Multilayer ultrathin interventional protective glove and preparation method thereof

Abstract

The invention relates to the technical field of protective tools for interventional operations, and particularly discloses a multi-layer ultrathin interventional protective glove and a preparation method thereof aiming at the problems that an effective protective effect cannot be achieved due to the fact that a common protective glove which can be used for interventional radiation at present is too thin, and the operation flexibility of medical staff is affected due to the fact that the protective glove is too thick. The multi-layer ultrathin interventional protective glove comprises a skin-friendly layer, at least one main protective layer and at least one secondary protective layer which are sequentially overlapped, and the thickness of the interventional protective glove is 0.20-0.30 mm; each of the main protective layer and the secondary protective layer comprises natural latex and a radiation protection functional filler, the radiation protection functional filler comprises radiation-proof particles in various size grading, and the filling mass of the radiation protection functional filler in the main protective layer is greater than that of the radiation protection functional filler in the secondary protective layer. By compounding and combining multiple layers of materials, it can be guaranteed that the glove has an effective anti-radiation effect, and the glove is small in thickness, large in elasticity and higher in use and wearing comfort.

Description

Technical Field

[0001] The present invention relates to the technical field of interventional surgical protective gear, and in particular to a multi-layer ultra-thin interventional protective glove and a preparation method thereof. Background Art

[0002] As interventional radiology becomes increasingly important in the medical field, more and more departments and physicians are beginning to introduce or apply interventional radiology techniques in clinical treatment. Interventional radiology involves inserting specialized catheters or instruments into the lesion site through percutaneous puncture or through pre-existing orifices of the human body, guided by imaging modalities such as X-rays, ultrasound, CT, and MRI, for diagnostic imaging and treatment, or tissue collection for cytological, bacteriological, and biochemical testing. However, medical personnel performing interventional radiology procedures face long-term close exposure to radioactive rays, which can have serious health risks, necessitating the use of high-performance protective equipment.

[0003] Among interventional protective equipment, gloves are particularly important for medical personnel. From lead-containing protective gloves to lead-free ones, interventional protective gloves have undergone several years of development. For example, patent publication number CN106213630A provides a multi-layer radiation protection glove and its manufacturing process. The glove comprises an overlapping gamma-ray shielding layer and a neutron shielding layer. The gamma-ray shielding material is one or more of tungsten oxide, bismuth oxide, gadolinium oxide, tin oxide, antimony oxide, cerium oxide, indium oxide, tantalum oxide, zirconium oxide, yttrium oxide, neodymium oxide, and praseodymium oxide. The glove body has a thickness of 0.2 to 2.5 mm.

[0004] However, in order to achieve a practical and effective protective effect, the average thickness of the interventional radiation protection gloves mentioned above is usually above 0.3 mm. In addition, the multi-layer composite material structure makes the total thickness of the interventional radiation protection gloves relatively thick, which greatly affects the operational flexibility of medical staff. Summary of the Invention

[0005] The purpose of the present invention is to solve the problem that currently common protective gloves that can be used for interventional radiology are too thin to achieve effective protection and too thick to affect the operational flexibility of medical staff.

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

[0007] The present invention provides a multi-layer ultra-thin interventional protective glove, comprising a skin-friendly layer, at least one primary protective layer and at least one secondary protective layer stacked in sequence, and the thickness of the interventional protective glove is 0.20-0.30 mm; the primary protective layer and the secondary protective layer both comprise natural rubber latex and radiation protection functional filler, the radiation protection functional filler comprises radiation protection particles of multiple size grades, and the filling mass of the radiation protection functional filler in the primary protective layer is greater than the filling mass of the radiation protection functional filler in the secondary protective layer.

[0008] Preferably, the radiation-proof particles include any one or more of bismuth and its oxides, gadolinium and its oxides, and erbium and its oxides; and according to the particle size range, the radiation-proof particles are divided into micron-level powders, submicron-level powders and nano-level powders, and the particle size range of micron-level powders is 1-10μm, the particle size range of submicron-level powders is 0.1-1μm, and the particle size range of nano-level powders is <100nm.

[0009] Preferably, the volume proportion of micron-sized powder is 10-25%, the volume proportion of submicron-sized powder is 70-80%, and the volume proportion of nano-sized powder is 5-10%.

