A diluent and treating agent for siliconization of injection needle surface and preparation process thereof

Abstract

The invention belongs to the technical field of lubricating additives, and particularly relates to a diluent and a treatment agent for silicifying the surface of an injection needle and a preparation process thereof. The diluent for silicifying the surface of an injection needle comprises the following raw materials in parts by weight: 40 to 100 parts of hydrofluoroether, 10 to 50 parts of isoparaffin, and 10 to 50 parts of siloxane. The solvent composition in the diluent provided by the invention will not have adverse effects on the earth's environment; it is non-flammable and safe to use; it has good compatibility with silicone oil and good dilution performance; it is non-corrosive and will not cause damage to product materials or human bodies. The treatment agent prepared by using the diluent and composite silicone oil of the invention has strong adhesion performance, high oil film strength formed on the needle surface, is not easy to break due to friction during use, and is helpful to improve the comfort and safety of medical injections.

Description

Technical Field

[0001] The invention belongs to the technical field of lubricating additives, and in particular relates to a diluent and a treating agent for siliconizing the surface of an injection needle and a preparation process thereof. Background Art

[0002] The needles of injection needles, infusion needles, and blood collection needles in the medical field are generally drawn from stainless steel pipes. After subsequent processing, they need to be cleaned. After assembly, the surface of the needles needs to be siliconized. The purpose of siliconization is to form a thin layer of organic silicone oil on the surface of the needles, so that the surface of the needle tip is easy to slide, thereby avoiding damage to the tissue membrane and causing inflammation, and at the same time relieving the pain experienced by the patients receiving treatment. So far, the world's most recognized safest lubricating substance is high molecular weight siloxane polymer (referred to as silicone oil), but silicone oil with good lubricating properties usually has a high viscosity and cannot be well coated on the syringe using existing spraying and other technologies. Instead, the organic silicone oil needs to be dissolved in a volatile solvent to form a dilute solution of organic silicone oil, and then the needle is immersed in the solution for a period of time, so that the needle is stained with a layer of solution, and dried for a period of time. After the volatile solvent in the solution evaporates, a thin layer of organic silicone oil is left on the surface of the needle, forming an extremely smooth surface, which minimizes the friction resistance during the puncture process. The diluted silicone oil needs to be easy to apply during construction, not easy to oxidize, have good high temperature stability, and the lubricating oil film formed is high in strength, not easy to break and fall off, durable, and can play a role in rust protection for the needle tip of the syringe. The main requirements for the diluent are: low surface tension, stable chemical properties, high flash point, moderate volatility, non-corrosive, no toxic side effects on the human body, and no adverse effects on the earth's environment.

[0003] At present, the commonly used solvents for dissolving and diluting silicone oils are 1,1-dichloro-1-fluoroethane, dichloromethane, trichlorotrifluoroethane, chloroform, hexane, toluene, methanol, ethanol, etc. At present, the siliconization diluents used in the production of disposable medical devices are mainly mixed compounds with HCFC-141b as the main component, but since HCFC-141b is an ozone depleting substance (ODS), it has begun to be eliminated. In addition, the diluents with HFC-365mfc and HFC-43-10mee as the main components, their core components also belong to HFC substances, and are also facing elimination. In order to prevent ODS from damaging the environment and the atmosphere, it is urgent to find a non-ODS substitute for 141b.

[0004] In addition, the surface siliconized treatment agents currently available on the market have a significant problem when applied to medical needles - low oil film strength and weak adhesion of the treatment agent to the needle. This defect is very obvious in actual medical operations. During the process of the needle puncturing the skin, the treatment agent can be easily rubbed off due to friction. This not only affects the role of the siliconized treatment agent in reducing friction and relieving pain, but also causes patients to still feel obvious pain when receiving injections, reducing the patient's medical experience. In addition, the easy shedding of the treatment agent may also have a negative impact on the lubricity of the needle, increase the resistance during puncture, and may further aggravate damage to the skin tissue, leading to damage and inflammation of the muscle tissue. Therefore, the development of an environmentally friendly siliconized treatment agent with stronger adhesion, which can firmly adhere to the surface of the needle and is not easily rubbed off is also of great significance for improving the comfort and safety of medical injections.

[0005] In view of this, this application is hereby filed. Summary of the invention

[0006] The purpose of the present invention is to provide a non-ODS injection needle surface siliconization diluent, treatment agent and preparation process thereof which are economical, environmentally friendly, have strong adhesion performance, high oil film strength and good lubrication effect in response to the above-mentioned technical problems.

[0007] In view of this, the present invention provides a diluent for siliconizing the surface of an injection needle, comprising the following raw materials in parts by weight:

[0008] 40-100 parts of hydrofluoroether;

[0009] 10-50 parts of isoparaffins;

[0010] 10~50 parts of siloxane.

[0011] Furthermore, the diluent for siliconizing the injection needle surface comprises the following raw materials in parts by weight:

[0012] 70-90 parts of hydrofluoroether;

[0013] 30-40 parts of isoparaffins;

[0014] 10~30 parts of siloxane.

[0015] Furthermore, the siloxane is a cyclic siloxane.

[0016] Furthermore, the diluent for siliconizing the injection needle surface also includes the following raw materials in parts by weight:

[0017] Surfactant 0.5~3 parts;

[0018] Wherein, the surfactant is an anionic surfactant.

[0019] A preparation process of a diluent for siliconizing the surface of an injection needle, the preparation process is used to prepare the diluent for siliconizing the surface of an injection needle, the preparation process comprises:

[0020] In a three-necked flask equipped with a thermometer, a condenser and a stirrer, isoparaffin and siloxane are added in order according to the weight ratio; after stirring and mixing at 30-50°C, a formulated amount of hydrofluoroether and a surfactant are added, and stirring is continued for 10-30 minutes, and then filtered to remove trace impurities, thereby obtaining the diluent for the silanization of the injection needle surface.

