose. The preparation method is the same as that of Example 1, and the obtained infusion hose is denoted as infusion hose III.

[0042] Example 4 This embodiment provides an infusion hose, which is made of an infusion hose material. The infusion hose material is obtained by co-extrusion of an outer layer material, an intermediate layer material, and an inner layer material with thicknesses of 55 μm, 880 μm, and 75 μm in sequence; wherein, the layer ratio of the outer layer material, the intermediate layer material, and the inner layer material is 5.5%: 87%: 7.5%.

[0043] Based on the total weight of the outer layer material being 100%, the outer layer material includes 30% by mass of PLLA-PLGA and 70% by mass of Bio-PET; Based on the total weight of the intermediate layer material being 100%, the intermediate layer material includes 70% by mass of PHB and 30% by mass of Bio-PET; Based on the total weight of the inner layer material being 100%, the inner layer material includes 45% by mass of PHB, 20% by mass of EVA, and 35% by mass of Bio-PET.

[0044] This embodiment also provides a preparation method of the above infusion hose. The preparation method is the same as that of Example 1, and the obtained infusion hose is denoted as infusion hose IV.

[0045] Example 5 This embodiment provides an infusion soft bag, and 2 infusion hoses provided in Example 1 are arranged in the infusion soft bag.

[0046] Comparative Example 1 This comparative example provides an infusion hose, which is made of infusion hose material. The infusion hose material and its thickness are basically the same as those in Example 1, except that: the composition of the outer layer material is replaced from "30% PLLA-PLGA by mass and 70% Bio-PET by mass" to "45% polypropylene (PP) by mass and 55% styrene-ethylene-butene-styrene copolymer (SEBS) by mass", and the composition of the remaining raw materials and the preparation process parameters remain unchanged. The obtained infusion hose is denoted as infusion hose pair Ⅰ.

[0047] Comparative Example 2 This comparative example provides an infusion hose, which is made of infusion hose material. The infusion hose material and its thickness are basically the same as those in Example 1, except that: the composition of the outer layer material is replaced from "30% PLLA-PLGA by mass and 70% Bio-PET by mass" to "30% PLLA-PLGA by mass and 70% polyethylene terephthalate (PET) by mass", and the composition of the remaining raw materials and the preparation process parameters remain unchanged. The obtained infusion hose is denoted as infusion hose pair Ⅱ.

[0048] Comparative Example 3 This comparative example provides an infusion hose, which is made of infusion hose material. The infusion hose material and its thickness are basically the same as those in Example 1, except that: the composition of the middle layer material is replaced from "75% PHB by mass and 25% Bio-PET by mass" to "55% polypropylene (PP) by mass and 45% styrene-ethylene-butene-styrene copolymer (SEBS) by mass", and the composition of the remaining raw materials and the preparation process parameters remain unchanged. The obtained infusion hose is denoted as infusion hose pair Ⅲ.

[0049] Comparative Example 4 This comparative example provides an infusion hose, which is made of infusion hose material. The infusion hose material and its thickness are basically the same as those in Example 1, except that: the composition of the inner layer material is replaced from "50% PHB by mass, 10% EVA by mass and 40% Bio-PET by mass" to "35% polypropylene (PP) by mass, 55% styrene-ethylene-butene-styrene copolymer (SEBS) by mass and ethylene-vinyl acetate copolymer (EVA)", and the composition of the remaining raw materials and the preparation process parameters remain unchanged. The obtained infusion hose is denoted as infusion hose pair Ⅳ.

[0050] Effect Example The longitudinal tensile strength, appearance, sealing performance, and insoluble particles of the infusion hoses prepared in the above examples and comparative examples were measured. The specific measurement methods are as follows: Longitudinal tensile strength: It was measured according to the tensile property determination method in General Chapter 4005 of the Fourth Part of the Chinese Pharmacopoeia (2020 Edition). The width of the test specimen was 15 mm, the test speed (no load) was 100 mm / min ± 10 mm / min, and the average value of the longitudinal tensile strength should not be lower than 10 MPa.

[0051] Appearance: Visually inspected directly in bright natural light. It should be transparent, smooth, and free of foreign matters visible to the naked eye; the infusion hose after sterilization should have no obvious deformation.

[0052] Insoluble particles: Take a test hose equivalent to a surface area of 100 cm² (about 40 cm in length), cut it into 5 cm long hoses, place them in a 250 mL conical flask, add 200 mL of injection water (cooled to room temperature), cover it, and rotate and shake it clockwise by hand. The rotation diameter is 50 mm, the rotation speed is about 1 circle / second, and the rotation and shaking time is about 20 seconds. After standing for 5 minutes, first detect the visible foreign matters in the water in the bottle, and then detect the insoluble particles. Pour the test solution into a sampling bottle (or directly place it on the sampler), let it stand, and continuously measure 4 times. Discard the first data and read the results of the last three measurements. There should be no visible foreign matters in the water in the bottle, the number of particles ≥ 10 μm should not exceed 15 particles / mL, and the number of particles ≥ 25 μm should not exceed 1.5 particles / mL.