[0010] Preferably, the mass proportion of the radiation protection functional filler in the primary protective layer is greater than the mass proportion of the radiation protection functional filler in the secondary protective layer.

[0011] Preferably, in the primary protective layer and the secondary protective layer, the mass ratio of the radiation protection functional filler to the natural rubber latex is 0.3-3.0:1.0.

[0012] Preferably, the number of layers of the primary protective layer is 1-5 layers; the number of layers of the secondary protective layer is 1-3 layers.

[0013] The present invention provides a method for preparing the above-mentioned multi-layer ultra-thin interventional protective gloves, comprising the following steps:

[0014] S1 Preparation of dispersion containing radiation protection functional filler:

[0015] Mixing radiation protection particles of various sizes to obtain composite filler particles; mixing the composite filler particles with a dispersant and ball milling; then adding a surface modifier in a water bath or oil bath at 25-80°C to carry out a modification reaction to obtain a dispersion containing a radiation protection filler;

[0016] S2 compound latex preparation:

[0017] Add the vulcanizing agent to the natural rubber latex, stir and mix, heat to 30-50°C, stir and mature for 3-5 hours to obtain a pre-vulcanized compounded latex; then add the dispersion prepared in step S1 to the pre-vulcanized compounded latex, stir and mix to obtain a composite latex;

[0018] S3 gloves dipping vulcanization:

[0019] The glove mold is cleaned and dried, immersed in a coagulant, taken out and dried, placed in the composite latex of the secondary protective layer, dipped once or multiple times, and dried; then taken out and placed in the composite latex of the primary protective layer, dipped once or multiple times, and dried; then taken out and placed in the composite latex of the skin-friendly layer, dipped once or multiple times, and dried; and finally curling, leaching, vulcanization, surface treatment, drying, and demoulding are performed in sequence to obtain the multi-layer ultra-thin interventional protective gloves.

[0020] Preferably, in step S2, the dispersant accounts for 0.5-5.0 wt% of the mass of the composite filler particles, and the surface modifier accounts for 1.0-3.0 wt% of the total mass of the ball-milled mixture.

[0021] Preferably, in step S2, after adding the surface modifier, the pH value of the reaction system is adjusted to 4.0-5.0 or 9.0-10.0 before the reaction is carried out.

[0022] Preferably, in step S2, before adding the dispersion to the pre-vulcanized compound latex, a pH regulator is added dropwise to the pre-vulcanized compound latex and the dispersion, respectively, so that the pH values ​​of the pre-vulcanized compound latex and the dispersion are adjusted to 10.0-13.5; wherein the pH regulator includes an inorganic base and / or an organic base, the inorganic base includes one or more of sodium hydroxide, potassium hydroxide, and water glass, and the organic base includes tetramethylammonium hydroxide.

[0023] The technical solution of the present invention has the following beneficial effects:

[0024] The multi-layer ultra-thin interventional protective gloves and the preparation method thereof proposed in the present invention prepare radiation-proof particles containing various size ranges through grading, so that they have a higher filling amount per unit volume of the rubber system; through ball milling dispersion and modification, the problem of easy sedimentation of radiation-proof particles and uneven composite latex system caused by high filling amount of conventional ingredients is solved; and by adopting different filling amounts, a primary protective layer and a secondary protective layer with primary and secondary protection effects are formed, and the middle primary protective layer provides a significant radiation shielding effect, which can achieve the protection effect required in this field, and the surface protective layer can have relatively outstanding softness and elasticity on the basis of auxiliary protection; combined with the skin-friendly layer, the gloves can be given good flexibility, elasticity and comfort, forming a multi-layer ultra-thin structure interventional protective gloves, which can improve the overall elasticity, flexibility and comfort of the gloves through different layers of materials while maintaining an effective radiation shielding effect, so as to facilitate medical staff in grasping and other operations during interventional surgery. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Schematic diagram of the arrangement of composite filler particles in the present invention;

[0026] Figure 2 Schematic diagram of the hierarchical structure of the multi-layer ultra-thin interventional protective gloves of the present invention. DETAILED DESCRIPTION

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed; and where the manufacturers of the instruments, equipment, reagents, and raw materials used are not specified, they are all commercially available conventional products.

