CN115990284A

CN115990284A - Slurry for coating hemostatic gauze and hemostatic gauze prepared from slurry

Info

Publication number: CN115990284A
Application number: CN202310020148.0A
Authority: CN
Inventors: 施益峰; 邓佳雨; 巨芙蓉; 万伟; 瞿应良
Original assignee: Hangzhou Feichuang Life Technology Co ltd
Current assignee: Hangzhou Feichuang Life Technology Co ltd
Priority date: 2023-01-06
Filing date: 2023-01-06
Publication date: 2023-04-21
Anticipated expiration: 2043-01-06
Also published as: CN115990284B

Abstract

The application relates to the technical field of inorganic powder-organic polymer mixed coating, in particular to slurry for coating hemostatic gauze and hemostatic gauze prepared by coating the slurry on a substrate. The slurry for coating hemostatic gauze mainly comprises solvent water, inorganic mineral hemostatic powder, polymer colloid emulsion and suspending agent; the mass of the binder component in the high polymer colloid emulsion accounts for 0.2-3% of the total content of the slurry; the mass of the suspending agent accounts for 0.01% -0.1% of the total content of the slurry; the inorganic mineral hemostatic powder accounts for 1% -15% of the total content of the slurry; the pH value of the slurry is controlled to be 6-10; the dispersing agent is water or a mixed dispersing agent formed by water and volatile organic solvent. The hemostatic gauze prepared from the slurry for coating the hemostatic gauze has the effects of high surface exposure proportion of inorganic components, good hemostatic effect, low powder falling rate, good safety, good flexibility of composite materials and good hand feeling.

Description

Slurry for coating hemostatic gauze and hemostatic gauze prepared from slurry

Technical Field

The application relates to the technical field of inorganic powder-organic polymer mixed coatings, in particular to slurry for coating hemostatic gauze and hemostatic gauze prepared by using the slurry.

Background

Nearly two million people die each year in war, traffic accident and natural disaster due to excessive blood loss after physical trauma. Numerous studies have shown that mortality is greatly reduced if bleeding conditions can be rapidly controlled.

At present, the materials used for rapid hemostasis at home and abroad mainly comprise the following three types:

(1) Inorganic minerals: including various zeolites, various clays (kaolin, montmorillonite), porous bioglass, mesoporous silica, and the like.

(2) Organic high molecular species: including chitosan, oxidized cellulose, modified starch, calcium alginate, etc.

(3) Biological products: including fibrin, thrombin, etc.

Among these hemostatic materials, inorganic mineral-based hemostatic materials have particular advantages:

(1) Short acting time and better hemostatic speed than organic polymer hemostatic materials.

(2) The material has stable property, does not need special low-temperature freezing and refrigerating preservation, and has obvious advantages in the requirements of storage and transportation compared with biological product hemostatic materials.

The common inorganic mineral hemostatic materials such as zeolite and clay are generally in the form of massive solids or powder. Since large solid bodies cannot be used directly, early inorganic mineral hemostatic materials were either in powder form or processed into small particles. However, the powder or small particle form material can only be directly thrown or poured on the bleeding part, and the auxiliary pressing, binding, packing and other operations are difficult to be carried out simultaneously. When the femoral artery, the carotid artery and the abdominal cavity are in massive hemorrhage, the powder is extremely easy to be dispersed by high-speed blood flow, the powder cannot be maintained in a damaged area of a blood vessel, and the effect of promoting rapid hemostasis is difficult to realize.

In view of the inconvenience of using powder particle materials, most of the related hemostatic products newly developed at present compound the powder materials with base materials with flexible forms such as gauze, non-woven fabrics, porous sponge and the like to form flexible compound hemostatic materials.

In the composite material, inorganic mineral powder is used as a hemostatic active material component, and a flexible substrate is used for giving a specific shape to the product. For example: kaolin combat gauze, Z-media, hangzhou, innovative zeolite hemostatic gauze, etc. The gauze shape makes the product convenient for carrying out auxiliary pressing, binding, packing and other operations simultaneously when stopping bleeding.

The mode of compounding inorganic mineral powder such as zeolite, clay and the like with a flexible substrate is a key technical problem of related product development. Such as: the combat gauze of Z-medium ca company is prepared by mixing kaolin powder with binder solution, coating on non-woven fabric substrate, and keeping the composite material in wet state. The obtained product has gauze shape, and can be used for pressing, binding, packing, etc. However, at least a portion of the solvent is retained on the gauze and is not in a completely dry form. The combat gauze is soaked in water or normal saline, and is slightly vibrated, and almost all kaolin powder can fall off from the gauze substrate. The shedding of a large amount of powder causes difficult wound surface cleaning after successful hemostasis.

For this reason, the U.S. Z-media company later developed a Control + hemostatic gauze material in which the binder solvent had been removed after the end of the coating and the product was in a dry form. The falling rate of the kaolin is successfully reduced to below 0.6-1% by improving the bonding mode of the adhesive. However, due to the use of a relatively large amount of binder, the flexibility of the gauze is greatly reduced, and the hemostatic gauze material is relatively stiff and poor in softness, and has little influence when being used for pressing and binding. However, when the hemostatic patch is used for operations such as filling, the frictional force on the surrounding wound surface is large, and the bleeding point is difficult to be tightly attached in a small hole-shaped wound, so that the hemostatic effect and the feeling of a wounded are affected. Meanwhile, when the gauze is rubbed with each other under the dry condition, a large amount of powder can still fall off from the base material.

The Hangzhou zeolite crystal particles are loaded on the absorbent cotton gauze substrate in an in-situ growth mode, so that strong interaction exists between the zeolite crystal material and the flexible fabric substrate, and the zeolite crystal particles cannot fall off due to contact with water. However, the possibility of cracking of the zeolite itself and the possibility of powder falling off due to friction between the zeolite gauze and the zeolite gauze in the use process still exist, and the falling off of the powder can still be obviously observed in the use process. In the oscillation experiment in water, the tested falling rate is still 0.5-1.5%. When the powder is rubbed against each other in a dry state, the powder is continuously dropped. Meanwhile, as the in-situ growth conditions of clay minerals such as kaolin are severe, the method cannot be directly used for preparing clay hemostatic gauze or zeolite-kaolin mixed hemostatic gauze and the like. Only zeolite hemostatic gauze is currently prepared by in situ growth.

Compared with the technical route of in-situ growth, the method has the advantages that the existing inorganic mineral active hemostatic powder and the adhesive are prepared into the slurry, the slurry is directly coated on the flexible substrate, the route process of forming the hemostatic active coating on the flexible substrate as a hemostatic material product after drying is simpler and more convenient, the production period is short, the yield of the finished product is high, and the production cost can be greatly reduced.

In most studies, in preparing coating slurries, solution-type binders are generally selected in the corresponding art. Specifically, when preparing the slurry, a polymer binder solution formed by dissolving a water-soluble polymer in water or an oil-soluble polymer in an organic solvent is used as a dispersion medium of the slurry, and then the dispersion medium is mixed with inorganic powder such as zeolite, kaolin and the like to prepare the coating slurry. The solution-type binder has the advantages that the polymer is easy to form a viscous solution after being dissolved in water, the high viscosity slows down the sedimentation speed of inorganic particles, and the slurry is particularly easy to prepare. The polymer used is used as a binder of the dried slurry, and also plays roles of a slurry thickener and a suspending agent, and the system composition can be very simple. The inorganic powder is easy to disperse in viscous polymer solution to form stable coating slurry in certain time, and is convenient for coating.