[0053] Sealing performance: Take five connectors (made of carbonate), with an outer diameter at least 0.8 mm larger than the inner diameter of the tube. Insert the connectors into the tube at least 7 mm respectively. Sterilize the tube with the inserted connectors at 121 °C for 20 min. After cooling, cut off the part of the tube extending from the connector, make a cut on one side of the tube with a knife, and then peel off the tube from the connector and observe. There should be an obvious bonding phenomenon between the connector part and the tube.

[0054] The measurement results of the performance of different infusion hoses are shown in Table 5.

[0055] Table 5 Statistical table of the measurement results of the performance of different infusion hoses

[0056] Compared with infusion hose pairs Ⅰ to Ⅱ, the infusion hose Ⅰ prepared in Example 1 exhibits higher mechanical strength and significant heat resistance performance advantages. In addition, compared with infusion hose pair Ⅰ, PLLA-PLGA and Bio-PET used in the present invention are bio-based materials, with a 30% to 40% reduction in carbon emissions. In contrast, the replaced formulations of PP and SEBS are non-degradable materials, with significantly inferior environmental performance. Compared with infusion hose pair Ⅱ, PET is a petroleum-based material that cannot be degraded and has a high carbon emissions. In contrast, Bio-PET in the present invention is a bio-based material, with a 30% to 40% reduction in carbon emissions, and has excellent environmental performance.

[0057] Compared with infusion hose pair Ⅲ, the infusion hose Ⅰ exhibits more excellent mechanical properties. In addition, PHB is a completely biodegradable material, and its environmental performance is significantly superior to that of non-degradable PP and SEBS.

[0058] Compared with infusion hose pair Ⅳ, the infusion hose Ⅰ exhibits more excellent mechanical properties. In addition, the combined carbon emissions of PHB and Bio-PET are significantly lower than those of PP and SEBS.

[0059] In the prior art, PP and SEBS of infusion hoses completely rely on petrochemical-based sources, do not have biodegradability, and have high carbon emissions. In contrast, PLLA-PLGA and PHB in the materials of the present invention are completely biodegradable materials, and Bio-PET is partially derived from plant-based ethylene glycol, with an overall 30% to 40% reduction in carbon emissions, demonstrating excellent environmental performance. The infusion hose provided by the present invention meets or exceeds the key indicators such as longitudinal tensile strength, appearance, sealing performance, and particle release of the replacement materials. At the same time, due to the introduction of bio-based components, the materials of the present invention have significant advantages in environmental performance, meet the requirements of green medical devices, and demonstrate high technological innovation and application value.

[0060] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, or improvements made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A material for an infusion tube, characterized in that, It includes an outer layer material, an intermediate layer material, and an inner layer material; Among them, the outer layer material includes a polylactic acid - lactide copolymer and a bio - based polyethylene terephthalate; The intermediate layer material includes a polyhydroxybutyrate and a bio - based polyethylene terephthalate; The inner layer material includes a polyhydroxybutyrate, an ethylene - vinyl acetate copolymer, and a bio - based polyethylene terephthalate.

2. The material for the infusion flexible tube according to claim 1, characterized in that, Based on the total weight of the outer layer material being 100%, the outer layer material includes 25% - 35% by mass of the polylactic acid - lactide copolymer and 65% - 75% by mass of the bio - based polyethylene terephthalate; and / or Based on the total weight of the intermediate layer material being 100%, the intermediate layer material includes 70% - 80% by mass of the polyhydroxybutyrate and 20% - 30% by mass of the bio - based polyethylene terephthalate; and / or Based on the total weight of the inner layer material being 100%, the inner layer material includes 45% - 55% by mass of the polyhydroxybutyrate, 10% - 25% by mass of the ethylene - vinyl acetate copolymer, and 35% - 45% by mass of the bio - based polyethylene terephthalate.

3. The material for an infusion tube according to claim 1 or 2, characterized in that, The layer ratio of the outer layer material, the intermediate layer material, and the inner layer material is 2.5% - 5.5%: 87% - 93%: 4.5% - 7.5%.

4. The material for the infusion tube according to claim 1, characterized in that, The bio - based polyethylene terephthalate is prepared from plant - based ethylene glycol and terephthalic acid, and its bio - based carbon content is 30% - 50%.

5. Use of the material for an infusion hose according to any one of claims 1 - 4 in the preparation of an infusion hose.

6. An infusion hose, characterized in that, It is co - extruded from the outer layer material, the intermediate layer material, and the inner layer material in the material for an infusion hose according to any one of claims 1 - 4.

7. The infusion hose according to claim 6, wherein, The thickness of the outer layer material is 25μm - 55μm; and / or The thickness of the intermediate layer material is 870μm - 930μm; and / or The thickness of the inner layer material is 45μm - 75μm.

8. The infusion hose according to claim 6, characterized in that, The thickness of the outer layer material is 45μm - 55μm; and / or The thickness of the intermediate layer material is 900μm - 920μm; and / or The thickness of the inner layer material is 45μm - 55μm.

9. An infusion soft bag, characterized in that, An infusion hose according to any one of claims 6 - 8 is provided in the infusion soft bag.

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