[0028] The present invention provides a multi-layer ultra-thin interventional protective glove. The gloves are made by using natural rubber latex as a base rubber, adding composite filler particles with radiation protection functions to form a functional composite latex, and then forming the gloves through hand mold dipping to produce an ultra-thin interventional protective glove with a multi-layer structure. The preparation method includes the following steps:

[0029] (1) Preparation of dispersion containing radiation protection functional filler

[0030] Take radiation-proof particles, including but not limited to any one or more of bismuth, gadolinium, erbium, bismuth trioxide, gadolinium oxide and erbium oxide, and grade them to obtain composite filler particles, which are precisely and evenly arranged to achieve a high filling amount per unit volume. The arrangement of the composite filler particles is as follows: Figure 1 shown.

[0031] The composite filler particles are graded composite particles comprising micron-sized powder, submicron-sized powder and nano-sized powder. Specifically, the grading is as follows: the particle size range of the micron-sized powder is 1-10 μm, accounting for 10-25% by volume; the particle size range of the submicron-sized powder is 0.1-1 μm, accounting for 70-80% by volume; the particle size range of the nano-sized powder is <100 nm, accounting for 5-10% by volume.

[0032] Incorporating the aforementioned mixed-size composite filler particles into the preparation of natural rubber latex gloves can yield a soft film. Specifically, excessive micron-sized powders can lead to poor stability of the composite, while excessive nano-sized powders can increase film hardness and reduce softness.

[0033] 0.5-5.0 wt% of a dispersant is added to the composite filler particles, and the mixture is dispersed by ball milling to form a primary dispersion. The primary dispersion is then placed in a water bath or oil bath at 25-80° C., 1.0-3.0 wt% of a surface modifier is added, and the surface modifier can be a silane or titanate coupling agent. The pH value of the material system is adjusted to 4.0-5.0 or 9.0-10.0, and the mixture is reacted for 0.5-5.0 hours under stirring to obtain a highly dispersed radiation protection functional filler containing the radiation protection functional filler.

[0034] During the ball milling process, the composite filler particles and dispersant undergo friction, collision, and shear, breaking up filler particle clusters or pseudoparticles that have been agglomerated by hydrogen bonding or charge adsorption, thereby forming a primary dispersion. Surface modification treatment then imparts a certain degree of hydrophobicity to the surface of the composite filler particles. Specifically, the resulting surface-modified radiation-protective filler exhibits a contact angle of 60°-120°. When the contact angle is too small, the radiation-protective filler readily settles in the composite latex. However, when the contact angle is too large, the hydrophobicity of the radiation-protective filler is too strong, preventing it from being fully dispersed in the latex to form a uniform system.

[0035] In the present invention, the primary dispersion obtained by grinding and dispersion has reversible depolymerization and agglomeration, and secondary agglomeration will still occur when it is left at rest. Based on this, the present invention further proposes to use a surface modifier to modify the surface of the powder, grafting hydrophobic groups to the surface of the powder, reducing the surface energy of the particles, thereby hindering the secondary agglomeration between the powder particles. Specifically, the hydrophobic groups grafted to the surface of the powder have a dual effect. First, the hydrophobic groups are more affinity with rubber molecules, making them less likely to settle in the composite rubber, thereby improving the stability of the composite rubber; second, the hydrophobic groups will participate in the later rubber vulcanization process, which can improve the mechanical properties of the film to a certain extent.

[0036] (2) Preparation of composite latex

[0037] Add the vulcanizing compounding agent to the natural rubber latex, stir and mix at a low speed, heat to 30-50°C, stir and mature for 3-5 hours to obtain a pre-vulcanized compounded latex; mix the dispersion containing the radiation protection functional filler and the pre-vulcanized compounded latex at a mass ratio of 0.3-3.0:1.0, stir slowly at room temperature for more than 24 hours to obtain a composite latex.

[0038] Before adding the dispersion to the pre-vulcanized compound latex, a pH regulator is added dropwise to the pre-vulcanized compound latex and the dispersion, respectively, so that the pH values ​​of the pre-vulcanized compound latex and the dispersion are adjusted to 10.0-13.5; wherein the pH regulator includes an inorganic base and / or an organic base, the inorganic base includes one or more of sodium hydroxide, potassium hydroxide, and water glass, and the organic base includes tetramethylammonium hydroxide.