[0021] A treatment agent for siliconizing the surface of an injection needle, wherein the treatment agent for siliconizing comprises the following raw materials in parts by weight:

[0022] 2~7 parts of composite silicone oil;

[0023] 80~100 parts of diluent;

[0024] Wherein, the diluent is the above-mentioned diluent for siliconization of the injection needle surface.

[0025] Furthermore, the composite silicone oil comprises:

[0026] 70-150 parts of polydimethylsiloxane;

[0027] 20-30 parts of the first modified silicone oil;

[0028] 10-20 parts of the second modified silicone oil;

[0029] 5-10 parts of the third modified silicone oil;

[0030] 10-15 parts of amino silicone oil.

[0031] Furthermore, the first modified silicone oil is a linear hydroxy silicone oil that has been subjected to chain extension treatment;

[0032] The preparation process of the first modified silicone oil is as follows:

[0033] Linear hydroxy silicone oil, chain extender and catalyst are added into the reactor according to a weight ratio, wherein the weight ratio of the linear hydroxy silicone oil, chain extender and catalyst is (1-2): (0.8-1): (0.01-0.05), mixed evenly and heated, and reacted at 50-65° C. for 4-6 hours to obtain the first modified silicone oil.

[0034] Furthermore, the second modified silicone oil comprises the following raw materials in parts by weight:

[0035] 80-100 parts of vinyl-containing polydimethylsiloxane;

[0036] 10-20 parts of Si-H group-containing polysiloxane;

[0037] Catalyst 0.01~0.03 parts;

[0038] The preparation process of the second modified silicone oil is as follows:

[0039] The vinyl-containing polydimethylsiloxane, the Si-H-containing polysiloxane and the catalyst are added into the reactor according to a weight ratio, stirred at 30-50° C. and reacted for 5-10 minutes to obtain the second modified silicone oil.

[0040] A preparation process of a treatment agent for siliconizing the surface of an injection needle, the preparation process is used to prepare the above-mentioned treatment agent for siliconizing the surface of an injection needle, and the preparation process comprises the steps of:

[0041] S1, preparation of composite silicone oil: weigh the polydimethylsiloxane, the first modified silicone oil, the second modified silicone oil, the third modified silicone oil and the amino silicone oil in a weight ratio, then mix the polydimethylsiloxane and the second modified silicone oil at room temperature, and stir for 3 to 5 minutes; add the first modified silicone oil, and stir at room temperature for 10 to 30 minutes; then heat the mixed solution to 40 to 50° C., first add the third modified silicone oil, stir and react for 5 to 10 minutes, then add the amino silicone oil in a formula amount, and continue to stir and react at 40 to 50° C. for 20 to 30 minutes to obtain the composite silicone oil;

[0042] S2, preparation of a surface siliconization treatment agent: weigh a formulated amount of diluent and composite silicone oil according to a weight ratio, mix the diluent and composite silicone oil, and stir and mix at 20-30° C. for 3-5 minutes to obtain the surface siliconization treatment agent.

[0043] The beneficial effects of the present invention are:

[0044] 1. The diluent of the present invention uses hydrofluoroether to replace the traditional diluent, realizing the technical update and progress of HCFC→HFC→HFE, and the diluent composition of the present invention has good silicone oil solubility, compatibility with equipment, and non-flammability, and can meet the silicone oil dilution requirements during siliconization;

[0045] 2. The addition of isoalkanes in the diluent of the present invention can adjust the volatilization rate of the hydrofluoroether, making the performance of the diluent more stable; at the same time, the addition of isoalkanes can also enhance the solubility of the hydrofluoroether, improve the environmental performance of the diluent, and reduce the production cost of the diluent.

[0046] 3. In the present invention, by adding siloxane, especially cyclic siloxane, to hydrofluoroether, the viscosity and surface tension of hydrofluoroether can be further reduced, the fluidity of the diluent can be improved, and it can be easily coated, spread and film-formed. At the same time, the addition of cyclic siloxane can also reduce the surface tension of the final treatment agent, inhibit the generation of foam, and improve the film-forming and lubricating properties of the treatment agent;

[0047] 3. In the treatment agent for siliconization of the injection needle surface of the present invention, a second modified silicone oil with a network structure is firstly added to the polydimethylsiloxane to improve the continuity, lubricity and strength of the composite silicone oil film; on this basis, by adding the modified linear hydroxy silicone oil treated with chain extension, i.e., the first modified silicone oil, the reactive groups on the linear segments of the first modified silicone oil can be further cross-linked with the second modified silicone oil or the linear long-chain molecules can be physically interlaced in the network structure to form a long-chain branched network structure, thereby further improving the continuity, lubricity, strength and compatibility with the needle film. Furthermore, by adding the third modified silicone oil and amino silicone oil, on the one hand, the high reactivity between the third modified silicone oil and the amino silicone oil can be used to make them react, and on the basis of further improving the continuity, lubricity and strength of the composite silicone oil film, the amino silicone oil can also improve the ability of the oil film to combine with the needle surface through the electrostatic adsorption effect with the surfactant in the diluent, and finally make the oil film formed on the needle surface after siliconization treatment have good lubrication performance, high strength, high adhesion, not easy to fall off, and will not cause damage to the environment and the atmosphere. In addition, there are a variety of reactive groups that can react and combine with each other between the first modified silicone oil, the second modified silicone oil, the third modified silicone oil and the amino silicone oil. Through their combination, the performance of the oil film can be further improved. DETAILED DESCRIPTION

[0048] The following will be combined with the embodiments in this application to clearly describe the technical solutions in the embodiments of this application. Obviously, the described embodiments are part of the embodiments of this application, rather than all the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field belong to the scope of protection of this application.