However, the slurry for coating hemostatic gauze formed by the above system has the following problems:

1. after the water-soluble polymer is coated, the water-soluble polymer is soluble in water, and if a cross-linking agent is not additionally added, the water-soluble polymer can be partially or completely redissolved after contacting blood in the use process, so that powder is dropped. If a cross-linking agent is additionally added to the water-soluble polymer to reduce re-dissolubility after drying, the cross-linking agent is often toxic substances such as formaldehyde, glutaraldehyde, epichlorohydrin and the like. The hemostatic material is used as a medical appliance product, and a large number of procedures of controlling and detecting the amount of residual crosslinking agent are additionally added in the production process, so that the safety is ensured. The oil-soluble polymer has no problem of re-dissolving in water after drying, but the direct volatilization and drying of a large amount of organic solvent are the processes avoided as much as possible in industrial production, and have great hidden troubles in environmental protection and safety.

2. After the water-soluble polymer is dissolved in water, a uniform solution is formed, and the polymer is uniformly distributed in all solvent spaces. In the post-coating drying process, the polymer concentration gradually increases as the solvent evaporates, but remains a homogeneous solution with the polymer present in all solvent spaces. And finally, after drying, forming a uniform coating on all solid surfaces, so that the prepared hemostatic material has poor hemostatic effect. The thickness of the coating is determined by the coating weight and the concentration of the polymeric binder in the slurry, and can be considered to be continuously controllable, from a few nanometers up to hundreds of nanometers, even microns. However, the film structure is close to a complete continuous polymer film regardless of thickness. Therefore, the inorganic material inevitably covers the surface of the inorganic material after drying to form a film, which hinders the hemostatic ability of the inorganic active material. In the partial coating, a water-insoluble polymer is dissolved in an organic solution to form a binder, and an inorganic powder is added to form an oily slurry coating, and there is a problem that the surface of zeolite is coated after drying.

3. Common water-soluble polymers include carboxymethyl cellulose, modified starch, soluble starch, gelatin, sodium alginate, chitosan, polyvinyl alcohol, polyethylene glycol and the like, and the hard and brittle adhesive film layer is obtained after drying and film forming. Therefore, the product obtained after coating has poor flexibility and higher stiffness. The hand feeling friction force is large, and the hand feeling friction force is not smooth and smooth. In particular, the polymer is used for improving the water resistance, and the product crosslinked by adding the crosslinking agent is more rigid during coating.

For example: the water-soluble polyvinyl alcohol or sodium carboxymethyl cellulose is directly used as a binder, and the zeolite can be conveniently dispersed in the water-soluble polyvinyl alcohol or sodium carboxymethyl cellulose by strong stirring due to extremely high viscosity of the aqueous solution of polyvinyl alcohol and sodium carboxymethyl cellulose. After coating, the zeolite gauze with good hemostatic effect is obtained. However, the product can be subject to zeolite shedding in water due to the re-dissolution of the binder in water, and the product has higher stiffness when dried.

In the development of hemostatic materials loaded with inorganic mineral hemostatic agents, the coagulation effect, the product flexibility and the powder shedding rate are three approximately contradictory targets. The usage amount of the binder is large, the small value of the powder falling rate can be ensured, but a large amount of the binder can coat the active mineral powder, so that the coagulation effect is affected, and meanwhile, the composite material is easy to have high stiffness and is not soft; the binder is small in usage amount, the proportion of the active inorganic particles completely embedded is small, the coagulation effect is good, the material is soft, but the powder falling rate is difficult to ensure to be small.

In summary, the solution-type binder cannot meet three requirements of the zeolite hemostatic gauze coated product due to the above defects: the inorganic component has high surface exposure proportion, low powder falling rate and good flexibility of the composite material. On the premise of ensuring the maintenance of the coagulation effect, the method for obtaining the inorganic mineral flexible hemostatic material with high flexibility and low shedding rate is still a challenging technical problem.

Disclosure of Invention

In order to solve the technical problems, the application provides a sizing agent for coating hemostatic gauze and hemostatic gauze prepared by using the sizing agent.

In a first aspect, the present application provides a slurry for coating hemostatic gauze, which is realized by the following technical scheme:

the slurry for coating hemostatic gauze mainly comprises a dispersing agent, inorganic mineral hemostatic powder, high polymer colloid emulsion and a suspending agent; the mass of the binder component in the high polymer colloid emulsion accounts for 0.2-3% of the total content of the slurry; the mass of the suspending agent accounts for 0.01% -0.1% of the total content of the slurry; the inorganic mineral hemostatic powder accounts for 1% -15% of the total content of the slurry; the pH value of the slurry is controlled to be 6-10; the dispersing agent is water or a mixed dispersing agent formed by water and volatile organic solvent.

The method solves three problems in the prior art, firstly, the slurry is coated to ensure that most of the surfaces of inorganic materials are still exposed and are not completely covered by the adhesive, and the exposed proportion of the surfaces of inorganic components is high, so that calcium ions in zeolite can be quickly exchanged into blood, and meanwhile, proteins in the blood can be adsorbed and fixed on the surfaces of the zeolite to play a good role in promoting coagulation, and the prepared hemostatic gauze is ensured to have excellent hemostatic effect; second,: the dropping rate is required to be as low as possible after coating, and the safety is good. The falling of a small amount of zeolite powder does not have a significant effect on the hemostatic effect, but has serious negative effects on other aspects. For example: in the subsequent cutting, folding and packaging procedures, dust falling causes air pollution, a workshop dust removing system needs to be added, and health risks of dust contact of workshop production staff and the like are increased. In addition, under the dry condition, operations such as filling, folding, binding and the like can cause mutual friction between the surfaces of zeolite gauze among different layers, part of zeolite can be scraped from a gauze substrate to become dust, the dust can be possibly inhaled by users, and also falling objects can remain on a wound surface after hemostasis is finished, so that medical staff can additionally and specially clear the wound surface again after hemostasis is finished. In a word, the powder falling off in various processing and using processes has important influence on the production and safety in the using process, and is also an important premise for expanding the market acceptance of the products. Third, the softness of the hemostatic product must be maintained after application. In the use process of the hemostatic product, a user can select pressing, dressing, packing and other operations according to the shape and the position of the wound. At this time, the hemostatic material must be capable of changing shape according to the wound and the position of the wound, and tightly clinging to the wound surface, and can be kept tightly clinging to the wound surface under the pressing, so that a good hemostatic effect can be achieved, and therefore, the hemostatic material prepared by the method must have enough softness. Besides the hemostatic effect, the softness has great influence on the comfort level of use. When the product with high stiffness is packed and bandaged, the product has obvious scraping effect on the wound surface, and can cause severe pain, so that the softness is also an important index of gauze hemostatic products.

