CN111962307B - Antibacterial material capable of providing nitric oxide by itself and preparation method and application thereof - Google Patents

Antibacterial material capable of providing nitric oxide by itself and preparation method and application thereof Download PDF

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CN111962307B
CN111962307B CN202010784891.XA CN202010784891A CN111962307B CN 111962307 B CN111962307 B CN 111962307B CN 202010784891 A CN202010784891 A CN 202010784891A CN 111962307 B CN111962307 B CN 111962307B
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nitric oxide
self
antibacterial
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antibacterial material
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CN111962307A (en
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陆秋仙
陈涛
秦玉
曹贵平
毛雯
朱庆生
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Guangxi Nuogang Biotechnology Co ltd
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Nanjing Nuoling Biotechnology Co ltd
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    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
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Abstract

The invention relates to an antibacterial material capable of self-providing nitric oxide, a preparation method and application thereof, wherein the antibacterial material capable of self-providing nitric oxide comprises a substrate material and a functional material loaded on the substrate material; the functional material includes a NO donor material, a binder, a dispersant, and a water repellent. The NO donor material in the antibacterial material capable of providing nitric oxide can release NO under the stimulation of light, heat or water vapor, so that the antibacterial material has the functions of inhibiting the growth of microorganisms, sterilizing and resisting viruses; the NO donor material is stably adhered to the substrate material by adding the adhesive, the dispersing agent is added to ensure that the NO donor material is uniformly distributed on the substrate material, the waterproof agent helps the slow controlled release behavior of NO, the four materials supplement each other to realize synergistic interaction, meanwhile, the comfort and the air permeability of the antibacterial material can be ensured, and the antibacterial material is particularly suitable for being used as a preparation raw material of sanitary towels or protection pad products, and the duration time of NO release is kept to be about 2-5 hours under the triggering of water vapor.

Description

一种可自提供一氧化氮的抗菌材料及其制备方法和应用An antibacterial material capable of self-supplying nitric oxide, its preparation method and application

技术领域technical field

本发明属于抗菌材料技术领域,具体涉及一种抗菌材料及其制备方法和应用,尤其涉及一种可自提供一氧化氮的抗菌材料及其制备方法和其在制备卫生巾或护垫中的应用。The invention belongs to the technical field of antibacterial materials, in particular to an antibacterial material and its preparation method and application, especially to an antibacterial material capable of self-providing nitric oxide, its preparation method and its application in the preparation of sanitary napkins or protective pads .

背景技术Background technique

卫生巾或护垫,是一种具吸收力的物质,主要的材质为棉、不织布、纸浆或以上材质复合物所形成的高分子聚合物和高分子聚合物复合纸,用来吸收女性月经来潮时,自阴道流出的经血。由于女性在经期期间,会排出大量的经血,在卫生巾与阴道之间会形成一个局部潮湿的小环境,非常适宜于细菌的滋生。同时,配合以经血的成分组成特征,可以为细菌的滋生提供营养成分,更加的利于细菌的繁殖。而且,女性在经期期间,抵抗力下降,若此时阴道附近有大量细菌聚集,很容易会发生细菌感染,进而导致一系列的妇科疾病,体现在临床表现中,通常会出现有阴部瘙痒、白带增多以及腰酸等症状。然而,现有技术中某些有抗菌功效的卫生巾,存在着针对性不强,无法有效地起到抗菌功效的弊端。Sanitary napkin or panty liner is an absorbent material, the main material is cotton, non-woven fabric, pulp or polymer composite paper formed by a composite of the above materials, used to absorb women's menstrual cramps menstrual blood from the vagina. Because women will discharge a large amount of menstrual blood during menstruation, a small local moist environment will be formed between the sanitary napkin and the vagina, which is very suitable for the growth of bacteria. At the same time, combined with the composition characteristics of menstrual blood, it can provide nutrients for the growth of bacteria, which is more conducive to the reproduction of bacteria. Moreover, women’s resistance decreases during menstruation. If a large number of bacteria gather near the vagina at this time, bacterial infection is easy to occur, which in turn leads to a series of gynecological diseases, which are reflected in clinical manifestations, usually genital itching, leucorrhea Increase and backache and other symptoms. However, some sanitary napkins with antibacterial effect in the prior art have the disadvantages that they are not highly targeted and cannot effectively play an antibacterial effect.

CN102961773A公开了一种甲壳素抗菌卫生巾的制备方法,制备甲壳素抗菌纤维,质量比为(20%-40%):(80%-60%)的甲壳素抗菌纤维和ES纤维经开松机开松混合,根据克重要求设定经热风定型、铺网、收卷、分切,制成甲壳素生物抗菌无纺布;在制作卫生巾时,制成芯体材料后,喷胶覆甲壳素生物抗菌无纺布材料;然后,凹道成形,覆底膜,粘贴背翼离型纸,周封定型,外切成形,覆包膜及快易贴,横封、切断,制成甲壳素生物抗菌卫生巾。CN102961773A discloses a preparation method of chitin antibacterial sanitary napkin, preparing chitin antibacterial fiber, the mass ratio is (20%-40%): (80%-60%) chitin antibacterial fiber and ES fiber are passed through an opener Opening and mixing, setting according to the weight requirements, setting by hot air, net laying, winding, and cutting, to make chitin biological antibacterial non-woven fabrics; when making sanitary napkins, after making core materials, spray glue to cover the carapace Su biological antibacterial non-woven material; then, groove forming, cover the bottom film, paste the back wing release paper, seal the shape, cut and form, cover the film and quick and easy paste, horizontally seal, cut, and make the carapace Antibacterial Sanitary Napkins.

CN204798138U公开了一种设有矿植物复方保健抗菌芯片层的卫生巾,包括护围和卫生巾本体,所述卫生巾本体包括超细纤无纺布、纤维导流片、360度包覆的无尘纸、木棉层和矿植物复方保健抗菌芯片;该设有矿植物复方保健抗菌芯片层的卫生巾,内部设有矿植物复方保健抗菌芯片,能协助中和氧化物质,缓解月经期不适,使氧气和营养充分被吸收到细胞内。CN204798138U discloses a sanitary napkin provided with mineral-plant compound health-care antibacterial chip layer, including a skirt and a sanitary napkin body, and the sanitary napkin body includes a superfine fiber non-woven fabric, a fiber deflector, and a 360-degree coated non-woven fabric. Dust paper, kapok layer and mineral-plant compound health-care antibacterial chip; the sanitary napkin with mineral-plant compound health-care antibacterial chip layer is equipped with mineral-plant compound health-care antibacterial chip inside, which can help neutralize oxidative substances and relieve menstrual discomfort. Oxygen and nutrients are fully absorbed into the cells.

一氧化氮广泛存在于人体各种组织和细胞中,具有重要的生理功能。一氧化氮又称“血管内皮舒张因子”,能松弛血管平滑肌,并抑制血小板凝聚,还能够通过扩散,作用于相邻的周围神经元如突触前神经末梢和星状胶质细胞,再激活鸟苷酸环化酶从而提高环磷酸鸟苷水平从而产生生理效应,如诱导与学习、记忆有关的长时程增强效应。一氧化氮同时也是一种有效的广谱抗细菌和真菌试剂,正常鼻粘膜上皮细胞能够产生高浓度一氧化氮以防止呼吸道感染。巨噬细胞产生的一氧化氮能够杀灭多种病原体,包括常见医疗器械感染相关的大肠杆菌和金黄色葡萄球菌。研究表明,nM级别的一氧化氮就足以有效地破坏多种菌株形成的生物膜。含有一氧化氮供体的高分子材料也可以有效控制细菌感染,一氧化氮是半衰期极短的自由基气体分子,作用过程中不易产生抗药性和毒副作用,而伴随其的劣势是,一氧化氮自身气体及半衰期短的性质不利于存储和实际使用,这使得一氧化氮作为卫生用品抑菌剂或抗菌剂的应用受到很大限制。Nitric oxide widely exists in various tissues and cells of the human body and has important physiological functions. Nitric oxide, also known as "vascular endothelial relaxation factor", can relax vascular smooth muscle and inhibit platelet aggregation. It can also act on adjacent peripheral neurons such as presynaptic nerve endings and astrocytes through diffusion, and reactivate Guanylate cyclase thus increases the level of cyclic guanosine monophosphate to produce physiological effects, such as inducing long-term potentiation effects related to learning and memory. Nitric oxide is also an effective broad-spectrum antibacterial and fungal agent. Normal nasal mucosal epithelial cells can produce high concentrations of nitric oxide to prevent respiratory tract infections. Nitric oxide produced by macrophages can kill a variety of pathogens, including Escherichia coli and Staphylococcus aureus associated with common medical device infections. Studies have shown that nitric oxide at the nM level is sufficient to effectively destroy biofilms formed by various bacterial strains. Polymer materials containing nitric oxide donors can also effectively control bacterial infections. Nitric oxide is a free radical gas molecule with a very short half-life, and it is not easy to produce drug resistance and toxic side effects during the action process. The properties of nitrogen itself gas and short half-life are not conducive to storage and practical use, which greatly limits the application of nitric oxide as a bacteriostat or antibacterial agent for sanitary products.