[0049] In the description of the present application, it should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. For ease of description, the techniques, methods and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but in appropriate cases, the techniques, methods and devices should be considered as part of the authorization specification. In all examples shown and discussed here, any specific value should be interpreted as being merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values.

[0050] It should be noted that the term "and / or" in the specification and claims of the present application represents at least one of the connected objects, and the character " / " generally indicates that the objects associated before and after are in an "or" relationship. In addition, in the present application, the term "include", "comprise" or any other variant thereof is intended to cover non-exclusive inclusion, so that the process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "including one..." do not exclude the existence of other identical elements in the process, method, article or device including the element. In addition, it should be pointed out that the scope of the method and device in the embodiment of the present application is not limited to performing functions in the order shown or discussed, and may also include performing functions in a substantially simultaneous manner or in reverse order according to the functions involved, for example, the described method may be performed in an order different from that described, and various steps may also be added, omitted, or combined. In addition, the features described with reference to certain examples may be combined in other examples.

[0051] A diluent for siliconizing the surface of an injection needle, comprising the following raw materials in parts by weight:

[0052] 40-100 parts of hydrofluoroether;

[0053] 10-50 parts of isoparaffins;

[0054] 10~50 parts of siloxane.

[0055] As some examples of the present invention, the hydrofluoroether is selected from one or more of HFE-347, HFE-254, HFE-449mec-f, HFE-7100, etc.

[0056] As an organic solvent, hydrofluoroether has excellent thermal stability, chemical stability and low surface tension, as well as good solubility and low toxicity. It can quickly penetrate into oils and fats to dissolve and dilute them. At the same time, hydrofluoroether has a low boiling point, such as HFE-449mec-f with a boiling point of 72°C, HFE-347 with a boiling point of 56.2°C, and HFE-7100 with a boiling point of 61°C. It can be used as a diluent for the siliconization of the injection needle surface, which can achieve rapid volatilization of the diluent; and the viscosity of hydrofluoroether is also low, which is convenient for coating. For example, the kinematic viscosity of HFE-449mec-f is 0.61cst; in addition, the surface tension of hydrofluoroether is also low, such as the surface tension of HFE-7100 is 13.6mN / m; and the chemical properties of hydrofluoroether are stable, not easy to ignite, friendly to the human body, non-corrosive and non-toxic. More importantly, the ozone digestion value (ODP) of hydrofluoroether is zero, the global greenhouse potential (GWP) is low, and the atmospheric residence time is very short. It can be used as a diluent for the siliconization of the injection needle surface, which can replace the existing use of HCFC and HFC, prevent ODS from damaging the environment and the atmosphere, and is more environmentally friendly.

[0057] The diluent of the present invention uses hydrofluoroether to replace the traditional diluent, realizing the technical update and progress of HCFC→HFC→HFE. The diluent composition of the present invention has good silicone oil solubility, compatibility with equipment, and non-flammability, and can meet the silicone oil dilution requirements during siliconization.

[0058] As some examples of the present invention, the isoalkane is selected from one or more of isodecane, isododecane, isotridecane / tetradecane, and isohexadecane.

[0059] Isoalkanes have good solubility and can dissolve many organic substances. The flash point of isoalkanes is usually high, and its flash point is usually greater than 63°C. In addition, isoalkanes have low viscosity and surface tension. At the same time, the chemical properties of isoalkanes are relatively stable and are not prone to oxidation, reduction and other reactions. Isoalkanes have low toxicity, and the waste liquid of isoalkanes can be naturally degraded and will not cause long-term pollution to the environment. When used as the diluent described in the present invention, it can be mixed with hydrofluoroether to form a solvent with good solubility, high flash point, low viscosity and surface tension, relatively stable chemical properties, non-corrosiveness and low toxicity, which has a good dissolving and diluting effect on silicone oil.

[0060] In addition, the addition of isoalkanes can adjust the volatilization rate of hydrofluoroether, making the performance of the diluent more stable; at the same time, the addition of isoalkanes can also enhance the solubility of hydrofluoroether, improve the environmental performance of the diluent, and reduce the production cost of the diluent.

[0061] Preferably, the siloxane is a cyclic siloxane.

[0062] As some examples of the present invention, the cyclic siloxane is selected from one or more of tetramethylcyclotetrasiloxane, pentamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

[0063] Preferably, the surface tension of the siloxane is less than 20 mN / m.

[0064] In the present invention, by adding siloxane, especially cyclic siloxane, to the hydrofluoroether, the viscosity and surface tension of the hydrofluoroether can be further reduced, the fluidity of the diluent can be improved, and the diluent can be easily coated, spread and formed into a film. At the same time, the addition of cyclic siloxane can also reduce the surface tension of the final treatment agent, inhibit the generation of foam, and improve the film-forming and lubricating properties of the treatment agent.

[0065] Preferably, the diluent for siliconizing the injection needle surface comprises the following raw materials in parts by weight:

[0066] 70-90 parts of hydrofluoroether;

[0067] 30-40 parts of isoparaffins;

[0068] 10~30 parts of siloxane.

[0069] Furthermore, the diluent for siliconizing the injection needle surface also includes the following raw materials in parts by weight:

[0070] 0.5~3 parts of surfactant.

[0071] Preferably, the surfactant is an anionic surfactant.

[0072] As some examples of the present invention, the surfactant is selected from one or more of sodium oleate, sodium rosinate, sodium dodecylbenzene sulfonate, sodium linear alkylbenzene sulfonate, and sodium polyoxyethylene lauryl ether sulfate.