In conclusion, the preparation method of the sizing agent for coating the hemostatic gauze has the advantages of simpler route and process, short production period, high yield of the hemostatic gauze prepared by the sizing agent, and capability of greatly reducing the production cost of the hemostatic gauze. The hemostatic gauze prepared from the slurry for coating the hemostatic gauze has the effects of high surface exposure proportion of inorganic components, good hemostatic effect, low powder falling rate, good safety, good flexibility of composite materials and good hand feeling.

Preferably, the polymer colloid emulsion is composed of a dispersion solvent and colloid particles dispersed in the solvent; the surface of the colloid particles in the high polymer colloid emulsion is provided with negative charges or nonionic surfactant components; glass transition temperature T of the polymer colloid emulsion _g Below 25 ℃.

In order to maintain dispersion stability of the colloidal particles in the present application, the colloidal particles in the selected latex have a negative charge or a nonionic surfactant component, that is, the latex used in the present application is referred to as an anionic latex and a nonionic latex, respectively, in that order. In this application, latex particles need to be co-dispersed with the inorganic mineral hemostatic powder within the system. The zeolite powder and clay powder are in most pH ranges, the surfaces of the zeolite powder and clay powder are naturally negatively charged, and the zeolite powder and clay powder belong to negatively charged particles. Cationic latex and zeolite are subject to flocculation and sedimentation, so that the slurry provided by the application is preferably anionic latex or nonionic latex. Glass transition temperature T of high molecular colloid emulsion _g The flexibility and the handfeel of the prepared hemostatic material can be improved below 25 ℃.

After the polymer solution type adhesive in the prior art is dried, a uniform adhesive film is easy to form while the adhesive film plays a role in adhesion, and the adhesive film is coated on the surfaces of all inorganic particles, and the coating blocks the direct contact capability of the surfaces of inorganic mineral hemostatic powder and blood, so that the procoagulant capability is greatly influenced. Unlike the solution type adhesive, the polymer in the colloidal emulsion adhesive is insoluble in water and is dispersed in the emulsion in the form of solid particles, and after the polymer is added into the slurry, the emulsion particles and the inorganic mineral powder are uniformly dispersed in water at the same time. After being coated on flexible matrixes such as gauze, non-woven fabrics and the like, concentration is firstly carried out in the drying process, the average distance between inorganic mineral powder and latex particle particles is gradually shortened, finally, after drying, colloid particles are used as bridges to adhere the mineral powder around the inorganic mineral powder to form a dot bridging coating structure, so that most surfaces of the inorganic mineral powder are still exposed, most surfaces of inorganic materials in the hemostatic material prepared by the application are still exposed, the hemostatic material is not completely covered by an adhesive, the surface exposure proportion of inorganic components is high, and the hemostatic effect is excellent.

Preferably, the polymer colloid emulsion is one or more of chloroprene rubber latex, styrene-butadiene rubber latex, carboxyl styrene-butadiene rubber latex, polyurethane latex, pure propylene rubber latex, styrene-propylene rubber latex, polyacrylate latex, oxidized polyethylene latex and polytetrafluoroethylene emulsion; the diameter of colloid particles in the polymer colloid emulsion is between 50 and 500 nm; glass transition temperature T of the polymer colloid emulsion _g Below 0 ℃.

Each of the above-listed latices is a generic name for a broad class of latices and is not meant to be a completely defined chemical composition. For example: the polyacrylate latex can be methyl acrylate, propyl acrylate, butyl acrylate and mixtures thereof, and even other types of monomers such as acrylic acid monomers, acrylonitrile monomers and the like can be added to realize the regulation and control of indexes such as glass transition temperature, surface charge, cohesion and the like. The glass transition temperature of the product can be adjusted according to the selection and the proportion of the monomers. For another example: the main monomers of the carboxylated styrene-butadiene latex comprise styrene, butadiene and acrylic acid, and the glass transition temperature of the material can be adjusted by changing the proportion of the styrene to the butadiene; the above-mentioned regulation technology is the prior art in the field, and is a technical means known to those skilled in the art, and will not be described in detail below.

By adopting the technical scheme, the preferable high-molecular colloid emulsion can ensure that most of the surfaces of inorganic materials in the prepared hemostatic material are still exposed and are not completely covered by the adhesive, the surface exposure proportion of inorganic components is high, the hemostatic effect is excellent, and the glass transition temperature T of the high-molecular colloid emulsion is high _g The flexibility and the handfeel of the prepared hemostatic material can be further improved below 0 ℃.

Preferably, the inorganic mineral hemostatic powder comprises zeolite hemostatic powder and clay hemostatic powder, wherein the zeolite hemostatic powder is at least one of A-type zeolite, X-type zeolite, Y-type zeolite, P-type zeolite, clinoptilolite, mordenite, chabazite and ZSM-5 zeolite; the clay styptic powder is at least one of kaolin, montmorillonite, bentonite, attapulgite, diatomite, illite and halloysite; the average particle size of the inorganic mineral hemostatic powder is 50 nm-50 mu m.

Different hemostatic materials have different procoagulant mechanisms, and kaolin is mainly involved in the activation of surface factor (factor XII) in the coagulation cascade; zeolite does not activate factor XII as much as kaolin, but at the same time provides calcium ions (factor IV) involved in the activation and stabilization of procoagulant fibrinogen (factor V) and autologous prothrombin C (factor X); montmorillonite can absorb water in large quantity, enrich coagulation factor concentration, and simultaneously can participate in activation of surface factor (XII factor) and provide calcium ion (IV factor). Thus, further compounding of various inorganic hemostatic materials in the slurry of the present application may further enhance the clotting effect. The slurry may also incorporate a second, even third, different inorganic component. The effect of the product is improved by compounding hemostatic minerals.

In the technical scheme of the application, the influence of different types of binders on the coating degree of the zeolite surface is characterized by utilizing the cation exchange capacity and the cation exchange speed of the zeolite, so that the good hemostatic effect, the use safety and the flexibility of the hemostatic material prepared by the application are ensured, and the hand feeling is good.

Preferably, the average particle size of the inorganic mineral hemostatic powder is 100 nm-20 μm.

Preferably, the average particle size of the inorganic mineral hemostatic powder is 400 nm-4 μm.

Through adopting above-mentioned technical scheme, optimize the average particle chi of powder inorganic mineral hemostatic powder, avoid the too little binder that needs more of granule, the problem that the proportion of surface embedded is also high brings, avoid the powder granule too big simultaneously, the thick liquids stability that brings is poor, the product is coarse, friction power is big, the problem of feeling poor, and then can guarantee the flexibility and the feel of the hemostatic material of preparation and guarantee simultaneously to have good hemostatic effect and security.

Preferably, the pH value of the slurry is controlled to be 7.0-9.0; the suspending agent is at least one of xanthan gum, locust bean gum and konjac gum.

In the slurry composition, the suspending agent has the function of ensuring that the zeolite does not flocculate and settle in the mixed slurry and can be stably dispersed and suspended in the slurry. The slurry is uniform and stable, and the stable and uniform loading capacity of the coated product can be ensured. In order to avoid the complete coverage of the zeolite surface by the binder, the binder selected in the application is not a common solution type binder, but a colloidal emulsion type binder using water as a solvent, has extremely low viscosity after dilution, is equivalent to water and has poor suspending capacity, so that a specific suspending agent needs to be added to improve the suspending capacity of the system.