发明内容Contents of the invention

针对现有技术的不足,本发明的目的在于提供一种抗菌材料及其制备方法和应用,尤其提供一种可自提供一氧化氮的抗菌材料及其制备方法和其在制备卫生巾或护垫中的应用。Aiming at the deficiencies in the prior art, the object of the present invention is to provide a kind of antibacterial material and its preparation method and application, especially to provide a kind of antibacterial material which can self-provide nitric oxide and its preparation method and its use in the preparation of sanitary napkin or panty liner in the application.

为达到此发明目的,本发明采用以下技术方案:To achieve this purpose of the invention, the present invention adopts the following technical solutions:

第一方面,本发明提供一种可自提供一氧化氮的抗菌材料,所述可自提供一氧化氮的抗菌材料包括基底材料和负载于所述基底材料的功能材料;所述功能材料包括NO供体材料、粘合剂、分散剂和防水剂。In a first aspect, the present invention provides an antibacterial material that can self-provide nitric oxide, the antibacterial material that can self-provide nitric oxide includes a base material and a functional material loaded on the base material; the functional material includes NO Donor materials, binders, dispersants and water repellents.

本发明所涉及的可自提供一氧化氮的抗菌材料中NO供体材料在光、热或水汽的刺激下能释放NO,起到抑制微生物生长、杀菌抗病毒的作用;但单纯的NO供体材料在基底材料上分布不均匀且极易掉落,最终影响材料的抗菌性能,本发明通过加入粘合剂使NO供体材料稳定地粘附于基底材料上,加入分散剂保证NO供体材料在基底材料上分布均匀,防水剂帮助NO的缓控释行为,四者相辅相成,协同增效,同时能保证抗菌材料的舒适性和透气性,特别适用于作为卫生巾或护垫产品的制备原料,在水汽的触发下,使NO释放的持续时间保持在2-5h左右。The NO donor material in the antibacterial material that can self-provide nitric oxide involved in the present invention can release NO under the stimulation of light, heat or water vapor, and play the role of inhibiting microbial growth, sterilization and anti-virus; but the simple NO donor The material is unevenly distributed on the base material and is easy to fall off, which ultimately affects the antibacterial performance of the material. The present invention makes the NO donor material adhere to the base material stably by adding an adhesive, and adds a dispersant to ensure that the NO donor material Evenly distributed on the base material, the water repellent helps the slow and controlled release of NO, the four complement each other and synergize, and at the same time can ensure the comfort and air permeability of the antibacterial material, especially suitable for the preparation of sanitary napkins or panty liners , under the trigger of water vapor, the duration of NO release is kept at about 2-5h.

优选地,所述功能材料以质量份数计包括NO供体材料4-7份、粘合剂1-5份、分散剂0.1-10份和防水剂1-30份。Preferably, the functional material includes 4-7 parts by mass of NO donor material, 1-5 parts of binder, 0.1-10 parts of dispersant and 1-30 parts of waterproofing agent.

本发明所涉及的可自提供一氧化氮的抗菌材料中四种功能材料在上述质量份数的配比下,能够使材料的粘附性、稳定性、分散均匀性、NO供体材料利用率、抗菌性达到更好的效果。若粘合剂相对于NO供体材料的份数过多会导致无纺布硬度增大,无纺布之间的结构孔隙遭堵塞,造成卫生巾护垫局部透气性下降,份数过少会使供体粘附于基底材料上的总量减少,从而导致NO供体利用率降低;分散剂相对于NO供体材料的份数过多会导致粘合剂附着力下降和浓度衰减,从而减弱其粘连的作用,份数过少会使供体未完全均匀分布于溶液中,分散不稳定易形成供体沉降,导致喷涂于无纺布上时呈现颗粒状,同时NO供体在无纺布上分布不均匀;防水剂相对于NO供体材料的份数过多会在人体使用卫生巾用品过程中至更换时间,供体未能完全释放,份数过少会在人体使用卫生巾用品过程中,供体释放NO时间过快,不能满足所需佩戴的时长。The four kinds of functional materials in the antibacterial material that can self-provide nitric oxide involved in the present invention can make the adhesion, stability, dispersion uniformity, and NO donor material utilization rate of the material under the proportioning ratio of the above-mentioned parts by mass. , antibacterial to achieve better results. If the number of adhesives relative to the NO donor material is too large, the hardness of the non-woven fabric will increase, and the structural pores between the non-woven fabrics will be blocked, resulting in a decrease in the local air permeability of the sanitary napkin pad. Reduce the total amount of donors adhering to the base material, resulting in a decrease in the utilization of NO donors; too many parts of the dispersant relative to the NO donor material will lead to a decrease in adhesive adhesion and concentration decay, thereby weakening The role of its adhesion, if the number of parts is too small, the donor will not be completely evenly distributed in the solution, and the dispersion will be unstable and easy to form donor sedimentation, resulting in the appearance of particles when sprayed on the non-woven fabric. The distribution on the surface is uneven; the number of parts of the waterproofing agent relative to the NO donor material is too large, and the donor will not be completely released during the process of using sanitary napkins by the human body until the replacement time, and the number of parts is too small. In , the donor releases NO time too fast to meet the required wearing time.

所述NO供体材料的质量份数可以为4份、5份、6份或7份等,上述数值范围内的任意具体点值均可选择,在此便不再一一赘述。The mass parts of the NO donor material can be 4 parts, 5 parts, 6 parts or 7 parts, etc. Any specific point value within the above numerical range can be selected, and details will not be repeated here.

所述防水剂的质量份数可以为1份、3份、5份、8份、10份、12份、13份、15份、18份、20份、25份或30份等,上述数值范围内的任意具体点值均可选择,在此便不再一一赘述。The mass parts of the waterproofing agent can be 1 part, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 13 parts, 15 parts, 18 parts, 20 parts, 25 parts or 30 parts, etc., the above numerical range Any specific point value in can be selected, and will not be repeated here.

所述粘合剂的质量份数可以为1份、2份、3份、4份或5份等,上述数值范围内的任意具体点值均可选择,在此便不再一一赘述。The mass parts of the adhesive can be 1 part, 2 parts, 3 parts, 4 parts or 5 parts, etc. Any specific point value within the above numerical range can be selected, and details will not be repeated here.

所述分散剂的质量份数可以为0.1份、0.2份、0.6份、1份、2份、3份、4份、5份、6份、8份或10份等,上述数值范围内的任意具体点值均可选择,在此便不再一一赘述。The number of parts by mass of the dispersant can be 0.1 part, 0.2 part, 0.6 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 8 parts or 10 parts, etc. The specific point values can be selected, and will not be repeated here.

优选地,所述NO供体材料在所述基底材料上的负载率为50%-90%。Preferably, the loading rate of the NO donor material on the base material is 50%-90%.

本发明所涉及的抗菌芯片中NO供体材料在所述基底材料上的负载率特定选择为50%-90%,是因为,若负载率过高会造成成品无纺布硬度大,透气性下降,负载率过低会造成供体利用率降低,成本升高。In the antibacterial chip involved in the present invention, the loading rate of the NO donor material on the base material is specifically selected as 50%-90%, because if the loading rate is too high, the finished non-woven fabric will have high hardness and decreased air permeability. , If the load rate is too low, the donor utilization rate will decrease and the cost will increase.