[0039] (3) Molding vulcanization treatment

[0040] The glove mold for making interventional protective gloves is cleaned, immersed in a calcium salt coagulant, taken out and dried, placed in the composite latex of the secondary protective layer, dipped once or multiple times, and dried; then taken out and placed in the composite latex of the primary protective layer, dipped once or multiple times, and dried; finally taken out and placed in the composite latex of the skin-friendly layer, dipped once or multiple times, and dried, and the steps of curling, leaching, vulcanization, surface treatment, drying, and demoulding are sequentially performed to obtain interventional protective gloves with a multi-layer ultra-thin structure. The hierarchical structure of the interventional protective gloves is as follows: Figure 2 The total thickness of the interventional protective gloves is 0.20-0.30 mm, and the thickness of the main protective layer is ≥ 0.20 mm.

[0041] The present invention can prepare a multi-layer ultra-thin protective glove through the above-mentioned multiple dipping and drying processes, including a skin-friendly layer, a main protective layer with a high radiation protection filling amount, and a secondary protective layer with a low radiation protection filling amount stacked in sequence. On the basis of having a significant and effective radiation protection effect, the protective glove has a thinner total thickness and comfortable properties such as high elasticity, which can provide medical staff with higher operational flexibility and comfort when using it.

[0042] Example 1

[0043] Step 1: Take bismuth trioxide, gadolinium particles and erbium oxide respectively, mix them, grind them, and sieve them to separate micron-level powder with a particle size of 3.5-5μm, submicron-level powder with a particle size of 0.2-0.5μm and nano-level powder with a particle size of 50-75nm, and mix the above radiation-proof particles of different sizes in a volume ratio of 18:75:7 to obtain composite filler particles.

[0044] Step 2: Take composite filler particles, add 3.2wt% of sodium methylenebisnaphthalene sulfonate based on the mass of the composite filler particles, mix and place in a ball mill for ball milling to fully and evenly disperse the materials to obtain a primary dispersion; then place the primary dispersion in a 60°C water bath, add 1.6wt% of a titanate coupling agent based on the mass of the primary dispersion, and adjust the pH value of the material system to 4.7 by dropwise addition of acetic acid. Continue stirring at 180rpm and react for 1.5h to obtain a dispersion containing a radiation protection functional filler.

[0045] Step 3: Add 2.2 wt% of a vulcanizing compounding agent (Octocure TC01, purchased from Tiarco Chemical Company) to the natural rubber latex, place the above materials in a 40° C. water bath, and stir at 300 rpm for 5.0 h to obtain a pre-vulcanized compounded latex.

[0046] Step 4: Adjust the pH value of the above dispersion and pre-vulcanized compound latex to 12.8 with 10wt% potassium hydroxide solution respectively; then mix the above dispersion with natural rubber latex at a mass ratio of 2.0:1.0 to obtain a high-filled composite latex; similarly, adjust the mass ratio of the dispersion to natural rubber latex to 0.5:1.0 in the above manner, and keep other processes unchanged to prepare a low-filled composite latex.

[0047] Step 5: Take the glove mold for making interventional protective gloves, clean it and dry it; impregnate the glove mold with a coagulant, take it out and dry it; then impregnate the glove mold with a low-filling composite latex, take it out and dry it to form a secondary protective layer with a thickness of about 0.03 mm; then place the glove mold in a high-filling composite latex, impregnate it, take it out and dry it, and repeat the impregnation and drying process three times to form a primary protective layer with a total thickness of about 0.20 mm; finally, impregnate the glove mold with a pre-vulcanized compound latex, take it out and dry it to form a skin-friendly layer with a thickness of about 0.02 mm; the primary gloves are curled, leached, vulcanized, surface treated, dried and demolded in sequence to obtain interventional protective gloves.

[0048] Example 2

[0049] Step 1: Take bismuth trioxide, gadolinium particles and erbium oxide respectively, mix them, grind them, and sieve them to separate micron-level powder with a particle size of 3.5-5μm, submicron-level powder with a particle size of 0.2-0.5μm and nano-level powder with a particle size of 50-75nm, and mix the above radiation-proof particles of different sizes in a volume ratio of 12:78:10 to obtain composite filler particles.

[0050] Step 2: Take the composite filler particles, add 2.5wt% of sodium dodecylbenzenesulfonate based on the mass of the composite filler particles, mix and place in a ball mill for ball milling to fully and evenly disperse the materials to obtain a primary dispersion; then place the primary dispersion in a 60°C water bath, add 2.0wt% of silane coupling agent A-171 based on the mass of the primary dispersion, and adjust the pH value of the material system to 4.5 by adding acetic acid, continue stirring at 250rpm, and react for 2.5h to obtain a dispersion of radiation protection functional filler.