The zeolite particles have a size of about 1.5 to 2 times the density of water on the micrometer scale, and are extremely likely to settle after being added into the system, resulting in unstable slurry. In the production process, the slurry is required to be kept stable for at least 4-8 hours, otherwise, the zeolite coating amount is easy to change gradually along with the extension of the coating time, the loading amount of the final product is unstable, and the quality stability of the finished product in the same batch is difficult to ensure.

In the prior art, the suspending capacity is generally improved by a thickening mode, and the thickening agent is added to dissolve the suspending agent in water to increase the viscosity of the system, so that the viscosity of the inorganic particle dispersion slurry is a main method for increasing the stability of the inorganic particle dispersion slurry. Common thickeners, such as sodium carboxymethyl cellulose, modified starch, polyvinyl alcohol, sodium polyacrylate, etc., require relatively high concentrations to keep the zeolite particles from settling, often requiring concentrations in excess of 1% and even 2% to obtain a stable slurry. However, too much thickener material can result in the softness of the coated product being destroyed, resulting in a coated product having a stiffness significantly exceeding that required for hemostatic gauze. Meanwhile, the thickener is also an adhesive, and after the thickener is added in too much amount, a continuous polymer film can be formed on the surface of the zeolite to cover the surface of the zeolite, so that the whole hemostatic function of the hemostatic material is affected.

Therefore, unlike the general application, the suspending agent preferred in the present application requires high flexibility of the hemostatic product after coating in the present application, and the suspending agent is required to be added to the slurry in an amount as small as possible, specifically controlled to be 0.01% to 0.1%. The suspension effect in the application is not completely derived from high viscosity, and after the suspension effect is dissolved in water, a special structure is formed, so that better suspension effect can be obtained under lower viscosity than other high molecules.

Preferably, the suspending agent is a mixture of xanthan gum and konjak gum or a mixture of xanthan gum and locust bean gum, and the mass of the suspending agent accounts for 0.01-0.10% of the total content of the slurry; when the suspending agent is a mixture of xanthan gum and konjac gum, the mass ratio of the xanthan gum to the konjac gum is (9:1) - (3:7); when the suspending agent is a mixture of xanthan gum and locust bean gum, the mass ratio of the xanthan gum to the locust bean gum is (7:3) - (2:8).

By adopting the technical scheme, a great deal of researches show that the xanthan gum and the konjak gum are compounded or the xanthan gum and the locust bean gum are compounded to obtain better suspension dispersion effect than the single component gum. Furthermore, there is no theoretical preferred formulation of suspending agent type, concentration and ratio that can be directly applied for a new system. This is why there are still a number of studies on screening of suspending agents in different systems. Each specific system requires separate inventive suspension selection and optimization of formulation.

In this application, it was found that when zeolite, clay and rubber particles are present at the same time, the compounding of xanthan gum and locust bean gum, or xanthan gum and konjac gum, can achieve a total suspending agent concentration as low as 0.01%, a stable mixed system of suspension slurries can still be formed.

It has also been found in experiments that the order of addition of the materials can significantly influence the suspension effect at the same suspension concentration. The zeolite is mixed with the xanthan gum and then the konjak gum is added, and the suspension stability is obviously higher than that of the zeolite mixed with the konjak gum and then the xanthan gum is added, or the xanthan gum and the konjak gum are mixed in advance and then the zeolite is added. Obviously, the phenomenon shows that the xanthan gum or the konjac gum can have stronger interaction with the surface of zeolite, and the whole mixed system zeolite also participates in the construction of a suspension system, and is not just an inert passive suspended solid particle.

In a second aspect, the present application provides a hemostatic gauze prepared by using a slurry for coating hemostatic gauze, which is realized by the following technical scheme:

a hemostatic gauze prepared from a slurry for hemostatic gauze coating, comprising a flexible substrate and an inorganic mineral powder coating made from the slurry for hemostatic gauze coating of claims 1-8; the average bending length of the hemostatic gauze prepared by the slurry for coating the hemostatic gauze is less than 3.0 cm, the falling rate in water is less than 0.2%, and the in-vitro coagulation time is less than three minutes.

The hemostatic gauze prepared from the slurry for coating the hemostatic gauze has the advantages of high surface exposure ratio of inorganic components, good hemostatic effect, low powder falling rate, good safety, good flexibility of composite materials and good hand feeling, and the preparation method has the advantages of simpler route process, short production period, high yield of finished products and capability of greatly reducing the production cost.

Preferably, the flexible substrate is one of absorbent cotton gauze, all-cotton non-woven fabric, polyester-viscose blended non-woven fabric, polyurethane sponge sheet, melamine resin sponge sheet and sponge strip.

The preparation method of the hemostatic gauze has the advantages of simpler route process, short production period and high yield of finished products, and can greatly reduce the production cost.

In summary, the present application has the following advantages:

1. the hemostatic gauze prepared from the slurry for coating the hemostatic gauze has the effects of high surface exposure proportion of inorganic components, good hemostatic effect, low powder falling rate, good safety, good flexibility of composite materials and good hand feeling.

2. The preparation method has the advantages of simpler route process, short production period and high yield of finished products, and can greatly reduce the production cost.

Detailed Description

The present application is described in further detail below in conjunction with comparative examples and examples.

The preferable scheme of the polymer colloid emulsion is as follows: water-soluble polymers such as polyvinyl alcohol (PVA 0588, PVA 2488), oxidized starch, soluble starch, carboxymethyl cellulose, chitosan, sodium alginate, and gelatin are purchased. All are prepared into aqueous solutions with four concentration ratios of 0.5%,1.0%, 2.0% and 5.0% of solid content. Part of water-soluble polymer materials with poor water solubility are promoted to be dissolved by adding acid to adjust the pH value (chitosan) or heating to be dissolved (soluble starch, oxidized starch and gelatin), and all water-soluble polymer materials obtain clear solution.

Aqueous emulsions such as polyurethane latex, neoprene latex A, neoprene latex B, styrene-butadiene latex, carboxylated styrene-butadiene latex, pure acrylic latex, styrene-acrylic latex, polyacrylate latex, oxidized polyethylene emulsion and the like are purchased. The latex was diluted with water to a solids content of 0.5% and 1.0%. Four concentrations of 2.0% and 5.0%.

The adhesive was uniformly applied to absorbent gauze (absorbent gauze material itself having an average bending length of 1.25 cm) by a coater using the absorbent gauze as a base material. The coating amount was 1.5 grams of binder solution per gram of absorbent cotton gauze. After coating, the gauze is vertically hung and dried under the condition of no tension, the drying temperature is 105 ℃, the drying time is 30 minutes, and the gauze is cooled in a dryer after being dried.

The samples were cut into 2 cm wide strips and stored at room temperature for 20 hours in an environment with a humidity of 60-70%. The average bending length was tested on a 702 stiffness tester according to the test method of national standard GB/T18318.1-2009.

Table 1 average flexural length test parameters of materials prepared from the resulting coatings at concentrations of 0.5%, 1.0%, 2.0%, 5.0% for the different binders.