优选地,所述基底材料包括无纺布、熔喷布、过滤棉、聚丙烯不织布或海绵,优选无纺布。Preferably, the base material includes non-woven fabric, melt-blown fabric, filter cotton, polypropylene non-woven fabric or sponge, preferably non-woven fabric.

本发明所涉及的可自提供一氧化氮的抗菌材料中基底材料可任选上述类型,单一因素对比上述各基底材料的性质发现,过滤棉、聚丙烯不织布和海绵的透水性和透水汽性均较好,功能材料在上面的分散均匀性较差;熔喷布的透水性和透水汽性均较差,功能材料在上面的分散均匀性也较差;无纺布的透水性差,但透水汽性能好,且功能材料在上面的分散均匀性也较好,因此更优选无纺布作为基底材料。The base material that the present invention relates to can self-provide the antibacterial material of nitric oxide can choose above-mentioned type, single factor compares the property of above-mentioned each base material and finds, the water permeability and water vapor permeability of filter cotton, polypropylene non-woven fabric and sponge are all Better, the dispersion uniformity of functional materials on it is poor; the water permeability and water vapor permeability of melt blown cloth are poor, and the dispersion uniformity of functional materials on it is also poor; the water permeability of non-woven fabrics is poor, but the water vapor permeability The performance is good, and the dispersion uniformity of functional materials on it is also good, so non-woven fabric is more preferred as the base material.

优选地,所述NO供体材料包括亚硝基铁氢化钠、S-亚硝基-N-乙酰青霉胺、S-亚硝基谷胱甘肽、偶氮烯翁二醇系列化合物或偶氮烯翁二醇负载高分子中的任意一种或至少两种的组合,所述至少两种的组合例如S-亚硝基谷胱甘肽和S-亚硝基-N-乙酰青霉胺的组合、亚硝基铁氢化钠和偶氮烯翁二醇系列化合物的组合等,其他任意的组合方式均可选择,在此便不再一一赘述。优选S-亚硝基谷胱甘肽。Preferably, the NO donor material includes nitrosoferric sodium hydride, S-nitroso-N-acetylpenicillamine, S-nitrosoglutathione, azodiol series compounds or even Any one or a combination of at least two of the carbazole-loaded polymers, such as S-nitrosoglutathione and S-nitroso-N-acetylpenicillamine The combination of sodium nitrosoferric hydride and azocenediol series compounds, etc., any other combination can be selected, and will not be repeated here. S-nitrosoglutathione is preferred.

本发明所涉及的可自提供一氧化氮的抗菌材料中NO供体材料可任选上述类型,其中优选S-亚硝基谷胱甘肽(GSNO)或S-亚硝基-N-乙酰青霉胺(SNAP)两种材料作为NO供体材料,S-亚硝基谷胱甘肽粉末呈淡粉色,S-亚硝基-N-乙酰青霉胺粉末呈淡绿色,使得抗菌功能材料整体呈现淡粉色或淡绿色,在实际使用过程中,随着NO的释放,材料逐渐由淡粉色或淡绿色变成无色,时间越长颜色越淡,这对使用者起到一个指示作用,从侧面反映出NO的释放速度以及材料抗菌活性的高低。若将其用于制备卫生巾或护垫,在使用过程中,由于水汽的作用,能够刺激释放NO,从而抑制局部环境中的微生物,且随着使用时间的延长,卫生巾或护垫颜色会由淡粉色或淡绿色逐渐变为无色,这提示使用者“抗菌活性的剩余量”以及及时更换卫生巾或护垫。In the antibacterial material that can provide nitric oxide involved in the present invention, the NO donor material can be selected from the above-mentioned types, wherein preferred S-nitrosoglutathione (GSNO) or S-nitroso-N-acetylcyanine Mycamine (SNAP) two materials are used as NO donor materials, S-nitrosoglutathione powder is light pink, and S-nitroso-N-acetylpenicillamine powder is light green, making the antibacterial functional material overall It is light pink or light green. In actual use, with the release of NO, the material gradually changes from light pink or light green to colorless. The longer the time, the lighter the color, which serves as an indicator for the user. The side reflects the release rate of NO and the antibacterial activity of the material. If it is used to prepare sanitary napkins or panty liners, during use, due to the effect of water vapor, it can stimulate the release of NO, thereby inhibiting microorganisms in the local environment, and with the prolongation of use time, the color of sanitary napkins or panty liner pads will change. It gradually changes from light pink or light green to colorless, which reminds users of "the remaining amount of antibacterial activity" and timely replacement of sanitary napkins or panty liners.

而对比S-亚硝基谷胱甘肽和S--亚硝基-N-乙酰青霉胺两种材料,前者是一种内源性物质,无气味,后者不是内源性物质,且有一定气味,后续使用还需采取其他方式去除或掩盖其气味。因此,更优选S-亚硝基谷胱甘肽作为本发明的可自提供一氧化氮的抗菌材料中的NO供体材料。While comparing the two materials of S-nitrosoglutathione and S-nitroso-N-acetylpenicillamine, the former is an endogenous substance without odor, while the latter is not an endogenous substance, and There is a certain smell, and subsequent use needs to take other methods to remove or cover up the smell. Therefore, S-nitrosoglutathione is more preferred as the NO donor material in the antibacterial material capable of self-supplying nitric oxide of the present invention.

优选地,所述粘合剂包括糊精、羟甲基纤维素、硅胶、果胶或聚醋酸乙烯乳胶中的任意一种或至少两种的组合,所述至少两种的组合例如糊精和羟甲基纤维素的组合、硅胶和果胶的组合、果胶和聚醋酸乙烯乳胶的组合等,其他任意的组合方式均可选择,在此便不再一一赘述。优选聚醋酸乙烯乳胶。Preferably, the binder includes any one or a combination of at least two of dextrin, hydroxymethyl cellulose, silica gel, pectin or polyvinyl acetate latex, the combination of at least two such as dextrin and The combination of hydroxymethyl cellulose, the combination of silica gel and pectin, the combination of pectin and polyvinyl acetate latex, etc., any other combination can be selected, and will not be repeated here. Polyvinyl acetate latex is preferred.

相比于其他粘合剂类型,聚醋酸乙烯乳胶在促进功能材料在基底材料上的粘附能力方面更胜一筹。Compared to other adhesive types, polyvinyl acetate latex is superior in its ability to promote the adhesion of functional materials to substrate materials.

优选地,所述分散剂包括聚乙烯醇、聚乙二醇、十二烷基硫酸钠或十二烷基磺酸钠中的任意一种或至少两种的组合,所述至少两种的组合例如聚乙烯醇和聚乙二醇的组合、十二烷基硫酸钠和十二烷基磺酸钠的组合、聚乙烯醇和十二烷基硫酸钠的组合等,其他任意的组合方式均可选择,在此便不再一一赘述。优选聚乙烯醇和十二烷基硫酸钠的组合。Preferably, the dispersant includes any one or a combination of at least two of polyvinyl alcohol, polyethylene glycol, sodium lauryl sulfate or sodium dodecyl sulfate, and the combination of at least two For example, the combination of polyvinyl alcohol and polyethylene glycol, the combination of sodium lauryl sulfate and sodium lauryl sulfate, the combination of polyvinyl alcohol and sodium lauryl sulfate, etc., any other combination can be selected, I won’t go into details here. A combination of polyvinyl alcohol and sodium lauryl sulfate is preferred.

相比于其他分散剂类型,聚乙烯醇和十二烷基硫酸钠的组合在促进功能材料在基底材料上的分散均匀性方面更加显著。Compared with other dispersant types, the combination of polyvinyl alcohol and sodium lauryl sulfate is more significant in promoting the uniformity of dispersion of functional materials on substrate materials.