[0051] Step 3: Add 2.5 wt% of a vulcanizing compounding agent (Octocure TC01, purchased from Tiarco Chemical Company) to the natural rubber latex, place the above materials in a 50° C. water bath, and stir at 300 rpm for 3.0 h to obtain a pre-vulcanized compounded latex.

[0052] Step 4: Adjust the pH value of the above dispersion and pre-vulcanized compound latex to 13.2 with 10wt% sodium hydroxide solution respectively; then mix the above dispersion with natural latex at a mass ratio of 2.2:1.0 to obtain a high-filling composite latex; similarly, adjust the mass ratio of the dispersion to natural latex to 0.3:1.0 in the above manner, and keep other processes unchanged to prepare a low-filling composite latex.

[0053] Step 5: Take the glove mold for making interventional protective gloves, clean it and dry it; impregnate the glove mold with a coagulant, take it out and dry it; then impregnate the glove mold with a low-filling composite latex, take it out and dry it to form a secondary protective layer with a thickness of about 0.05 mm; then place the glove mold in a high-filling composite latex, impregnate it, take it out and dry it, and repeat the impregnation and drying process three times to form a primary protective layer with a total thickness of about 0.22 mm; finally, impregnate the glove mold with pre-vulcanized compound latex, take it out and dry it to form a skin-friendly layer with a thickness of about 0.02 mm; the primary gloves are curled, leached, vulcanized, surface treated, dried and demolded in sequence to obtain interventional protective gloves.

[0054] Example 3

[0055] Step 1: Take bismuth trioxide, gadolinium particles and erbium oxide respectively, mix them, grind them, and sieve them to separate micron-level powder with a particle size of 3.5-5μm, submicron-level powder with a particle size of 0.2-0.5μm and nano-level powder with a particle size of 50-75nm, and mix the above radiation-proof particles of different sizes in a volume ratio of 18:75:7 to obtain composite filler particles.

[0056] Step 2: Take the composite filler particles, add 1.0wt% of polyvinyl pyrrolidone based on the mass of the composite filler particles, mix and place in a ball mill for ball milling to fully and evenly disperse the materials to obtain a primary dispersion; then place the primary dispersion in a 60°C water bath, add 1.0wt% of the silane coupling agent KH-570 based on the mass of the primary dispersion, and adjust the pH value of the material system to 5.5 by adding acetic acid, continue stirring at 300rpm, and react for 3.0h to obtain a dispersion of radiation protection functional filler.

[0057] Step 3: Add 2.0 wt% of a vulcanizing compounding agent (Octocure TC01, purchased from Tiarco Chemical Company) to the natural rubber latex, place the above materials in a 50° C. water bath, and stir at 300 rpm for 3.0 h to obtain a pre-vulcanized compounded latex.

[0058] Step 4: Adjust the pH value of the above dispersion and pre-vulcanized compound latex to 13.0 respectively using a water glass solution with a modulus of 1.8; then mix the above dispersion with natural latex at a mass ratio of 1.8:1.0 to obtain a high-filled composite latex; similarly, adjust the mass ratio of the dispersion to natural latex to 0.75:1.0 in the above manner, and keep other processes unchanged to prepare a low-filled composite latex.

[0059] Step 5: Take the glove mold for making interventional protective gloves, clean it and dry it; impregnate the glove mold with a coagulant, take it out and dry it; then impregnate the glove mold with a low-filling composite latex, take it out and dry it to form a secondary protective layer with a thickness of about 0.02 mm; then place the glove mold in a high-filling composite latex, impregnate it, take it out and dry it, and repeat the impregnation and drying process three times to form a primary protective layer with a total thickness of about 0.24 mm; finally, impregnate the glove mold with a pre-vulcanized compound latex, take it out and dry it to form a skin-friendly layer with a thickness of about 0.02 mm; the primary gloves are curled, leached, vulcanized, surface treated, dried and demolded in sequence to obtain interventional protective gloves.