As can be seen from table 1: after the water-soluble polymer solution is coated, the bending length of the gauze is obviously increased along with the increase of the concentration of the binder. When the concentration of the water-soluble polymer solution is 2%, the average bending length of all samples exceeds 2.5 cm and is more than twice of the average bending length of the raw materials before coating; when the concentration of the water-soluble polymer solution is 5%, the average bending length of all samples exceeds 4.0 cm and exceeds three times of the average bending length of the raw materials before coating; it is demonstrated that such binders tend to significantly reduce the softness of the substrate material. However, when the latex-type adhesive with low glass transition temperature is coated, the bending length of the material is slightly increased, even if the concentration is increased to 5%, and the bending length of partial data points is even lower than that of the raw material, so that the adhesive can be used for better maintaining the softness of the substrate.

Examples

Example 1

A slurry for coating hemostatic gauze is prepared from dispersing agent, inorganic mineral hemostatic powder, polymer colloid emulsion and suspending agent. The mass of the binder component in the polymer colloid emulsion accounts for 0.2-3% of the total content of the slurry, the mass of the suspending agent accounts for 0.01-0.1% of the total content of the slurry, and the inorganic mineral hemostatic powder accounts for 1-15% of the total content of the slurry. The pH value of the slurry is controlled to be 6-10, preferably 7.0-9.0.

The dispersing agent is water or a mixed dispersing agent formed by water and volatile organic solvent. Volatile organic solvents such as ethanol, methanol, acetone, etc.

The polymer colloid emulsion is composed of a dispersion solvent and colloid particles dispersed in the solvent.

The surface of the colloid particles in the high polymer colloid emulsion is provided with negative charges or nonionic surfactant components, namely the high polymer colloid emulsion is anionic latex or nonionic latex.

The high molecular colloid emulsion is one or a combination of a plurality of neoprene rubber latex, styrene-butadiene rubber latex, carboxyl styrene-butadiene rubber latex, polyurethane latex, pure propylene rubber latex, styrene-acrylic rubber latex, polyacrylate latex, oxidized polyethylene latex and polytetrafluoroethylene emulsion.

The diameter of the colloidal particles in the polymer colloidal emulsion is 50-500 nm, preferably 100-300nm.

Glass transition temperature T of high molecular colloid emulsion _g Below 25 ℃, preferably the glass transition temperature T of the polymer colloid emulsion _g It is further preferable that the glass transition temperature Tg of the polymer colloid emulsion is lower than-15 ℃.

The inorganic mineral hemostatic powder comprises zeolite hemostatic powder and clay hemostatic powder, wherein the zeolite hemostatic powder is at least one of A-type zeolite, X-type zeolite, Y-type zeolite, P-type zeolite, clinoptilolite, mordenite, chabazite and ZSM-5 zeolite; wherein the clay styptic powder is at least one of kaolin, montmorillonite, bentonite, attapulgite, diatomite, illite and halloysite. The average particle size of the inorganic mineral hemostatic powder is 50nm to 50 μm, preferably 100nm to 20 μm, and more preferably 400nm to 4 μm.

The suspending agent is at least one of xanthan gum, locust bean gum and konjak gum, preferably the suspending agent is a mixture of the xanthan gum and the konjak gum or a mixture of the xanthan gum and the locust bean gum, and the mass of the suspending agent accounts for 0.01-0.10% of the total content of the slurry; the suspending agent is a mixture of xanthan gum and konjac gum, and the mass ratio of the xanthan gum to the konjac gum is (9:1) - (3:7); when the suspending agent is a mixture of xanthan gum and locust bean gum, the mass ratio of the xanthan gum to the locust bean gum is (7:3) - (2:8).

A method for preparing a sizing agent for coating hemostatic gauze, which comprises the following steps:

(1) Weighing inorganic mineral hemostatic powder according to a proportion; meanwhile, preparing a binder colloid emulsion diluent, preparing a xanthan gum solution and preparing a locust bean gum or konjak gum solution;

(2) Adding the pre-prepared adhesive colloid emulsion diluent, and stirring and mixing uniformly;

(3) Adjusting the pH value of the system to 7.0-9.0 by using sodium hydroxide aqueous solution;

(3) Adding pre-prepared xanthan gum solution, and uniformly mixing and stirring;

(4) Adding pre-prepared locust bean gum or konjac gum solution, and mixing to obtain slurry for coating hemostatic gauze.

A hemostatic gauze prepared from slurry for coating hemostatic gauze comprises a flexible substrate and an inorganic mineral powder coating, wherein the inorganic mineral powder coating is prepared from the slurry for coating hemostatic gauze. The flexible substrate is one of absorbent cotton gauze, all-cotton non-woven fabric, polyester-viscose blended non-woven fabric, polyurethane sponge sheet, melamine resin sponge sheet and sponge strip. The average bending length of the hemostatic gauze prepared by the slurry for coating the hemostatic gauze is less than 3.0 cm, the falling rate in water is less than 0.2%, and the in-vitro coagulation time is less than three minutes.

A method for preparing hemostatic gauze by using slurry for coating hemostatic gauze, which comprises the following steps: uniformly coating the prepared slurry for coating the hemostatic gauze on a flexible substrate by using the purchased flexible substrate as the substrate through a coating machine, wherein the coating weight is 1.5-3.0 g of the slurry for coating the hemostatic gauze per g of the gauze substrate; after coating, the gauze coated with the sizing agent is dried through a drying tunnel on a coating machine under the traction of a mechanical device, the drying temperature is 105 ℃, and after the gauze comes out of the drying tunnel, the hemostatic gauze is guided to the rear end of the coating machine through the mechanical device and is wound up, so that the hemostatic gauze of a final finished product is obtained.

In the embodiment, the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 2% of inorganic mineral styptic powder-A zeolite (average particle size is 600 nm), 0.4% of high molecular colloid emulsion (neoprene emulsion, solid content is 50%), 0.02% of xanthan gum, 0.02% of konjak gum and the balance of deionized water.

(1) Weighing inorganic mineral hemostatic powder according to a proportion; meanwhile, preparing a prepared binder colloid emulsion diluent, a prepared xanthan gum solution and a prepared locust bean gum or konjak gum solution;

(3) Adjusting the pH value of the system to 8.0-9.0 by using sodium hydroxide aqueous solution;

Hemostatic gauze was prepared using the slurry for hemostatic gauze coating in example 1, and its specific preparation method: uniformly coating the prepared sizing agent for coating the hemostatic gauze on a flexible substrate by using the purchased absorbent cotton gauze as a substrate through a coating machine, wherein the coating weight of the sizing agent for coating the hemostatic gauze is 2.5 grams of sizing agent for coating the hemostatic gauze per gram of absorbent cotton gauze; the gauze coated with the sizing agent is dried through a drying tunnel on a coating machine under the traction of a mechanical device, and the drying temperature is 115 ℃; after drying, the hemostatic gauze is guided to the rear end of the coater to be rolled up through a mechanical device after coming out of the drying tunnel, and the hemostatic gauze is finally obtained.

Example 2

Example 2 differs from example 1 in that:

the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 16% of inorganic mineral styptic powder-P zeolite (average particle size is 10 mu m), 3.0% of high molecular colloid emulsion (styrene-butadiene rubber latex, solid content is 50%), 0.06% of xanthan gum, 0.01% of konjak gum and the balance of deionized water.