优选地,所述防水剂包括二甲硅油、液体石蜡、固体石蜡、有机硅树脂、羊毛脂、天然树脂或凡士林中的任意一种或至少两种的组合;所述至少两种的组合例如液体石蜡和固体石蜡的组合、二甲硅油和有机硅树脂的组合、有机硅树脂和羊毛脂的组合等,其他任意的组合方式均可选择,在此便不再一一赘述。优选天然树脂。Preferably, the waterproofing agent includes any one or a combination of at least two of simethicone, liquid paraffin, solid paraffin, silicone resin, lanolin, natural resin or petrolatum; The combination of paraffin wax and solid paraffin, the combination of simethicone and silicone resin, the combination of silicone resin and lanolin, etc., any other combination can be selected, and will not be repeated here. Natural resins are preferred.

相比于其他防水剂类型,天然树脂,在用于卫生巾护垫抗菌芯片的场景时,外观形态更佳,无粘感,不会脱落,同时能使抗菌芯片经水系后一氧化氮供体缓慢释放出NO,且防水方面具有更好的效果。Compared with other types of waterproofing agents, natural resins have a better appearance, no stickiness, and no falling off when used in the scene of antibacterial chips in sanitary napkin pads. At the same time, they can make the antibacterial chips donate nitric oxide after passing through the water system It releases NO slowly and has a better effect in waterproofing.

第二方面,本发明提供一种如上所述的可自提供一氧化氮的抗菌材料的制备方法,所述制备方法包括:In a second aspect, the present invention provides a method for preparing an antibacterial material that can self-provide nitric oxide as described above, the preparation method comprising:

(1)将NO供体材料、粘合剂、分散剂和溶剂混合制备涂层液;(1) mixing NO donor material, binder, dispersant and solvent to prepare coating liquid;

(2)将步骤(1)制得的涂层液喷淋至基底材料上,干燥,最后将防水剂涂覆于基底材料表面,得到所述可自提供一氧化氮的抗菌材料。(2) Spray the coating solution prepared in step (1) onto the base material, dry, and finally apply a waterproofing agent on the surface of the base material to obtain the antibacterial material that can provide nitric oxide by itself.

所述喷淋需要匀速缓慢地喷淋,速度不宜过大,以免溶液的水分子穿透基底材料的孔隙不能达到滞留的效果。本发明所涉及的可自提供一氧化氮的抗菌材料的制备方法工艺简单,易操作,适合于工业化生产。The spray needs to be sprayed slowly at a uniform speed, and the speed should not be too high, so as to prevent the water molecules of the solution from penetrating through the pores of the base material and fail to achieve the retention effect. The preparation method of the antibacterial material capable of self-providing nitric oxide involved in the present invention has simple process, easy operation and is suitable for industrial production.

优选地,步骤(1)具体包括如下步骤:Preferably, step (1) specifically includes the following steps:

(a)将分散剂与溶剂混合,搅拌,制得溶液A;将NO供体材料与溶剂混合,搅拌,再与粘合剂混合,搅拌,制得溶液B;(a) mixing the dispersant with the solvent and stirring to prepare solution A; mixing the NO donor material with the solvent and stirring, then mixing with the binder and stirring to obtain solution B;

(b)将步骤(a)制得的溶液A和溶液B混合,搅拌,制得涂层液。(b) Mix and stir the solution A and solution B prepared in step (a) to prepare a coating liquid.

步骤(a)中溶液B的配制将影响涂层后抗菌材料的视觉效果,若供体材料没有充分地溶解于溶剂中,喷涂后会形成大小不一的粉色斑块,影响材料的整体美感。The preparation of solution B in step (a) will affect the visual effect of the antibacterial material after coating. If the donor material is not fully dissolved in the solvent, pink plaques of different sizes will be formed after spraying, which will affect the overall aesthetic feeling of the material.

本发明制备抗菌材料时,上述特定的涂层液配制顺序,不仅保证了NO供体材料的释放,同时有利于供体材料和基底材料的粘合,最终发挥抑制微生物的自清洁性能。When the antibacterial material is prepared in the present invention, the above specific preparation sequence of the coating solution not only ensures the release of the NO donor material, but also facilitates the adhesion of the donor material and the base material, and finally exerts the self-cleaning performance of inhibiting microorganisms.

所述干燥的目的是为了让NO供体更好地附着于基底材料上,可以选择一个干净平整的平面台,在规定的时间内挥发干燥,供体材料渗入基底材料内部,这时溶液中的粘合剂发挥粘连的功能,将供体更好的锁定在基底材料上。其不能在阳光下暴晒、也不能在热强风下进行烘干,阳光以及热风会导致供体提早释放出NO,从而导致供体的有效含量减少。The purpose of the drying is to allow the NO donors to better adhere to the base material. You can choose a clean and flat platform, volatilize and dry within a specified time, and the donor material penetrates into the base material. At this time, the NO donors in the solution The adhesive acts as an adhesive to better lock the donor to the base material. It cannot be exposed to sunlight or dried under hot and strong wind. Sunlight and hot wind will cause the donor to release NO early, resulting in a decrease in the effective content of the donor.

优选地,步骤(2)所述干燥的温度为20-40℃,例如20℃、25℃、30℃、35℃或40℃等,范围内的其他具体点值均可选择,在此便不再一一赘述。Preferably, the drying temperature in step (2) is 20-40°C, such as 20°C, 25°C, 30°C, 35°C or 40°C, etc. Other specific point values in the range can be selected, and it will not be mentioned here Let me repeat them one by one.

优选地,所述干燥的时间为1-3h,例如1h、1.5h、2h、2.5h或3h等,范围内的其他具体点值均可选择,在此便不再一一赘述。Preferably, the drying time is 1-3h, such as 1h, 1.5h, 2h, 2.5h or 3h, etc. Other specific points within the range can be selected, and will not be repeated here.

优选地,步骤(2)所述涂层液喷淋至基底材料上的操作共进行1-5次,例如1次、2次、3次、4次或5次。Preferably, the operation of spraying the coating liquid onto the base material in step (2) is performed 1-5 times in total, such as 1 time, 2 times, 3 times, 4 times or 5 times.

第三方面,本发明提供一种如上所述的可自提供一氧化氮的抗菌材料在制备卫生巾或护垫中的应用。In a third aspect, the present invention provides an application of the above-mentioned self-providing nitric oxide antibacterial material in the preparation of sanitary napkins or panty liners.

相对于现有技术,本发明具有以下有益效果:Compared with the prior art, the present invention has the following beneficial effects:

本发明所涉及的可自提供一氧化氮的抗菌材料中NO供体材料在光、热或水汽的刺激下能释放NO,起到抑制微生物生长、杀菌抗病毒的作用;但单纯的NO供体材料在基底材料上分布不均匀且极易掉落,最终影响材料的抗菌性能,本发明通过加入粘合剂使NO供体材料稳定地粘附于基底材料上,加入分散剂保证NO供体材料在基底材料上分布均匀,防水剂帮助NO的缓控释行为,四者相辅相成,协同增效,同时能保证抗菌材料的舒适性和透气性,特别适用于作为卫生巾或护垫产品的制备原料,在水汽的触发下,使NO释放的持续时间保持在2-5h左右。The NO donor material in the antibacterial material that can self-provide nitric oxide involved in the present invention can release NO under the stimulation of light, heat or water vapor, and play the role of inhibiting microbial growth, sterilization and anti-virus; but the simple NO donor The material is unevenly distributed on the base material and is easy to fall off, which ultimately affects the antibacterial performance of the material. The present invention makes the NO donor material adhere to the base material stably by adding an adhesive, and adds a dispersant to ensure that the NO donor material Evenly distributed on the base material, the water repellent helps the slow and controlled release of NO, the four complement each other and synergize, and at the same time can ensure the comfort and air permeability of the antibacterial material, especially suitable for the preparation of sanitary napkins or panty liners , under the trigger of water vapor, the duration of NO release is kept at about 2-5h.

当使用GSNO或SNAP作为NO供体时,若将该可自提供一氧化氮的抗菌材料用于制备卫生巾或护垫,在使用过程中,随着使用时间的延长,颜色会由淡粉色或淡绿色逐渐变为无色,这提示使用者“抗菌活性的剩余量”以及及时更换卫生巾或护垫。When GSNO or SNAP is used as NO donor, if the antibacterial material that can self-provide nitric oxide is used to prepare sanitary napkins or panty liners, the color will change from pale pink or The light green gradually turns colorless, which reminds the user of the "remaining amount of antibacterial activity" and timely replacement of sanitary napkins or panty liners.