[0073] Furthermore, the preparation method of the diluent for siliconization of the injection needle surface is as follows:

[0074] In a three-necked flask equipped with a thermometer, a condenser and a stirrer, isoparaffin and siloxane are added in order according to the weight ratio; after stirring and mixing at 30-50°C, a formulated amount of hydrofluoroether and a surfactant are added, and stirring is continued for 10-30 minutes, and then filtered to remove trace impurities, thereby obtaining the diluent product for the silanization of the injection needle surface.

[0075] The solvent composition in the diluent provided by the present invention will not have adverse effects on the earth's environment; it is non-flammable and safe to use; it has good compatibility with silicone oil and good dilution performance; it is non-corrosive and will not cause damage to product materials or human bodies.

[0076] In addition, the present invention also provides a treatment agent for siliconization of injection needle surface, which comprises the following raw materials in parts by weight:

[0077] 2~7 parts of composite silicone oil;

[0078] 80~100 parts of diluent;

[0079] Wherein, the diluent is the above-mentioned diluent for siliconization of the injection needle surface.

[0080] Furthermore, the composite silicone oil comprises:

[0081] 70-150 parts of polydimethylsiloxane;

[0082] 20-30 parts of the first modified silicone oil;

[0083] 10-20 parts of the second modified silicone oil;

[0084] 5-10 parts of the third modified silicone oil;

[0085] 10-15 parts of amino silicone oil.

[0086] Preferably, the kinematic viscosity of the polydimethylsiloxane is 500 to 1000 cSt.

[0087] Preferably, the polydimethylsiloxane contains 10-20% hydroxypolydimethylsiloxane.

[0088] Furthermore, the composite silicone oil also includes 0.1 to 0.5 parts by weight of methyltri(isopropyleneoxy)silane and 0.1 to 0.3 parts by weight of butyl titanate.

[0089] Under the catalytic action of the butyl titanate, the methyl tri(isopropyleneoxy) silane can undergo a cross-linking reaction with the polydimethylsiloxane. More importantly, this cross-linking reaction requires the participation of moisture, so it is mainly carried out after the methyl tri(isopropyleneoxy) silane encounters moisture, such as water vapor in the air. Therefore, the addition of the methyl tri(isopropyleneoxy) silane can improve the strength of the lubricating oil film and the ability of the oil film to bind to the needle surface through further cross-linking during the curing process after the needle silanization is completed.

[0090] Preferably, the first modified silicone oil is a linear hydroxy silicone oil that has been subjected to chain extension treatment.

[0091] Furthermore, the preparation process of the first modified silicone oil is as follows:

[0092] The linear hydroxy silicone oil, the chain extender and the catalyst are added into the reactor according to the weight ratio, mixed evenly and heated, and reacted at 50-65° C. for 4-6 hours to obtain the first modified silicone oil.

[0093] Preferably, the weight ratio of the linear hydroxy silicone oil, the chain extender and the catalyst is (1-2): (0.8-1): (0.01-0.05).

[0094] Preferably, the chain extender is selected from GH-100, a carboxyl chain extender, an epoxy chain extender, such as 5,5-dimethyl-1,3-di(oxiranylmethyl)imidazolidine-2,4-dione, and the like.

[0095] In the present invention, by modifying the linear hydroxy silicone oil, the condensation reaction between the terminal hydroxyl groups on the linear hydroxy silicone oil and the chain extender can be used to not only extend the molecular chain of the linear silicone oil, but also, since the linear segments of the linear hydroxy silicone oil after the reaction carry reactive groups such as hydroxyl groups or epoxy groups, the first modified silicone oil can also combine with other components, especially amino, hydroxyl, carboxyl, etc. in other types of organic silicone oils in the treatment agent, to form a network structure. More importantly, the extended molecular chain can make the structure of the lubricating oil film formed on the needle tube surface after siliconization treatment more compact, provide better protection during friction, reduce direct contact of the friction interface, and reduce wear; at the same time, the lubricating oil film formed by long-chain molecules has higher adsorption capacity, greater thickness, stronger stability, higher oil film strength, and better lubrication performance.

[0096] As some examples of the present invention, the catalyst is selected from one or more of tetraoctylammonium chloride, cobalt trioxide, and the like.

[0097] As some examples of the present invention, the linear hydroxy silicone oil is selected from one or more of Dow Corning's PMX-0156, Wacker's WS62M, and the like.

[0098] Furthermore, the second modified silicone oil comprises the following raw materials in parts by weight:

[0099] 80-100 parts of vinyl-containing polydimethylsiloxane;

[0100] 10-20 parts of Si-H group-containing polysiloxane;

[0101] Catalyst 0.01~0.03 parts.

[0102] Preferably, the catalyst is hexachloroplatinic acid.

[0103] Preferably, the Si-H group-containing polysiloxane is a methyl hydrogen siloxane-dimethyl siloxane copolymer.

[0104] Furthermore, the preparation process of the second modified silicone oil is as follows:

[0105] The vinyl-containing polydimethylsiloxane, the Si-H-containing polysiloxane and the catalyst are added into the reactor according to a weight ratio, stirred at 30-50° C. and reacted for 5-10 minutes to obtain the second modified silicone oil.

[0106] During the preparation of the second modified silicone oil, vinyl-containing polydimethylsiloxane and Si-H-containing polysiloxane can form a network structure through a cross-linking reaction. This network structure can improve the continuity and strength of the lubricating oil film. At the same time, it can also serve as the basis for subsequent cross-linking and interlacing network structures.

[0107] Furthermore, the third modified silicone oil is epoxy modified silicone oil.