[0060] Example 4

[0061] Step 1: Take bismuth trioxide, gadolinium particles and erbium oxide respectively, mix them, grind them, and sieve them to separate micron-level powder with a particle size of 3.5-5μm, submicron-level powder with a particle size of 0.2-0.5μm and nano-level powder with a particle size of 50-75nm, and mix the above radiation-proof particles of different sizes in a volume ratio of 10:80:10 to obtain composite filler particles.

[0062] Step 2: Take the composite filler particles, add 2.5wt% of sodium methylenebisnaphthalene sulfonate and 1.5wt% of PEG-4000 based on the mass of the composite filler particles, mix and place in a ball mill for ball milling to fully and evenly disperse the materials to obtain a primary dispersion; then place the primary dispersion in a 60°C water bath, add 1.5wt% of the silane coupling agent WD-51 based on the mass of the primary dispersion, and adjust the pH value of the material system to 9.5 by adding acetic acid, continue stirring at 300rpm, and react for 5.0h to obtain a dispersion of radiation protection functional filler.

[0063] Step 3: Add 2.5 wt% of a vulcanizing compounding agent (Octocure TC01, purchased from Tiarco Chemical Company) to the natural rubber latex, place the above materials in a 40° C. water bath, and stir at 300 rpm for 4.5 hours to obtain a pre-vulcanized compounded latex.

[0064] Step 4: Adjust the pH value of the above dispersion and pre-cured compound latex to 13.5 with 15wt% tetramethylammonium hydroxide solution respectively; then mix the above dispersion with natural latex at a mass ratio of 2.5:1.0 to obtain a high-filling composite latex; similarly, adjust the mass ratio of the dispersion to natural latex to 0.5:1.0 in the above manner, and keep other processes unchanged to prepare a low-filling composite latex.

[0065] Step 5: Take the glove mold for making interventional protective gloves, clean it and dry it; impregnate the glove mold with a coagulant, take it out and dry it; then impregnate the glove mold with a low-filling composite latex, take it out and dry it to form a secondary protective layer with a thickness of about 0.05 mm; then place the glove mold in a high-filling composite latex, impregnate it, take it out and dry it, and repeat the impregnation and drying process three times to form a primary protective layer with a total thickness of about 0.23 mm; finally, impregnate the glove mold with a pre-vulcanized compound latex, take it out and dry it to form a skin-friendly layer with a thickness of about 0.02 mm; the primary gloves are curled, leached, vulcanized, surface treated, dried and demolded in sequence to obtain interventional protective gloves.

[0066] Example 5

[0067] Step 1: Take bismuth trioxide, gadolinium particles and erbium oxide respectively, mix them, grind them, and sieve them to separate micron-level powder with a particle size of 3.5-5μm, submicron-level powder with a particle size of 0.2-0.5μm and nano-level powder with a particle size of 50-75nm, and mix the above radiation-proof particles of different sizes in a volume ratio of 15:80:5 to obtain composite filler particles.

[0068] Step 2: Take composite filler particles, add 2.0wt% of sodium dodecylbenzenesulfonate and 1.0wt% of polyvinylpyrrolidone based on the mass of the composite filler particles, mix and place in a ball mill for ball milling to fully and evenly disperse the materials to obtain a primary dispersion; then place the primary dispersion in a 60°C water bath, add 0.5wt% of silane coupling agent KH-570 and 1.0wt% of silane coupling agent Si-75 based on the mass of the primary dispersion, and adjust the pH value of the material system to 5.0 by adding acetic acid, continue stirring at 300rpm, and react for 4.0h to obtain a dispersion of radiation protection functional filler.

[0069] Step 3: Add 2.8 wt% of a vulcanizing compounding agent (Octocure TC01, purchased from Tiarco Chemical Company) to the natural rubber latex, place the above materials in a 30° C. water bath, and stir at 300 rpm for 5.0 h to obtain a pre-vulcanized compounded latex.

[0070] Step 4: Adjust the pH value of the above dispersion and pre-vulcanized compound latex to 13.2 with 10wt% potassium hydroxide solution respectively; then mix the above dispersion with natural latex at a mass ratio of 3.0:1.0 to obtain a high-filled composite latex; similarly, adjust the mass ratio of the dispersion to natural latex to 0.3:1.0 in the above manner, and keep other processes unchanged to prepare a low-filled composite latex.