附图说明Description of drawings

图1是实施例1制备产品在释放NO前后的颜色变化图;Fig. 1 is the color change diagram of the product prepared in Example 1 before and after releasing NO;

图2是实施例1产品在进行抗菌性考察时的平板菌落图;Fig. 2 is the plate colony diagram when the product of embodiment 1 is carrying out antibacterial investigation;

图3是卡那霉素组在进行抗菌性考察时的平板菌落图;Fig. 3 is the plate colony figure of kanamycin group when carrying out antibacterial investigation;

图4是银离子组在进行抗菌性考察时的平板菌落图;Fig. 4 is the plate colony diagram when silver ion group is carrying out antibacterial investigation;

图5是空白对照组在进行抗菌性考察时的平板菌落图。Figure 5 is a plate colony diagram of the blank control group when the antibacterial property was investigated.

具体实施方式Detailed ways

下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。The technical solutions of the present invention will be further described below through specific embodiments. It should be clear to those skilled in the art that the embodiments are only for helping to understand the present invention, and should not be regarded as specific limitations on the present invention.

实施例1Example 1

本实施例制备一种可自提供一氧化氮的抗菌材料,包括基底材料(无纺布)和负载于所述无纺布上的功能材料;所述功能材料包括NO供体材料(GSNO)、粘合剂(聚醋酸乙烯乳胶)、分散剂(聚乙烯醇和十二烷基硫酸钠)和防水剂(天然树脂)。其制备方法如下:This embodiment prepares a kind of antibacterial material that can self-provide nitric oxide, comprises base material (non-woven fabric) and the functional material loaded on the described non-woven fabric; Said functional material comprises NO donor material (GSNO), Binders (polyvinyl acetate latex), dispersants (polyvinyl alcohol and sodium lauryl sulfate) and water repellents (natural resins). Its preparation method is as follows:

(1)将20mg聚乙烯醇、5mg十二烷基硫酸钠与10mL水混合,23℃下搅拌10min,制得溶液A;将500mg GSNO与10mL水混合,23℃下搅拌5min,再与250mg聚醋酸乙烯乳胶混合,23℃下搅拌5min,制得溶液B;(1) Mix 20mg of polyvinyl alcohol, 5mg of sodium lauryl sulfate with 10mL of water, and stir at 23°C for 10min to prepare solution A; mix 500mg of GSNO with 10mL of water, stir at 23°C for 5min, then mix with 250mg of polystyrene Mix vinyl acetate latex and stir at 23°C for 5 minutes to prepare solution B;

(2)将步骤(1)制得的溶液A和溶液B混合,23℃下搅拌5min,制得涂层液;(2) Mix solution A and solution B prepared in step (1), and stir at 23° C. for 5 minutes to obtain a coating solution;

(3)将步骤(2)得到的涂层液均匀喷淋至厚度为0.185mm的无纺布上,挥发干燥,再重复一次喷淋,最终GSNO在无纺布上的负载率为83%,再次挥发干燥;(3) Evenly spray the coating solution obtained in step (2) onto a nonwoven fabric with a thickness of 0.185 mm, volatilize and dry, and repeat the spraying again. Finally, the loading rate of GSNO on the nonwoven fabric is 83%. volatilize and dry again;

(4)将800mg防水剂(天然树脂)置于滚轮两侧均匀涂覆于步骤(3)产品表面的正反面,得到所述可自提供一氧化氮的抗菌材料。(4) Place 800mg of waterproofing agent (natural resin) on both sides of the roller and evenly coat the front and back of the product surface in step (3) to obtain the antibacterial material that can provide nitric oxide by itself.

实施例2Example 2

本实施例制备一种可自提供一氧化氮的抗菌材料,包括基底材料(无纺布)和负载于所述无纺布上的功能材料;所述功能材料包括NO供体材料(SNAP)、粘合剂(聚醋酸乙烯乳胶)、分散剂(聚乙烯醇和十二烷基硫酸钠)和防水剂(天然树脂)。其制备方法如下:This embodiment prepares a kind of antibacterial material that can self-provide nitric oxide, comprises base material (non-woven fabric) and the functional material loaded on the described non-woven fabric; Said functional material comprises NO donor material (SNAP), Binders (polyvinyl acetate latex), dispersants (polyvinyl alcohol and sodium lauryl sulfate) and water repellents (natural resins). Its preparation method is as follows:

(1)将10mg聚乙烯醇、2.5mg十二烷基硫酸钠与5mL水混合,23℃下搅拌10min,制得溶液A;将250mg SNAP与2mL水混合,23℃下搅拌5min,再与125mg聚醋酸乙烯乳胶混合,23℃下搅拌5min,最后加入SNAP促溶剂3mL无水乙醇23℃下搅拌5min,制得溶液B;(1) Mix 10mg of polyvinyl alcohol, 2.5mg of sodium lauryl sulfate with 5mL of water, and stir at 23°C for 10min to prepare solution A; mix 250mg of SNAP with 2mL of water, stir at 23°C for 5min, then mix with 125mg Mix polyvinyl acetate latex, stir at 23°C for 5 minutes, and finally add SNAP solubilizer 3mL absolute ethanol and stir at 23°C for 5 minutes to prepare solution B;

(2)将步骤(1)制得的溶液A和溶液B混合,23℃下搅拌5min,制得涂层液;(2) Mix solution A and solution B prepared in step (1), and stir at 23° C. for 5 minutes to obtain a coating solution;

(3)将步骤(2)得到的涂层液均匀喷淋至0.185mm的无纺布上,挥发干燥,再重复一次喷淋,最终SNAP在无纺布上的负载率为84%,再次挥发干燥;(3) Evenly spray the coating solution obtained in step (2) onto a 0.185mm non-woven fabric, volatilize and dry, and repeat the spraying again. Finally, the loading rate of SNAP on the non-woven fabric is 84%, and volatilizes again dry;

(4)将500mg防水剂(天然树脂)置于滚轮两侧涂覆于步骤(3)产品正反面,得到所述可自提供一氧化氮的抗菌材料。(4) Put 500mg of waterproofing agent (natural resin) on both sides of the roller and apply it on the front and back of the product in step (3), to obtain the antibacterial material that can provide nitric oxide by itself.

实施例3Example 3

本实施例制备一种可自提供一氧化氮的抗菌材料,其结构组成与实施例1的区别仅在于将分散剂(聚乙烯醇和十二烷基硫酸钠)替换为同等分量的分散剂(十二烷基硫酸钠),制备方法步骤(1)中为:将25mg十二烷基硫酸钠与10mL水混合。其他条件均保持不变。This embodiment prepares a kind of antimicrobial material that can self-provide nitric oxide, and the difference of its structural composition and embodiment 1 is only that dispersant (polyvinyl alcohol and sodium lauryl sulfate) is replaced with the dispersant of equal weight (ten Dialkyl sodium sulfate), in the preparation method step (1): 25mg sodium lauryl sulfate is mixed with 10mL water. All other conditions remain unchanged.

实施例4Example 4

本实施例制备一种可自提供一氧化氮的抗菌材料,其结构组成与实施例1的区别仅在于将粘合剂聚醋酸乙烯乳胶替换为同等分量的粘合剂硅胶,其他条件均保持一致。其制备方法参考实施例1。This example prepares an antibacterial material that can self-provide nitric oxide. The difference between its structure and composition and Example 1 is that the adhesive polyvinyl acetate latex is replaced by an equal amount of adhesive silica gel, and other conditions are kept the same. . Its preparation method refers to Example 1.