[0108] As some examples of the present invention, the epoxy-modified silicone oil may be a side chain epoxy-modified silicone oil in which the epoxy group is located on the side chain of polymethylsiloxane or a terminal epoxy-modified silicone oil with active epoxy groups at both ends.

[0109] As some examples of the present invention, the amino silicone oil is selected from one or more of primary amino silicone oil, secondary amino silicone oil, primary-secondary amino silicone oil, polyether-modified amino silicone oil, and the like.

[0110] Preferably, the amino value of the amino silicone oil is 0.5-0.7 mmol / g.

[0111] In addition, the present invention also provides a preparation process of a treatment agent for siliconizing the surface of an injection needle, the preparation process is used to prepare the above-mentioned treatment agent for siliconizing the surface of an injection needle, and the preparation process comprises the steps of:

[0112] S1, preparation of composite silicone oil: weigh the polydimethylsiloxane, the first modified silicone oil, the second modified silicone oil, the third modified silicone oil and the amino silicone oil in a weight ratio, then mix the polydimethylsiloxane and the second modified silicone oil at room temperature, and stir for 3 to 5 minutes; add the first modified silicone oil, and stir at room temperature for 10 to 30 minutes; then heat the mixed solution to 40 to 50° C., first add the third modified silicone oil, stir and react for 5 to 10 minutes, then add the amino silicone oil in a formula amount, and continue to stir and react at 40 to 50° C. for 20 to 30 minutes to obtain the composite silicone oil;

[0113] S2, preparation of a surface siliconization treatment agent: weigh a formulated amount of diluent and composite silicone oil according to a weight ratio, mix the diluent and composite silicone oil, and stir and mix at 20-30° C. for 3-5 minutes to obtain the surface siliconization treatment agent.

[0114] It should be noted that when the composite silicone oil contains methyl tri(isopropyleneoxy)silane and butyl titanate, in step S1, after the amino silicone oil is added and stirred for the set time, the reactor needs to be evacuated to a vacuum degree of 0.5*10 -5 pa~1*10 -5 After pa, add the formulated amount of methyltri(isopropyleneoxy)silane and butyl titanate, and stir evenly to obtain the composite silicone oil; and in the step S2, the diluent and the composite silicone oil need to be mixed in a closed container. In the subsequent use process, the needle is first immersed in the treatment agent in the closed container, and then taken out after standing and keeping for a certain period of time, and then the needle immersed in the treatment agent is placed in the air for cross-linking and curing.

[0115] Furthermore, the method for using the surface siliconization treatment agent of the present invention is as follows:

[0116] At room temperature, immerse the needle in the siliconizing agent for the injection needle surface, let it stand for 5 to 10 minutes, then take it out and place it in clean air to cure it at room temperature for 10 to 30 hours.

[0117] In the treatment agent for siliconizing the surface of the injection needle described in the present invention, a second modified silicone oil with a network structure is firstly added to the polydimethylsiloxane to improve the continuity, lubricity and strength of the composite silicone oil film-forming; on this basis, by adding a modified linear hydroxy silicone oil that has been subjected to chain extension treatment, i.e., the first modified silicone oil, the reactive groups on the linear segments of the first modified silicone oil can be utilized to further crosslink with the second modified silicone oil or the linear long-chain molecules can be physically interlaced in the network structure to form a long-chain branched network structure, thereby further improving the continuity, lubricity, strength and ability to bind to the needle surface of the film-forming. On this basis, by adding the third modified silicone oil and amino silicone oil, on the one hand, the high reactivity between the third modified silicone oil and the amino silicone oil can be used to make them react, and on the basis of further improving the continuity, lubricity and strength of the composite silicone oil film, the amino silicone oil can also improve the ability of the oil film to combine with the needle surface through the electrostatic adsorption effect with the surfactant in the diluent and the high reactivity between it and the third modified silicone oil, and finally make the oil film formed on the needle surface after siliconization treatment have the characteristics of good lubrication performance, high strength, high adhesion, not easy to fall off, and will not cause damage to the environment and the atmosphere. In addition, there are a variety of reactive groups that can react and combine with each other between the first modified silicone oil, the second modified silicone oil, the third modified silicone oil and the amino silicone oil, and through their combination, the performance of the oil film can be further improved.

[0118] The following is an illustration of the diluent, treatment agent and preparation process for siliconizing the surface of the injection needle of the present invention through specific examples.

[0119] Embodiment 1

[0120] A diluent for silicification of injection needle surfaces, comprising the following raw materials in parts by weight: 100 parts of HFE-347; 10 parts of isodecane; 30 parts of tetramethylcyclotetrasiloxane;

[0121] The preparation process of the diluent for siliconization of the injection needle surface is as follows:

[0122] In a three-necked flask equipped with a thermometer, a condenser and a stirrer, isodecane and tetramethylcyclotetrasiloxane are added in order according to the weight ratio; after stirring and mixing evenly at 30°C, a formulated amount of HFE-347 is added, and stirring is continued for 30 minutes, and then filtered to remove trace impurities, to obtain the diluent product for the surface silicification of the injection needle.

[0123] Embodiment 2

[0124] A diluent for siliconizing the surface of an injection needle, comprising the following raw materials in parts by weight: 70 parts of HFE-254, 30 parts of isododecane, 30 parts of pentamethylcyclopentasiloxane, and 0.5 parts of sodium oleate;

[0125] The preparation process of the diluent for siliconization of the injection needle surface is as follows:

[0126] In a three-necked flask equipped with a thermometer, a condenser and a stirrer, isododecane and pentamethylcyclopentasiloxane are added in order according to the weight ratio; after stirring and mixing evenly at 40°C, the formulated amount of HFE-254 and sodium oleate are added, and stirring is continued for 20 minutes, and then filtered to remove trace impurities, thereby obtaining the diluent product for the silanization of the injection needle surface.