[0071] Step 5: Take the glove mold for making interventional protective gloves, clean it and dry it; impregnate the glove mold with a coagulant, take it out and dry it; then impregnate the glove mold with a low-filling composite latex, take it out and dry it to form a secondary protective layer with a thickness of about 0.04 mm; then place the glove mold in a high-filling composite latex, impregnate it, take it out and dry it, and repeat the impregnation and drying process three times to form a primary protective layer with a total thickness of about 0.20 mm; finally, impregnate the glove mold with a pre-vulcanized compound latex, take it out and dry it to form a skin-friendly layer with a thickness of about 0.02 mm; the primary gloves are curled, leached, vulcanized, surface treated, dried and demolded in sequence to obtain interventional protective gloves.

[0072] Comparative Example 1

[0073] Step 1: Bismuth trioxide, gadolinium particles, and erbium oxide are each prepared, wherein the particle size of the bismuth trioxide, gadolinium particles, and erbium oxide is 0.5-1 μm, and the mixture is mixed. 3.5 wt% sodium methylene bisnaphthalene sulfonate and 1.5 wt% titanate coupling agent are then added to the mixture. The pH of the mixture is adjusted to 5.0 with acetic acid. The mixture is stirred at 180 rpm in a 60°C water bath for 1.5 hours to obtain a dispersion of a radiation protection filler.

[0074] Step 2: Adjust the pH value of the pre-vulcanized compound latex and the radiation protection functional filler dispersion to 12.0; then mix the dispersion with natural rubber latex at a mass ratio of 1.5:1.0 to obtain a glove composite latex.

[0075] Step 3: Take the glove mold used to make interventional protective gloves, clean it, dry it, dip the glove mold into the coagulant, take it out and dry it; then dip the glove mold into the glove composite latex, take it out and dry it, and repeat the dipping and drying process three times to form a latex glove with a total thickness of about 0.21 mm.

[0076] Comparative Example 2

[0077] Step 1: Bismuth trioxide, gadolinium particles, and erbium oxide are each prepared, wherein the particle size of the bismuth trioxide, gadolinium particles, and erbium oxide is 0.5-1 μm, and the mixture is mixed. 1.0 wt% of polyvinyl pyrrolidone and 2.0 wt% of silane coupling agent A-171 are then added to the mixture. The pH of the mixture is adjusted to 4.5 with acetic acid. The mixture is stirred at 180 rpm in a 60°C water bath for 2.5 hours to obtain a dispersion of a radiation protection functional filler.

[0078] Step 2: Adjust the pH value of the pre-vulcanized compound latex and the radiation protection functional filler dispersion to 13.0; then mix the dispersion with natural rubber latex at a mass ratio of 1.8:1.0 to obtain a glove composite latex.

[0079] Step 3: Take the glove mold used to make interventional protective gloves, clean it, dry it, dip the glove mold into the coagulant, take it out and dry it; then dip the glove mold into the glove composite latex, take it out and dry it, and repeat the dipping and drying process 5 times to form a latex glove with a total thickness of about 0.35 mm.

[0080] Test example

[0081] Sample: interventional protective gloves prepared in Examples 1-5 and Comparative Examples 1-2

[0082] The above samples were taken separately, and the thickness, tear force, and elongation at break of the above samples were measured according to the requirements for interventional protective gloves in GBZ 130-2020 "Radiological Protection Requirements for Diagnostic Radiology" and GB / T 7543-2020 "Single-Use Sterilized Rubber Surgical Gloves". Then, the shielding performance of the above samples against X-rays was measured according to the test method provided in GBZ / T 147-2002 "Determination of Attenuation Properties of X-ray Protective Materials". The measurement results are shown in Table 1 below:

[0083] Table 1 Material properties test results of different samples

[0084]

[0085] The performance test results of the samples above demonstrate that the interventional protective gloves prepared in Examples 1 to 5 demonstrate significant X-ray shielding effectiveness at 120 kV tube voltage, and significantly outperform the radiation-protective latex gloves prepared using the conventional methods in Comparative Examples 1 and 2 in terms of tensile strength. Furthermore, their thickness and tensile strength demonstrate enhanced flexibility and comfort during use. This demonstrates that the interventional protective gloves proposed by the present invention, through their multi-layered structural design and optimized materials at each layer, achieve a balanced performance of radiation protection and comfort, effectively addressing the inflexibility inherent in existing protective gloves.