实施例5Example 5

本实施例制备一种可自提供一氧化氮的抗菌材料,其结构组成与实施例1一致。其制备方法与实施例1略有不同:In this example, an antibacterial material capable of self-supplying nitric oxide is prepared, and its structure and composition are consistent with Example 1. Its preparation method is slightly different from Example 1:

(1)将20mg聚乙烯醇、5mg十二烷基硫酸钠、500mg GSNO、250mg聚醋酸乙烯乳胶与20mL水混合,23℃下搅拌10min,制得涂层液;(1) Mix 20mg of polyvinyl alcohol, 5mg of sodium lauryl sulfate, 500mg of GSNO, 250mg of polyvinyl acetate latex with 20mL of water, and stir at 23°C for 10min to prepare a coating solution;

(2)将步骤(1)得到的涂层液均匀喷淋至厚度为0.185mm的无纺布上,挥发干燥,再重复一次喷淋,最终GSNO在无纺布上的负载率为80%,再次挥发干燥;(2) Evenly spray the coating solution obtained in step (1) onto a non-woven fabric with a thickness of 0.185mm, volatilize and dry, and repeat the spraying again. Finally, the loading rate of GSNO on the non-woven fabric is 80%. volatilize and dry again;

(3)将800mg防水剂(天然树脂)置于滚轮两侧涂覆于步骤(2)产品正反面,得到所述抗菌芯片。(3) Place 800mg of waterproofing agent (natural resin) on both sides of the roller and apply it to the front and back of the product in step (2) to obtain the antibacterial chip.

对比例1Comparative example 1

本对比例制备一种可自提供一氧化氮的抗菌材料,其结构组成与实施例1的区别仅在于不含有粘合剂成分,其他条件均保持一致。其制备方法如下:In this comparative example, an antibacterial material capable of self-supplying nitric oxide was prepared. The difference between its structure and composition and that of Example 1 is that it does not contain a binder component, and other conditions remain the same. Its preparation method is as follows:

(1)将20mg聚乙烯醇、5mg十二烷基硫酸钠与10mL水混合,23℃下搅拌10min,制得溶液A;将500mg GSNO与10mL水混合,23℃下搅拌5min,制得溶液B;(1) Mix 20mg of polyvinyl alcohol, 5mg of sodium lauryl sulfate with 10mL of water, and stir at 23°C for 10min to prepare solution A; mix 500mg of GSNO with 10mL of water, and stir at 23°C for 5min to prepare solution B ;

(2)将步骤(1)制得的溶液A和溶液B混合,23℃下搅拌5min,制得涂层液;(2) Mix solution A and solution B prepared in step (1), and stir at 23° C. for 5 minutes to obtain a coating solution;

(3)将步骤(2)得到的涂层液均匀喷淋至厚度为0.185mm的无纺布上,挥发干燥,再重复一次喷淋,最终GSNO在无纺布上的负载率为47%,再次挥发干燥;(3) Evenly spray the coating solution obtained in step (2) onto a nonwoven fabric with a thickness of 0.185mm, volatilize and dry, and repeat the spraying again. Finally, the loading rate of GSNO on the nonwoven fabric is 47%. volatilize and dry again;

(4)将800mg防水剂(天然树脂)置于滚轮两侧涂覆于步骤(3)产品表面,得到所述可自提供一氧化氮的抗菌材料。(4) Place 800mg of water repellent (natural resin) on both sides of the roller and apply it on the surface of the product in step (3) to obtain the antibacterial material that can self-provide nitric oxide.

对比例2Comparative example 2

本对比例制备一种可自提供一氧化氮的抗菌材料,其结构组成与实施例1的区别仅在于不含有分散剂成分,其他条件均保持一致。其制备方法如下:In this comparative example, an antibacterial material capable of self-supplying nitric oxide was prepared. The difference between its structure and composition and that of Example 1 is that it does not contain a dispersant component, and other conditions remain the same. Its preparation method is as follows:

(1)将500mg GSNO与10mL水混合,23℃下搅拌5min,再与250mg聚醋酸乙烯乳胶混合,23℃下搅拌5min,制得溶液B;(1) Mix 500mg GSNO with 10mL water, stir at 23°C for 5min, then mix with 250mg of polyvinyl acetate latex, stir at 23°C for 5min to prepare solution B;

(2)将步骤(1)制得的溶液A和溶液B混合,23℃下搅拌5min,制得涂层液;(2) Mix solution A and solution B prepared in step (1), and stir at 23° C. for 5 minutes to obtain a coating solution;

(3)将步骤(2)得到的涂层液均匀喷淋至厚度为0.185mm的无纺布上,挥发干燥,再重复一次喷淋,最终GSNO在无纺布上的负载率为70%,再次挥发干燥;(3) Evenly spray the coating solution obtained in step (2) onto a nonwoven fabric with a thickness of 0.185 mm, volatilize and dry, and repeat the spraying again. Finally, the loading rate of GSNO on the nonwoven fabric is 70%. volatilize and dry again;

(4)将800mg防水剂(天然树脂)置于滚轮两侧涂覆于步骤(3)产品表面,得到所述可自提供一氧化氮的抗菌材料。(4) Place 800mg of water repellent (natural resin) on both sides of the roller and apply it on the surface of the product in step (3) to obtain the antibacterial material that can self-provide nitric oxide.

对比例3Comparative example 3

本对比例制备一种可自提供一氧化氮的抗菌材料,其结构组成与实施例1的区别仅在于不含有防水剂成分,其他条件均保持一致。其制备方法如下:In this comparative example, an antibacterial material capable of self-supplying nitric oxide was prepared. The difference between its structure and composition and that of Example 1 is that it does not contain a water repellent component, and other conditions remain the same. Its preparation method is as follows:

(1)将20mg聚乙烯醇、5mg十二烷基硫酸钠与10mL水混合,23℃下搅拌10min,制得溶液A;将500mg GSNO与10mL水混合,23℃下搅拌5min,再与250mg聚醋酸乙烯乳胶混合,23℃下搅拌5min,制得溶液B;(1) Mix 20mg of polyvinyl alcohol, 5mg of sodium lauryl sulfate with 10mL of water, and stir at 23°C for 10min to prepare solution A; mix 500mg of GSNO with 10mL of water, stir at 23°C for 5min, then mix with 250mg of polystyrene Mix vinyl acetate latex and stir at 23°C for 5 minutes to prepare solution B;

(2)将步骤(1)制得的溶液A和溶液B混合,23℃下搅拌5min,制得涂层液;(2) Mix solution A and solution B prepared in step (1), and stir at 23° C. for 5 minutes to obtain a coating solution;

(3)将步骤(2)得到的涂层液均匀喷淋至厚度为0.185mm的无纺布上,挥发干燥,再重复一次喷淋,最终GSNO在无纺布上的负载率为83%,再次挥发干燥;得到所述可自提供一氧化氮的抗菌材料。(3) Evenly spray the coating solution obtained in step (2) onto a nonwoven fabric with a thickness of 0.185 mm, volatilize and dry, and repeat the spraying again. Finally, the loading rate of GSNO on the nonwoven fabric is 83%. Volatilize and dry again; obtain the antibacterial material that can self-provide nitric oxide.

评价试验:Evaluation test:

(1)粘附性评价:(1) Adhesion evaluation:

对实施例1-5和对比例1-3制得的产品进行粘附性考察,评价方法具体为:基于制备得到的样品,通过揉搓方式作用不同时间后,对比样品前后重量变化以此来评价粘附性,揉搓前后重量无明显变化,则表明粘附性好,揉搓前后重量变化明显,则表明粘附性差,结果如表1所示。The adhesiveness of the products prepared in Examples 1-5 and Comparative Examples 1-3 was inspected, and the evaluation method was as follows: based on the prepared samples, after rubbing for different times, the weight changes before and after the samples were compared to evaluate Adhesion, if there is no significant change in weight before and after rubbing, it indicates good adhesion, and if the weight changes significantly before and after rubbing, it indicates poor adhesion. The results are shown in Table 1.