[0127] Embodiment 3

[0128] A diluent for silicification of the surface of an injection needle, comprising the following raw materials in parts by weight: 90 parts of HFE-7100, 40 parts of isohexadecane, 15 parts of octamethylcyclotetrasiloxane, and 2 parts of sodium rosinate;

[0129] The preparation process of the diluent for siliconization of the injection needle surface is as follows:

[0130] In a three-necked flask equipped with a thermometer, a condenser and a stirrer, isohexadecane and octamethylcyclotetrasiloxane are added in order according to the weight ratio; after stirring and mixing evenly at 50°C, the formulated amount of HFE-7100 and sodium rosinate are added, and stirring is continued for 10 minutes, and then filtered to remove trace impurities, thereby obtaining the diluent product for the silanization of the injection needle surface.

[0131] Embodiment 4

[0132] Preparation of the first modified silicone oil:

[0133] 20 parts by weight of linear hydroxy silicone oil, 10 parts by weight of chain extender and 0.3 parts by weight of catalyst are added to a reactor according to a weight ratio, mixed evenly and heated, and reacted at 55°C for 5 hours to obtain a first modified silicone oil; wherein the linear hydroxy silicone oil is Dow Corning's PMX-0156, the chain extender is 5,5-dimethyl-1,3-di(oxiranylmethyl)imidazolidine-2,4-dione, and the catalyst is a mixture of tetraoctylammonium chloride and cobalt trioxide in a weight ratio of 1:1.

[0134] Embodiment 5

[0135] Preparation of the second modified silicone oil:

[0136] 100 parts by weight of vinyl-containing polydimethylsiloxane, 18 parts by weight of methylhydrogensiloxane-dimethylsiloxane copolymer and 0.02 parts by weight of catalyst hexachloroplatinic acid were added to the reactor according to a weight ratio, and stirred and reacted at 50° C. for 6 minutes to obtain a second modified silicone oil.

[0137] Embodiment 6

[0138] A treatment agent for siliconizing the surface of an injection needle, comprising the following raw materials by weight: 2 parts of composite silicone oil; 100 parts of diluent;

[0139] Wherein, the diluent is the diluent for silicification of the injection needle surface prepared in the above-mentioned embodiment 1;

[0140] In addition, the composite silicone oil includes: 70 parts of polydimethylsiloxane; 30 parts of the first modified silicone oil prepared in the above embodiment 4; 20 parts of the second modified silicone oil prepared in the above embodiment 5; and 10 parts of the third modified silicone oil and 15 parts of amino silicone oil;

[0141] The preparation process of the treatment agent for siliconization of the injection needle surface is as follows:

[0142] S1, preparation of composite silicone oil: weigh the formulated amount of polydimethylsiloxane, the first modified silicone oil, the second modified silicone oil, the third modified silicone oil and the amino silicone oil according to the weight ratio, then mix the polydimethylsiloxane and the second modified silicone oil at room temperature, and stir for 3 minutes; add the first modified silicone oil, and stir for 30 minutes at room temperature; then heat the mixed solution to 50°C, first add the third modified silicone oil, stir and react for 5 minutes, then add the formulated amount of amino silicone oil, and continue to stir and react at 50°C for 20 minutes to obtain the composite silicone oil;

[0143] S2, preparation of a surface siliconization treatment agent: weigh the diluent and the composite silicone oil in a weight ratio, mix the diluent and the composite silicone oil, and stir and mix at 20° C. for 3 minutes to obtain the surface siliconization treatment agent.

[0144] Embodiment 7

[0145] A treatment agent for siliconizing the surface of an injection needle, comprising the following raw materials by weight: 5 parts of composite silicone oil; 90 parts of diluent;

[0146] Wherein, the diluent is the diluent for silicification of the injection needle surface prepared in the above-mentioned Example 2;

[0147] In addition, the composite silicone oil includes: 100 parts of polydimethylsiloxane; 25 parts of the first modified silicone oil prepared in the fourth embodiment; 15 parts of the second modified silicone oil prepared in the fifth embodiment; and 5 parts of the third modified silicone oil and 10 parts of amino silicone oil;

[0148] The preparation process of the treatment agent for siliconization of the injection needle surface is as follows:

[0149] S1, preparation of composite silicone oil: weigh the formulated amount of polydimethylsiloxane, the first modified silicone oil, the second modified silicone oil, the third modified silicone oil and the amino silicone oil according to the weight ratio, then mix the polydimethylsiloxane and the second modified silicone oil at room temperature, and stir for 4 minutes; add the first modified silicone oil, and stir at room temperature for 20 minutes; then heat the mixed solution to 40°C, first add the third modified silicone oil, stir and react for 8 minutes, then add the formulated amount of amino silicone oil, and continue to stir and react at 40°C for 25 minutes to obtain the composite silicone oil;

[0150] S2, preparation of a surface siliconization treatment agent: weigh the diluent and the composite silicone oil in a weight ratio, mix the diluent and the composite silicone oil, and stir and mix at 25° C. for 4 minutes to obtain the surface siliconization treatment agent.