[0086] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A multi-layer ultra-thin interventional protective glove, characterized in that: The interventional protective gloves comprise a skin-friendly layer, at least one main protective layer and at least one secondary protective layer stacked in sequence, and the thickness of the interventional protective gloves is 0.20-0.30 mm; Both the primary protective layer and the secondary protective layer include natural latex and radiation protection functional fillers, wherein the radiation protection functional fillers include radiation protection particles of various size grades, and the filling mass of the radiation protection functional fillers in the primary protective layer is greater than the filling mass of the radiation protection functional fillers in the secondary protective layer.

2. The multi-layer ultra-thin interventional protective glove according to claim 1, characterized in that: The radiation-proof particles include any one or more of bismuth, gadolinium, erbium, bismuth trioxide, gadolinium oxide and erbium oxide; and according to the particle size range, the radiation-proof particles are divided into micron-level powder, submicron-level powder and nano-level powder, and the particle size range of micron-level powder is 1-10μm, the particle size range of submicron-level powder is 0.1-1μm, and the particle size range of nano-level powder is <100nm.

3. The multi-layer ultra-thin interventional protective glove according to claim 2, characterized in that: Micron-level powders account for 10-25% of the volume, submicron-level powders account for 70-80% of the volume, and nano-level powders account for 5-10% of the volume.

4. The multi-layer ultra-thin interventional protective glove according to claim 1, characterized in that: The mass proportion of the radiation protection functional filler in the primary protective layer is greater than the mass proportion of the radiation protection functional filler in the secondary protective layer.

5. The multi-layer ultra-thin interventional protective glove according to claim 4, characterized in that: In the primary protective layer and the secondary protective layer, the mass ratio of the radiation protection functional filler to the natural rubber latex is 0.3-3.0:1.

0.

6. The multi-layer ultra-thin interventional protective glove according to claim 1, characterized in that: The number of layers of the primary protective layer is 1-5; the number of layers of the secondary protective layer is 1-3.

7. A method for preparing the multi-layer ultra-thin interventional protective gloves according to any one of claims 1 to 6, characterized in that: The steps include: S1 Preparation of dispersion containing radiation protection functional filler: Mixing radiation protection particles of various sizes to obtain composite filler particles; mixing the composite filler particles with a dispersant and ball milling; then adding a surface modifier in a water bath or oil bath at 25-80°C to carry out a modification reaction to obtain a dispersion containing a radiation protection filler; S2 compound latex preparation: Add the vulcanizing agent to the natural rubber latex, stir and mix, heat to 30-50°C, stir and mature for 3-5 hours to obtain a pre-vulcanized compounded latex; then add the dispersion prepared in step S1 to the pre-vulcanized compounded latex, stir and mix to obtain a composite latex; S3 gloves dipping molding: The glove mold is cleaned and dried, immersed in a coagulant, taken out and dried, placed in the composite latex of the secondary protective layer, dipped once or multiple times, and dried; then taken out and placed in the composite latex of the primary protective layer, dipped once or multiple times, and dried; then taken out and placed in the composite latex of the skin-friendly layer, dipped once or multiple times, and dried; and finally curling, leaching, vulcanization, surface treatment, drying, and demoulding are performed in sequence to obtain the multi-layer ultra-thin interventional protective gloves.

8. The method for preparing the multi-layer ultra-thin interventional protective gloves according to claim 7, characterized in that: In step S1, the dispersant accounts for 0.5-5.0 wt% of the mass of the composite filler particles, and the surface modifier accounts for 1.0-3.0 wt% of the total mass of the ball-milled mixture.

9. The method for preparing the multi-layer ultra-thin interventional protective gloves according to claim 7, characterized in that: In step S1, after adding the surface modifier, the pH value of the reaction system is adjusted to 4.0-5.0 or 9.0-10.0 before the reaction is carried out.

10. The method for preparing the multi-layer ultra-thin interventional protective gloves according to claim 7, characterized in that: In step S2, before adding the dispersion to the pre-vulcanized compound latex, a pH regulator is added dropwise to the pre-vulcanized compound latex and the dispersion, respectively, so that the pH values ​​of the pre-vulcanized compound latex and the dispersion are adjusted to 10.0-13.5; wherein the pH regulator includes an inorganic base and / or an organic base, the inorganic base includes one or more of sodium hydroxide, potassium hydroxide, and water glass, and the organic base includes tetramethylammonium hydroxide.

Images