Hemostatic gauze was prepared using the slurry for hemostatic gauze coating in example 2, and its specific preparation method: uniformly coating the prepared sizing agent for coating the hemostatic gauze on a flexible substrate by using the purchased absorbent cotton gauze as a substrate through a coating machine, wherein the coating weight of the sizing agent for coating the hemostatic gauze is 2.5 grams of sizing agent for coating the hemostatic gauze per gram of absorbent cotton gauze; after coating is finished; the gauze coated with the sizing agent is dried through a drying tunnel on a coating machine under the traction of a mechanical device, and the drying temperature is 115 ℃; after drying, the hemostatic gauze is guided to the rear end of the coater to be rolled up through a mechanical device after coming out of the drying tunnel, and the hemostatic gauze is finally obtained.

Example 3

Example 3 differs from example 1 in that:

the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 5% of inorganic mineral styptic powder-X zeolite (average particle size is 1.6 mu m), 1.4% of high molecular colloid emulsion (pure propylene rubber latex with solid content of 50%), 0.02% of xanthan gum, 0.01% of konjak gum and the balance of deionized water.

Hemostatic gauze a was prepared using the slurry for hemostatic gauze coating in example 3, and its specific preparation method: uniformly coating the prepared sizing agent for coating the hemostatic gauze on a flexible substrate by using the purchased absorbent cotton gauze as a substrate through a coating machine, wherein the coating amount of the sizing agent for coating the hemostatic gauze is 2.0 g per g of absorbent cotton gauze, and after the coating is finished, drying the sizing agent-coated gauze through a drying channel on the coating machine under the traction of a mechanical device, wherein the drying temperature is 115 ℃; after drying, the hemostatic gauze is guided to the rear end of the coater to be rolled up through a mechanical device after coming out of the drying tunnel, and the hemostatic gauze is finally obtained.

Hemostatic gauze B was prepared using the slurry for hemostatic gauze coating in example 3, and its specific preparation method: uniformly coating the prepared slurry for coating the hemostatic gauze on a flexible substrate by using the purchased terylene non-woven fabric as a substrate through a coating machine, wherein the coating amount of the slurry for coating the hemostatic gauze is 1.6 g per g of the terylene non-woven fabric, and after the coating is finished, drying the gauze coated with the slurry through a drying channel on the coating machine under the traction of a mechanical device, wherein the drying temperature is 105 ℃; after drying, the hemostatic gauze is guided to the rear end of the coater to be rolled up through a mechanical device after coming out of the drying tunnel, and the hemostatic gauze is finally obtained.

Example 4

Example 4 differs from example 1 in that:

the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Y zeolite (average particle size is 900 nm), 3.0% of high molecular colloid emulsion (styrene-acrylic rubber latex, solid content is 50%), 0.01% of xanthan gum, 0.03% of locust bean gum and the balance of deionized water.

Hemostatic gauze a was prepared using the slurry for hemostatic gauze coating in example 4, and its specific preparation method: uniformly coating the prepared sizing agent for coating the hemostatic gauze on a flexible substrate by using the purchased absorbent cotton gauze as a substrate through a coating machine, wherein the coating amount of the sizing agent for coating the hemostatic gauze is 1.5 g per g of absorbent cotton gauze, and after the coating is finished, drying the sizing agent-coated gauze through a drying channel on the coating machine under the traction of a mechanical device, wherein the drying temperature is 85 ℃; after drying, the hemostatic gauze is guided to the rear end of the coater to be rolled up through a mechanical device after coming out of the drying tunnel, and the hemostatic gauze is finally obtained.

Hemostatic gauze B was prepared using the slurry for hemostatic gauze coating in example 4, and its specific preparation method: uniformly coating the prepared sizing agent for coating the hemostatic gauze on a flexible substrate by using the purchased polyester woven fabric as a substrate through a coating machine, wherein the coating amount of the sizing agent for coating the hemostatic gauze is 1.5 g per gram of the polyester woven fabric, and after the coating is finished, drying the sizing agent-coated gauze through a drying channel on the coating machine under the traction of a mechanical device, wherein the drying temperature is 85 ℃; after drying, the hemostatic gauze is guided to the rear end of the coater to be rolled up through a mechanical device after coming out of the drying tunnel, and the hemostatic gauze is finally obtained.

Example 5

Example 5 differs from example 1 in that:

the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 10% of inorganic mineral styptic powder-clinoptilolite (average particle size is 25 μm), 2.4% of polymer colloid emulsion (styrene-butadiene rubber latex, solid content is 50%), 0.02% of xanthan gum, 0.05% of locust bean gum and the balance of deionized water.

Example 6

Example 6 differs from example 1 in that:

the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 4% of inorganic mineral hemostatic powder-kaolin (average particle size is 2.0 μm), 1.4% of polymer colloid emulsion (styrene-acrylic rubber latex with solid content of 50%), 0.01% of xanthan gum, 0.01% of konjac gum and the balance of deionized water.

Example 7

Example 7 differs from example 1 in that:

the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 6% of inorganic mineral hemostatic powder-attapulgite (average particle size is 4.5 mu m), 1.6% of high polymer colloid emulsion (neoprene latex, solid content is 50%), 0.02% of xanthan gum, 0.03% of konjac gum and the balance of deionized water.

Hemostatic gauze a was prepared using the slurry for hemostatic gauze coating in example 7, and its specific preparation method: uniformly coating the prepared slurry for coating the hemostatic gauze on a flexible substrate by using the purchased terylene spunlaced non-woven fabric as a substrate through a coating machine, wherein the coating amount of the slurry for coating the hemostatic gauze is 2.0 g per g of the terylene spunlaced non-woven fabric, and after the coating is finished, drying the gauze coated with the slurry through a drying channel on the coating machine under the traction of a mechanical device, wherein the drying temperature is 85 ℃; after drying, the hemostatic gauze is guided to the rear end of the coater to be rolled up through a mechanical device after coming out of the drying tunnel, and the hemostatic gauze is finally obtained.

Hemostatic gauze B was prepared using the slurry for hemostatic sponge gauze coating in example 7, and its specific preparation method: the prepared slurry for coating the hemostatic gauze is uniformly coated on a flexible substrate by a coating machine by taking purchased melamine sponge as a substrate, wherein the coating amount is 3.2 g of the slurry for coating the hemostatic gauze coated on each g of absorbent cotton gauze, after the coating is finished, the sponge is vertically hung and dried under the tensionless condition, the drying temperature is 70 ℃, the drying time is 30 minutes, and after the drying, the sponge is cooled in a dryer, so that the hemostatic sponge gauze of a final finished product is obtained.

Example 8

Example 8 differs from example 1 in that:

the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 5% of inorganic mineral hemostatic powder-halloysite (average particle size is 450 nm), 2.0% of polymer colloid emulsion (neoprene latex, solid content is 50%), 0.02% of xanthan gum, 0.06% of locust bean gum and the balance of deionized water.

Example 9

Example 9 differs from example 1 in that:

the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 5% of inorganic mineral hemostatic powder-illite (average particle size is 1.2 mu m), 2.4% of polymer colloid emulsion (styrene-butadiene rubber latex, solid content is 50%), 0.05% of xanthan gum, 0.05% of locust bean gum and the balance of deionized water.