表1Table 1

组别group 未处理(mg)Untreated (mg) 揉搓1min(mg)Knead for 1min(mg) 揉搓2min(mg)Knead for 2min(mg) 实施例1Example 1 80.8280.82 80.4080.40 80.2180.21 实施例2Example 2 81.1681.16 80.6580.65 80.3280.32 实施例3Example 3 79.4979.49 78.5778.57 78.0278.02 实施例4Example 4 79.1779.17 78.5878.58 77.4977.49 实施例5Example 5 79.8979.89 79.5379.53 79.2079.20 对比例1Comparative example 1 68.8468.84 65.9765.97 63.9563.95 对比例2Comparative example 2 76.5076.50 75.4575.45 74.3874.38 对比例3Comparative example 3 80.8280.82 80.4080.40 79.8679.86

由表1数据可知:实施例1与实施例2相对于对比例1,抗菌芯片经揉搓后前后重量未发生明显变化,说明NO供体在粘合剂作用下能较好的粘附于基体材料上。From the data in Table 1, it can be seen that compared with Comparative Example 1, the weight of the antibacterial chip in Example 1 and Example 2 did not change significantly after rubbing, indicating that the NO donor can better adhere to the base material under the action of the adhesive. superior.

(2)稳定性评价:(2) Stability evaluation:

对实施例1-5和对比例1-3制得的产品进行稳定性考察,评价方法具体为:本实验为加速实验,分别将样品置于4℃冰箱、45℃恒温箱,每隔一星期进行称量(单位mg),并拍照,结果如表2(4℃)、表3(45℃)所示。The stability of the products prepared in Examples 1-5 and Comparative Examples 1-3 is investigated. The evaluation method is as follows: this experiment is an accelerated experiment, and the samples are placed in a 4°C refrigerator and a 45°C incubator respectively. Weigh (in mg) and take pictures, the results are shown in Table 2 (4°C) and Table 3 (45°C).

表2Table 2

Figure BDA0002621578200000131
Figure BDA0002621578200000131

Figure BDA0002621578200000141
Figure BDA0002621578200000141

表3table 3

组别group 0周(mg)0 weeks (mg) 4周(mg)4 weeks (mg) 9周(mg)9 weeks (mg) 18周(mg)18 weeks (mg) 实施例1Example 1 80.8980.89 80.8580.85 80.8380.83 80.7780.77 实施例2Example 2 81.0281.02 81.0081.00 80.9880.98 80.9580.95 实施例3Example 3 79.4679.46 79.4479.44 79.4179.41 79.3479.34 实施例4Example 4 79.1779.17 79.1579.15 79.1379.13 79.1079.10 实施例5Example 5 79.9079.90 79.8579.85 79.6079.60 79.4079.40 对比例1Comparative example 1 68.9268.92 68.9068.90 68.8768.87 68.7868.78 对比例2Comparative example 2 76.4176.41 76.3976.39 76.3576.35 76.2976.29 对比例3Comparative example 3 80.7980.79 80.6880.68 80.5480.54 80.2080.20

由表2和表3数据可知:各实施例与对比例的稳定性加速实验结果显示,在两种不同温度环境下,护垫芯片前后质量并无发生显著改变,同时颜色也未发生变化,说明护垫芯片表面涂覆的一氧化氮供体的稳定性较好,可稳定长期保存。From the data in Table 2 and Table 3, it can be known that the stability acceleration test results of each embodiment and comparative example show that under two different temperature environments, the quality of the front and back of the pad chip does not change significantly, and the color does not change at the same time, indicating that The nitric oxide donor coated on the surface of the pad chip has good stability and can be stored stably for a long time.

(3)分散均匀性评价:(3) Evaluation of dispersion uniformity:

对实施例1-5和对比例1-3制得的产品进行分散均匀性考察,评价方法具体为:由于NO供体有粉色和淡绿色两种供体,所以供体是否能均匀分布于无纺布上,可以粗略的通过人体视觉感官评价。喷涂后相同体积大小的无纺布无斑块状,整体颜色较均一,同时无供体颗粒的聚集,则评为分散均匀性良好,结果如表4所示。The dispersion uniformity of the products prepared in Examples 1-5 and Comparative Examples 1-3 was inspected, and the evaluation method was specifically: since there are two types of NO donors, pink and light green, can the donors be evenly distributed in the NO donor? On woven fabrics, it can be roughly evaluated by human visual senses. After spraying, the non-woven fabric with the same volume and size has no plaque, the overall color is relatively uniform, and there is no aggregation of donor particles at the same time, it is rated as good dispersion uniformity, and the results are shown in Table 4.

表4Table 4

组别group 有无斑块With or without plaque 实施例1Example 1 无斑块no plaque 实施例2Example 2 无斑块no plaque 实施例3Example 3 斑块少量small amount of plaque 实施例4Example 4 斑块少量small amount of plaque 实施例5Example 5 斑块少量small amount of plaque 对比例1Comparative example 1 无斑块no plaque 对比例2Comparative example 2 斑块多Many plaques 对比例3Comparative example 3 无斑块no plaque

由表4数据可知:斑块的形成由于供体颗粒未均匀分散,聚集一起的小块状物质,实际感官比较统计可知,实施例1和实施例2的均匀性较好,无斑块,而对比例2的斑块很多。From the data in Table 4, it can be seen that the formation of plaques is due to the uneven dispersion of the donor particles, and the small lumps of substances gathered together. The actual sensory comparison statistics show that the uniformity of Examples 1 and 2 is better, and there is no plaque, while Comparative Example 2 had many plaques.

(4)NO供体利用率评价:(4) Evaluation of NO donor utilization rate:

对实施例1-5和对比例1-3制得的产品进行NO供体利用率考察,NO供体的利用率为终产品实际供体负载量与供体投料量之比,结果如表5所示。The products obtained in Examples 1-5 and Comparative Examples 1-3 were investigated on the utilization rate of NO donors, and the utilization rate of NO donors was the ratio of the actual donor load of the final product to the amount of donor feed. The results are shown in Table 5 shown.

表5table 5

Figure BDA0002621578200000151
Figure BDA0002621578200000151

Figure BDA0002621578200000161
Figure BDA0002621578200000161

由表5数据可知:相比于对比例1,实施例1和实施例2供体使用率较高,表明粘合剂存在能有效地提高NO供体的使用率,增加供体在基材上的附着量,减少供体浪费。From the data in Table 5, it can be seen that compared with Comparative Example 1, the donor utilization rate of Example 1 and Example 2 is higher, indicating that the presence of the binder can effectively improve the utilization rate of the NO donor, and increase the donor on the substrate. The amount of attachment reduces donor waste.

(5)对实施例1-5和对比例1-3制得的产品在有水汽的环境中进行NO释放行为的考察,具体方法为:将样品在氮气环境下接触于水溶液中,作用不同时间:1h、2h、3h、4h;取上述不同时间段的溶液,通过一氧化氮检测试剂盒检测作用不同时间下NO释放浓度,记录各组的NO浓度(μmol)随时间(h)变化的结果,结果如表6所示。(5) The products prepared in Examples 1-5 and Comparative Examples 1-3 were investigated in an environment with water vapor, and the specific method was: the samples were exposed to the aqueous solution under a nitrogen environment, and the effect was different for different times. : 1h, 2h, 3h, 4h; take the solutions of the above different time periods, use the nitric oxide detection kit to detect the release concentration of NO at different times, and record the results of the NO concentration (μmol) of each group changing with time (h) , and the results are shown in Table 6.

表6Table 6

组别group 1h1h 2h2 hours 3h3 hours 4h4 hours 实施例1Example 1 18.6218.62 38.6038.60 55.7255.72 57.5457.54 实施例2Example 2 18.6218.62 39.2439.24 57.4757.47 58.1458.14 实施例3Example 3 17.9217.92 35.1235.12 52.0852.08 54.6354.63 实施例4Example 4 17.5017.50 36.2636.26 51.3851.38 53.9153.91 实施例5Example 5 18.4918.49 38.1038.10 53.8653.86 55.4655.46 对比例1Comparative example 1 17.2217.22 25.9025.90 29.9629.96 32.4832.48 对比例2Comparative example 2 16.1316.13 30.9430.94 44.8044.80 48.4448.44 对比例3Comparative example 3 45.2945.29 57.4557.45 57.1357.13 57.4357.43

由表6数据可知:实施例1和实施例2在模拟水汽条件下,3小时左右完全释放,在护垫芯片正常使用时间下,完全释放NO,达到长期抑菌作用;而对比例3的产品NO释放过快,不到2h就已达到平台期,无法实现长时间的抑菌效果。It can be seen from the data in Table 6 that: under the condition of simulated water vapor, Example 1 and Example 2 are completely released in about 3 hours, and under the normal use time of the pad chip, the NO is completely released to achieve long-term antibacterial effect; while the product of Comparative Example 3 The release of NO was too fast, reaching a plateau in less than 2 hours, and the long-term antibacterial effect could not be achieved.