[0151] Embodiment 8

[0152] A treatment agent for siliconizing the surface of an injection needle, comprising the following raw materials by weight: 7 parts of composite silicone oil; 80 parts of diluent;

[0153] Wherein, the diluent is the diluent for silicification of the injection needle surface prepared in the above-mentioned Example 3;

[0154] In addition, the composite silicone oil includes: 150 parts of polydimethylsiloxane; 20 parts of the first modified silicone oil prepared in the fourth embodiment; 10 parts of the second modified silicone oil prepared in the fifth embodiment; and 7 parts of the third modified silicone oil and 12 parts of amino silicone oil;

[0155] The preparation process of the treatment agent for siliconization of the injection needle surface is as follows:

[0156] S1, preparation of composite silicone oil: weigh the formulated amount of polydimethylsiloxane, the first modified silicone oil, the second modified silicone oil, the third modified silicone oil and the amino silicone oil according to the weight ratio, then mix the polydimethylsiloxane and the second modified silicone oil at room temperature, and stir for 5 minutes; add the first modified silicone oil, and stir for 10 minutes at room temperature; then heat the mixed solution to 45°C, first add the third modified silicone oil, stir and react for 10 minutes, then add the formulated amount of amino silicone oil, and continue to stir and react at 45°C for 30 minutes to obtain the composite silicone oil;

[0157] S2, preparation of a surface siliconization treatment agent: weigh a diluent and a compound silicone oil in a weight ratio, mix the diluent and the compound silicone oil, and stir and mix at 30° C. for 5 minutes to obtain the surface siliconization treatment agent.

[0158] Embodiment 9

[0159] A treatment agent for siliconizing the surface of an injection needle, comprising the following raw materials by weight: 7 parts of composite silicone oil; 80 parts of diluent;

[0160] Wherein, the diluent is the diluent for silicification of the injection needle surface prepared in the above-mentioned Example 3;

[0161] In addition, the composite silicone oil includes: 150 parts of polydimethylsiloxane; 20 parts of the first modified silicone oil prepared in the above embodiment 4; 10 parts of the second modified silicone oil prepared in the above embodiment 5; 7 parts of the third modified silicone oil, 12 parts of amino silicone oil, 0.3 parts by weight of methyltri(isopropyleneoxy)silane and 0.4 parts of butyl titanate;

[0162] The preparation process of the treatment agent for siliconization of the injection needle surface is as follows:

[0163] S1, preparation of composite silicone oil: weigh the polydimethylsiloxane, the first modified silicone oil, the second modified silicone oil, the third modified silicone oil and the amino silicone oil in a weight ratio, then mix the polydimethylsiloxane and the second modified silicone oil at room temperature, stir for 5 minutes; add the first modified silicone oil, and stir for 10 minutes at room temperature; then heat the mixed solution to 45°C, first add the third modified silicone oil, stir and react for 10 minutes, then add the amino silicone oil in a formula, continue to stir and react at 45°C for 30 minutes, and then evacuate the reactor to a vacuum degree of 1*10 -5 After pa, add the formulated amount of methyltri(isopropyleneoxy)silane and butyl titanate, and stir evenly to obtain the composite silicone oil;

[0164] S2, preparation of a surface siliconization treatment agent: weigh a formulated amount of diluent and compound silicone oil according to a weight ratio, mix the diluent and compound silicone oil in a sealed container, and stir and mix at 30° C. for 5 minutes to obtain the surface siliconization treatment agent.

[0165] Comparative Example 1

[0166] A treatment agent for siliconizing the surface of an injection needle, which differs from the above-mentioned embodiment 8 in that no isoparaffin is added to the diluent used.

[0167] Comparative Example 2

[0168] A treatment agent for siliconizing the surface of an injection needle, which differs from the eighth embodiment in that no siloxane is added to the diluent used.

[0169] Comparative Example 3

[0170] A treatment agent for siliconizing the surface of an injection needle, which differs from the above-mentioned embodiment 8 in that hexamethyldisiloxane is used in the diluent instead of the cyclic siloxane.

[0171] Comparative Example 4

[0172] A treatment agent for siliconizing the surface of an injection needle, which differs from the eighth embodiment in that no surfactant is added to the diluent used.

[0173] Comparative Example 5

[0174] A treatment agent for siliconizing the surface of an injection needle, which differs from the eighth embodiment in that the composite silicone oil used does not contain the first modified silicone oil.

[0175] Comparative Example 6

[0176] A treatment agent for siliconizing the surface of an injection needle, which differs from the eighth embodiment in that the composite silicone oil used does not contain a second modified silicone oil.

[0177] Comparative Example 7

[0178] A treatment agent for siliconizing the surface of an injection needle, which differs from the eighth embodiment in that the composite silicone oil used does not contain the third modified silicone oil.

[0179] Comparative Example 8

[0180] A treatment agent for siliconizing the surface of an injection needle, which differs from the above-mentioned embodiment 8 in that the composite silicone oil used does not contain amino silicone oil.

[0181] Comparative Example 9

[0182] A treatment agent for siliconizing the surface of an injection needle, which differs from the eighth embodiment in that unmodified linear hydroxy silicone oil is used in the composite silicone oil instead of the first modified silicone oil.

[0183] Comparative Example 10

[0184] A treatment agent for siliconizing the surface of an injection needle, which differs from the above-mentioned embodiment 8 in that 1,1-dichloro-1-fluoroethane is used to replace the diluent therein.

[0185] Comparative Example 11

[0186] A treatment agent for siliconizing the surface of an injection needle, which differs from the above-mentioned embodiment 8 in that polydimethylsiloxane is used to replace the composite silicone oil therein.

[0187] Comparative Example 12

[0188] A treatment agent for siliconization of injection needle surfaces, which differs from the above-mentioned embodiment 8 in that: in step S1, the reactor is not evacuated, and methyltri(isopropyleneoxy)silane and butyl titanate are directly added and stirred to obtain composite silicone oil.