Hemostatic gauze a was prepared using the slurry for hemostatic gauze coating in example 9, and its specific preparation method: uniformly coating the prepared sizing agent for coating the hemostatic gauze on a flexible substrate by using the purchased absorbent cotton gauze as a substrate through a coating machine, wherein the coating amount of the sizing agent for coating the hemostatic gauze is 1.5 g per g of absorbent cotton gauze, and after the coating is finished, drying the sizing agent-coated gauze through a drying channel on the coating machine under the traction of a mechanical device, wherein the drying temperature is 85 ℃; after drying, the hemostatic gauze is guided to the rear end of the coater to be rolled up through a mechanical device after coming out of the drying tunnel, and the hemostatic gauze is finally obtained.

Hemostatic gauze B was prepared using the slurry for hemostatic gauze coating in example 9, and its specific preparation method: uniformly coating the prepared slurry for coating the hemostatic gauze on a flexible substrate by using the purchased terylene-viscose blended non-woven fabric as a substrate through a coating machine, wherein the coating amount is 1.3 g of the slurry for coating the hemostatic gauze per g of the terylene-viscose blended non-woven fabric, and after the coating is finished, drying the gauze coated with the slurry through a drying channel on the coating machine under the traction of a mechanical device, wherein the drying temperature is 90 ℃; after drying, the hemostatic gauze is guided to the rear end of the coater to be rolled up through a mechanical device after coming out of the drying tunnel, and the hemostatic gauze is finally obtained.

Example 10

Example 10 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Y zeolite (average particle size is 900 nm), 3% of high molecular colloid emulsion (carboxyl styrene-butadiene latex with solid content of 50%), 0.015% of xanthan gum, 0.015% of locust bean gum and the balance of deionized water. The pH of the slurry for hemostatic gauze coating was adjusted to 7.0 using 0.1M hydrochloric acid and 0.1M aqueous sodium hydroxide.

Example 11

Example 11 differs from example 10 in that: the pH of the slurry for hemostatic gauze coating was controlled to 9.0.

Example 12

Example 12 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 4% of inorganic mineral hemostatic powder-X zeolite (average particle size is 1.6 mu m), 4% of inorganic mineral hemostatic powder-halloysite (average particle size is 450 nm), 3% of polymer colloid emulsion (carboxyl styrene-butadiene latex, solid content is 50%), 0.015% of xanthan gum, 0.015% of locust bean gum and the balance of deionized water. The pH of the slurry for hemostatic gauze coating was adjusted to 7.0 using 0.1M hydrochloric acid and 0.1M aqueous sodium hydroxide.

Example 13

Example 13 differs from example 12 in that: the pH of the slurry for hemostatic gauze coating was controlled to 9.0.

Example 14

Example 14 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral hemostatic powder-kaolin (average particle size is 2.0 μm), 3% of polymer colloid emulsion (carboxyl styrene-butadiene latex, solid content is 50%), 0.015% of xanthan gum, 0.015% of locust bean gum and the balance of deionized water. The pH of the slurry for hemostatic gauze coating was adjusted to 7.0 using 0.1M hydrochloric acid and 0.1M aqueous sodium hydroxide.

Example 15

Example 15 differs from example 14 in that: the pH of the slurry for hemostatic gauze coating was controlled to 9.0.

Example 16

Example 16 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 10% of inorganic mineral styptic powder-Y zeolite (average particle size is 900 nm), 3.2% of high molecular colloid emulsion (styrene-butadiene rubber latex, solid content is 50%), 0.06% of xanthan gum, 0.02% of konjak gum and the balance of deionized water. The pH of the slurry for hemostatic gauze coating was adjusted to 9.0 using 0.1M hydrochloric acid and 0.1M aqueous sodium hydroxide.

Hemostatic gauze was prepared using the slurry for hemostatic gauze coating in example 16, and its specific preparation method: uniformly coating the prepared slurry for coating the hemostatic gauze on a flexible substrate by using 30 g/square meter of purchased terylene spunlaced non-woven fabric as a substrate through a coating machine, wherein the coating amount is 1.3 g of slurry for coating the hemostatic gauze per g of terylene spunlaced non-woven fabric, and after the coating is finished, drying the non-woven gauze coated with the slurry through a drying channel on the coating machine under the traction of a mechanical device, wherein the drying temperature is 100 ℃; after drying, the hemostatic gauze is guided to the rear end of the coater to be rolled up through a mechanical device after coming out of the drying tunnel, and the hemostatic gauze is finally obtained.

Example 17

Example 17 differs from example 16 in that:

the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 9% of inorganic mineral hemostatic powder-Y zeolite (average particle size is 900 nm), 1% of inorganic mineral hemostatic powder-kaolin (average particle size is 2.0 mu m), 3.2% of polymer colloid emulsion (polyurethane latex, solid content 50%), 0.06% of xanthan gum, 0.02% of konjac gum and the balance of deionized water. The pH of the slurry for hemostatic gauze coating was adjusted to 9.0 using 0.1M hydrochloric acid and 0.1M aqueous sodium hydroxide.

Example 18

Example 18 differs from example 17 in that:

the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral hemostatic powder-Y zeolite (average particle size is 900 nm), 2% of inorganic mineral hemostatic powder-kaolin (average particle size is 2.0 mu m), 3.2% of polymer colloid emulsion (polyurethane latex, solid content 50%), 0.06% of xanthan gum, 0.02% of konjac gum and the balance of deionized water. The pH of the slurry for hemostatic gauze coating was adjusted to 9.0 using 0.1M hydrochloric acid and 0.1M aqueous sodium hydroxide.

Example 19

Example 19 differs from example 17 in that:

the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 4% of inorganic mineral hemostatic powder-Y zeolite (average particle size is 900 nm), 6% of inorganic mineral hemostatic powder-kaolin (average particle size is 2.0 mu m), 3.2% of polymer colloid emulsion (polyurethane latex, solid content 50%), 0.06% of xanthan gum, 0.02% of konjac gum and the balance of deionized water. The pH of the slurry for hemostatic gauze coating was adjusted to 9.0 using 0.1M hydrochloric acid and 0.1M aqueous sodium hydroxide.

Example 20

Example 20 differs from example 17 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 7% of inorganic mineral hemostatic powder-X zeolite (average particle size is 1.6 μm), 3% of inorganic mineral hemostatic powder-halloysite (average particle size is 450 nm), 3.2% of polymer colloid emulsion (carboxyl styrene-butadiene latex, solid content is 50%), 0.06% of xanthan gum, 0.02% of konjac gum and the balance of deionized water. The pH of the slurry for hemostatic gauze coating was adjusted to 9.0 using 0.1M hydrochloric acid and 0.1M aqueous sodium hydroxide.

Example 21

Example 21 differs from example 17 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 6% of inorganic mineral hemostatic powder-X zeolite (average particle size is 1.6 mu m), 4% of inorganic mineral hemostatic powder-illite (average particle size is 1.2 mu m), 3.2% of polymer colloid emulsion (carboxyl styrene-butadiene latex, solid content is 50%), 0.06% of xanthan gum, 0.02% of konjac gum and the balance of deionized water. The pH of the slurry for hemostatic gauze coating was adjusted to 9.0 using 0.1M hydrochloric acid and 0.1M aqueous sodium hydroxide.