对实施例1制得的产品在测试前和测试3h后进行拍照和观察,结果如图1所示,其中,左侧为光照前产品图片,无纺布呈红色,右侧为光照后产品图片,红色消失。The product prepared in Example 1 was photographed and observed before the test and after 3 hours of the test, and the results are shown in Figure 1, wherein the left side is the product picture before illumination, the non-woven fabric is red, and the right side is the product picture after illumination , the red color disappears.

(6)抗菌性评价(6) Antibacterial evaluation

对实施例1-5和对比例1-3制得的产品进行抗菌性考察,评价方法具体为:本实验通过模拟抗菌芯片在卫生巾上应用的场景,NO供体在水中持续缓慢释放一氧化氮,时长为3h,同时在释放的过程也是变色的过程,从粉色逐渐变成无色,颜色可作为判断高分子材料供体含量的衡量标准与NO释放的表观现象。所以,我们采取直径为6mm圆形不同组的无纺布分别浸泡在相同菌量的菌液中3h,再抽取一定量的浸泡液进行培养计数菌落,通过菌落的多少判断不同组的抗菌效果。(以卡那霉素和银离子为阳性对照组,将浓度为1mg/mL卡那霉素溶液喷涂于无纺布,自然风干而得到;银离子无纺布购买得到;同时设置空白对照组),结果如表7所示(每组平行测定三次,表中数据为三次测定的平均值)。The antibacterial properties of the products prepared in Examples 1-5 and Comparative Examples 1-3 were investigated. The evaluation method was as follows: In this experiment, by simulating the application of antibacterial chips on sanitary napkins, NO donors continuously and slowly release monoxide in water. Nitrogen, the duration is 3 hours, and the process of release is also a process of color change, from pink to colorless gradually, the color can be used as a measure of judging the content of polymer material donors and the appearance of NO release. Therefore, we took different groups of non-woven fabrics with a diameter of 6mm and soaked them in the same amount of bacterial solution for 3 hours, and then took a certain amount of soaking solution to culture and count the colonies, and judge the antibacterial effect of different groups by the number of colonies. (With kanamycin and silver ions as the positive control group, the concentration of 1 mg/mL kanamycin solution is sprayed on the non-woven fabric and air-dried to obtain it; the silver ion non-woven fabric is purchased; a blank control group is set at the same time) , the results are shown in Table 7 (each group was measured in parallel three times, and the data in the table are the average value of three determinations).

表7Table 7

Figure BDA0002621578200000171
Figure BDA0002621578200000171

Figure BDA0002621578200000181
Figure BDA0002621578200000181

实施例1组、卡那霉素组、银离子组、空白对照组的杀菌情况分别如图2、3、4、5所示,由图可知:实施例1组能够有效地杀灭金黄色葡萄球菌,抗菌率高达98.2%,略低于卡那霉素组,值得一提的是,市场上使用的银离子护垫几乎无抗菌活性。The sterilizing conditions of Example 1 group, Kanamycin group, Silver ion group, and blank control group are shown in Figures 2, 3, 4, and 5 respectively, as can be seen from the figure: Example 1 group can effectively kill grapes aureus cocci, the antibacterial rate was as high as 98.2%, which was slightly lower than that of the kanamycin group. It is worth mentioning that the silver ion pads used in the market have almost no antibacterial activity.

申请人声明,本发明通过上述实施例来说明本发明的一种可自提供一氧化氮的抗菌材料及其制备方法和应用,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。The applicant declares that the present invention illustrates a self-providing nitric oxide antibacterial material and its preparation method and application through the above examples, but the present invention is not limited to the above examples, that is, it does not mean that the present invention Must rely on the above-mentioned embodiment to implement. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合,为了避免不必要的重复,本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

Claims (12)

1. An antibacterial material capable of self-supplying nitric oxide, which is characterized by comprising a base material and a functional material loaded on the base material; the functional material comprises, by mass, 4-7 parts of NO donor material, 1-5 parts of adhesive, 0.1-10 parts of dispersant and 1-30 parts of waterproofing agent;
the NO donor material comprises S-nitroso-N-acetylpenicillamine and/or S-nitrosoglutathione;
the waterproof agent is natural resin;
the dispersing agent is a combination of polyvinyl alcohol and sodium dodecyl sulfate.
2. The self-nitric oxide-supplying antimicrobial material according to claim 1, wherein said base material comprises a non-woven fabric, a filter cotton or a sponge.
3. The self-nitric oxide donating antimicrobial material of claim 1, wherein said base material is a nonwoven fabric.
4. The self-nitric oxide donating antimicrobial material of claim 1, wherein said NO donor material is S-nitrosoglutathione.
5. The self-nitric oxide donating antimicrobial material of claim 1, wherein said binding agent comprises any one or a combination of at least two of dextrin, hydroxymethyl cellulose, silica gel, pectin, or polyvinyl acetate latex.
6. The self-nitric oxide donating antimicrobial material of claim 1, wherein said adhesive comprises polyvinyl acetate latex.
7. The method of preparing the nitric oxide self-supplying antibacterial material according to any one of claims 1 to 6, comprising:
(1) Mixing NO donor material, adhesive, dispersant and solvent to prepare coating liquid;
(2) And (2) spraying the coating liquid prepared in the step (1) onto a substrate material, drying, and finally coating a waterproof agent on the surface of the substrate material to obtain the antibacterial material capable of self-providing nitric oxide.
8. The method for preparing the antibacterial material capable of self-supplying nitric oxide according to claim 7, wherein the step (1) comprises the following steps:
(a) Mixing a dispersant and a solvent, and stirring to prepare a solution A; mixing the NO donor material with a solvent, stirring, mixing with an adhesive, and stirring to obtain a solution B;
(b) And (B) mixing the solution A and the solution B prepared in the step (a), and stirring to prepare a coating liquid.
9. The method for preparing an antibacterial material capable of self-supplying nitric oxide according to claim 7, wherein the drying temperature in the step (2) is 20 to 40 ℃.
10. The method for preparing an antibacterial material capable of self-supplying nitric oxide according to claim 7, wherein the drying time is 1 to 3 hours.
11. The method for preparing an antibacterial material capable of self-supplying nitric oxide according to claim 7, wherein the spraying of the coating solution onto the base material in the step (2) is performed 1 to 5 times in total.
12. Use of the self-nitric oxide donating antibacterial material of any one of claims 1-6 in the manufacture of a sanitary napkin or panty liner.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1723778A (en) * 2004-07-20 2006-01-25 深圳市清华源兴生物医药科技有限公司 Silver-contg. type antibiotic agent, prepn. method and application thereof
CN1730804A (en) * 2005-08-26 2006-02-08 上海汽车集团股份有限公司 A kind of antibacterial fabric and preparation method thereof
CN104927348A (en) * 2014-03-20 2015-09-23 北京化工大学 Antibacterial and anticoagulant polymer material, preparation method and application thereof
CN109846113A (en) * 2018-11-29 2019-06-07 南京诺全生物医疗科技有限公司 One kind can be from the nitric oxide production mouth and nose amenities of offer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1723778A (en) * 2004-07-20 2006-01-25 深圳市清华源兴生物医药科技有限公司 Silver-contg. type antibiotic agent, prepn. method and application thereof
CN1730804A (en) * 2005-08-26 2006-02-08 上海汽车集团股份有限公司 A kind of antibacterial fabric and preparation method thereof
CN104927348A (en) * 2014-03-20 2015-09-23 北京化工大学 Antibacterial and anticoagulant polymer material, preparation method and application thereof
CN109846113A (en) * 2018-11-29 2019-06-07 南京诺全生物医疗科技有限公司 One kind can be from the nitric oxide production mouth and nose amenities of offer

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