[0189] Test Example 1

[0190] Coating performance test

[0191] At room temperature, the needle tip was immersed in the surface siliconization treatment agent prepared in the above-mentioned Examples 6 to 9 and Comparative Examples 1 to 12, respectively, and was taken out after standing and keeping for 10 minutes, and then placed in clean air and cured at room temperature for 15 hours. After that, the integrity of the oil film on the needle tip surface was observed and evaluated under a high-power microscope. The specific method is as follows: 5 areas (the width of the area is 1 / 4 of the circumference, and the length is 2 times the diameter of the needle tube surface) were selected at equal distances along the length direction of the needle tip, and the ratio of the oil film coverage area to the total area in the area was calculated, and then the average value of the 5 ratios was taken as the coverage rate of the oil film on the needle tip surface. The test results are shown in Table 1 below;

[0192] Table 1 Coverage of oil film on needle surface

[0193]

[0194] Test Example 2

[0195] Evaluation of oil film integrity after injection

[0196] The needles obtained by siliconization treatment in the above-mentioned test example 1 were respectively used for injection, and then the needles after injection were placed under a high-power microscope to observe and evaluate the integrity of the oil film on the surface of the needles. The specific method is: 5 areas were selected at equal distances along the length direction of the needles (the width of the area was 1 / 4 of the circumference, and the length was 2 times the diameter of the needle tube surface), and the ratio of the oil film coverage area in the area to the total area was calculated, and then the average value of the 5 ratios was taken as the coverage rate of the oil film on the needle surface. The test results are shown in Table 2 below;

[0197] Table 2 Coverage of oil film on needle surface

[0198]

[0199] The embodiments of the present application are described above. In the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present application is not limited to the above-mentioned specific implementation methods. The above-mentioned specific implementation methods are merely illustrative and not restrictive. Under the guidance of the present application, ordinary technicians in this field can also make many forms without departing from the purpose of the present application and the scope of protection of the claims, all of which are within the protection of the present application.

Claims

1. A treatment agent for siliconizing the surface of an injection needle, characterized in that: The siliconization treatment agent comprises the following raw materials in parts by weight: 2-7 parts of composite silicone oil; 80-100 parts of diluent; Wherein, the diluent comprises the following raw materials in parts by weight: Wherein, the isoalkane is selected from one or more of isodecane, isododecane, isotridecane, isotetradecane and isohexadecane; the siloxane is one or more of tetramethylcyclotetrasiloxane, pentamethylcyclopentasiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane; the surfactant is an anionic surfactant; The composite silicone oil comprises: Wherein, the first modified silicone oil is a linear hydroxy silicone oil that has been subjected to chain extension treatment; The second modified silicone oil comprises the following raw materials in parts by weight: 80-100 parts of vinyl-containing polydimethylsiloxane; 10 to 20 parts of Si-H group-containing polysiloxane; Catalyst 0.01-0.03 parts; Wherein, the Si-H group-containing polysiloxane is a methyl hydrogen siloxane-dimethyl siloxane copolymer; The preparation process of the second modified silicone oil is as follows: Adding vinyl-containing polydimethylsiloxane, Si-H-containing polysiloxane and a catalyst into a reactor according to a weight ratio, stirring and reacting at 30-50° C. for 5-10 minutes, thereby obtaining the second modified silicone oil; The third modified silicone oil is epoxy modified silicone oil.

2. The treatment agent for siliconizing the surface of an injection needle according to claim 1, characterized in that: The diluent comprises the following raw materials in parts by weight: 70-90 parts of hydrofluoroether; 30-40 parts of isoparaffins; 10 to 30 parts of siloxane.

3. The treatment agent for siliconizing the surface of an injection needle according to claim 1, characterized in that: The preparation process of the diluent comprises: In a three-necked flask equipped with a thermometer, a condenser and a stirrer, isoparaffin and siloxane are added in order according to weight ratio; after stirring and mixing at 30-50° C., a formulated amount of hydrofluoroether and a surfactant are added, and stirring is continued for 10-30 minutes, and then filtered to remove trace impurities to obtain the diluent.

4. The treatment agent for siliconizing the surface of an injection needle according to claim 1, characterized in that: The preparation process of the first modified silicone oil is as follows: Add linear hydroxy silicone oil, chain extender and catalyst into the reactor according to the weight ratio, wherein the weight ratio of the linear hydroxy silicone oil, chain extender and catalyst is (1-2): (0.8-1): (0.01-0.05), and the chain extender is selected from GH-100, carboxyl chain extender and epoxy chain extender; after mixing evenly, heat and react at 50-65° C. for 4-6 hours to obtain the first modified silicone oil.

5. A process for preparing a treatment agent for siliconizing the surface of an injection needle, characterized in that: The preparation process is used to prepare the treatment agent for siliconizing the surface of the injection needle according to any one of claims 1 to 4, and the preparation process comprises the steps of: S1, preparation of composite silicone oil: weigh the polydimethylsiloxane, the first modified silicone oil, the second modified silicone oil, the third modified silicone oil and the amino silicone oil in a weight ratio, then mix the polydimethylsiloxane and the second modified silicone oil at room temperature, and stir for 3 to 5 minutes; add the first modified silicone oil, and stir at room temperature for 10 to 30 minutes; then heat the mixed solution to 40 to 50° C., first add the third modified silicone oil, stir and react for 5 to 10 minutes, then add the amino silicone oil in a formula amount, and continue to stir and react at 40 to 50° C. for 20 to 30 minutes to obtain the composite silicone oil; S2, preparation of the surface siliconization treatment agent: weigh the diluent and the composite silicone oil in the formula according to the weight ratio, mix the diluent and the composite silicone oil, and stir and mix them at 20-30° C. for 3-5 minutes to obtain the surface siliconization treatment agent.

Images