Example 22

Example 22 differs from example 17 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral hemostatic powder-A zeolite (average particle size is 600 nm), 2% of inorganic mineral hemostatic powder-montmorillonite (average particle size is 3.2 μm), 3.2% of polymer colloid emulsion (polyacrylate latex, solid content 50%), 0.06% of xanthan gum, 0.02% of konjac gum and the balance of deionized water. The pH of the slurry for hemostatic gauze coating was adjusted to 9.0 using 0.1M hydrochloric acid and 0.1M aqueous sodium hydroxide.

Example 23

Example 23 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Ca-P zeolite (average particle size is 12 mu m), 4% of high molecular colloid emulsion (styrene-butadiene rubber latex, solid content is 50%), 0.02% of xanthan gum, 0.02% of konjak gum and the balance of deionized water. The pH of the slurry for hemostatic gauze coating was adjusted to 9.0 using 0.1M hydrochloric acid and 0.1M aqueous sodium hydroxide.

Hemostatic gauze was prepared using the slurry for hemostatic gauze coating in example 23, and its specific preparation method: uniformly coating the prepared slurry for coating the hemostatic gauze on a flexible substrate by using the purchased polyester fiber non-woven fabric as a substrate through a coating machine, wherein the coating amount of the slurry for coating the hemostatic gauze is 1.43 g per gram of the polyester fiber non-woven fabric, and after the coating is finished, drying the gauze coated with the slurry through a drying channel on the coating machine under the traction of a mechanical device, wherein the drying temperature is 105 ℃; after drying, the hemostatic gauze is guided to the rear end of the coater to be rolled up through a mechanical device after coming out of the drying tunnel, and the hemostatic gauze is finally obtained.

Example 24

Example 24 differs from example 23 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Ca-P zeolite (average particle size is 12 mu m), 6% of high molecular colloid emulsion (styrene-butadiene rubber latex, solid content is 50%), 0.02% of xanthan gum, 0.02% of konjak gum and the balance of deionized water.

Example 25

Example 25 differs from example 23 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Ca-P zeolite (average particle size is 12 mu m), 8% of high molecular colloid emulsion (styrene-butadiene rubber latex, solid content is 50%), 0.02% of xanthan gum, 0.02% of konjak gum and the balance of deionized water.

Example 26

Example 26 differs from example 23 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Ca-P zeolite (average particle size is 12 mu m), 4% of high polymer colloid emulsion (neoprene latex, solid content is 50%), 0.02% of xanthan gum, 0.02% of konjak gum and the balance of deionized water.

Example 27

Example 27 differs from example 26 in that: the neoprene latex is replaced with a carboxylated styrene-butadiene latex.

Example 28

Example 28 differs from example 26 in that: the neoprene latex is replaced with a pure propylene rubber latex.

Example 29

Example 29 differs from example 26 in that: the neoprene latex is replaced with a styrene-acrylic latex.

Example 30

Example 30 differs from example 26 in that: the neoprene latex is replaced with a polyurethane latex.

Example 31

Example 31 differs from example 26 in that: the neoprene latex is replaced with a polyacrylate latex.

Comparative example

Comparative example 1 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 6% inorganic mineral styptic powder-A zeolite (average particle size is 600 nm), 3% high molecular colloid emulsion (styrene-acrylic rubber emulsion, solid content is 50%), and the balance of deionized water.

Comparative example 2 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 6% of inorganic mineral styptic powder-P zeolite (average particle size is 10 mu m), 3% of polymer colloid emulsion (styrene-acrylic rubber emulsion, solid content is 50%), 0.05% of xanthan gum and the balance of deionized water.

Comparative example 3 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 6% of inorganic mineral styptic powder-A zeolite (average particle size is 600 nm), 3% of high molecular colloid emulsion (styrene-acrylic rubber emulsion, solid content is 50%), 0.10% of locust bean gum and the balance of deionized water.

Comparative example 4 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 6% of inorganic mineral styptic powder-P zeolite (average particle size is 10 mu m), 3% of polymer colloid emulsion (styrene-acrylic rubber emulsion, solid content is 50%), 0.10% of konjak gum and the balance of deionized water.

Comparative example 5 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 6% of inorganic mineral styptic powder-A zeolite (average particle size is 600 nm), 3% of polymer colloid emulsion (styrene-acrylic rubber emulsion, solid content is 50%), 0.1% of carrageenan and the balance of deionized water.

Comparative example 6 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 6% inorganic mineral styptic powder-P zeolite (average particle size is 10 μm), 3% high molecular colloid emulsion (styrene-acrylic rubber emulsion, solid content is 50%), 0.1% carbomer and the balance deionized water.

Comparative example 7 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 6% of inorganic mineral styptic powder-A zeolite (average particle size is 600 nm), 3% of polymer colloid emulsion (styrene-acrylic rubber emulsion, solid content is 50%), 0.05% of carrageenan, 0.05% of carbomer and the balance of deionized water.

Comparative example 8 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 4% of inorganic mineral hemostatic powder-P zeolite (10 mu m), 2% of polymer colloid emulsion (pure acrylic rubber emulsion, solid content of 50%), 0.03% of xanthan gum, 0.04% of carrageenan and the balance of deionized water.

Comparative example 9 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 4% of inorganic mineral styptic powder-P zeolite (average particle size is 10 mu m), 3% of high molecular colloid emulsion (pure acrylic rubber emulsion, solid content is 50%), 0.04% of carbomer, 0.06% of konjak gum and the balance of deionized water.

Comparative example 10 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 5% of inorganic mineral styptic powder-Y zeolite (average particle size is 900 nm), 2.4% of high molecular colloid emulsion (neoprene emulsion, solid content is 50%), 0.06% of xanthan gum, 0.04% of carbomer and the balance of deionized water.

Comparative example 11 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 2% of inorganic mineral styptic powder-X zeolite (average particle size is 1.6 mu m), 0.6% of high molecular colloid emulsion (neoprene emulsion, solid content is 50%), 0.03% of sodium alginate, 0.03% of konjak gum and the balance of deionized water.

Comparative example 12 differs from example 1 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral hemostatic powder-kaolin (average particle size of 2.0 μm), 4% of polymer colloid emulsion (neoprene emulsion, solid content of 50%), 0.03% of chitosan, 0.07% of locust bean gum and the balance of deionized water.

Comparative example 13 differs from example 10 in that: the pH of the slurry for hemostatic gauze coating was controlled to 5.0.

Comparative example 14 differs from example 12 in that: the pH of the slurry for hemostatic gauze coating was controlled to 5.0.

Comparative example 15 differs from example 14 in that: the pH of the slurry for hemostatic gauze coating was controlled to 5.0.

Comparative example 16 differs from example 23 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Ca-P zeolite (average particle size is 12 μm), 2% of gelatin, 0.1% of glutaraldehyde as a cross-linking agent, 0.02% of xanthan gum, 0.02% of konjak gum and the balance of deionized water.

Comparative example 17 differs from example 23 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Ca-P zeolite (average particle size is 12 μm), 3% of gelatin, 0.1% of glutaraldehyde as a cross-linking agent, 0.02% of xanthan gum, 0.02% of konjak gum and the balance of deionized water.

Comparative example 18 differs from example 23 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Ca-P zeolite (average particle size is 12 mu m), 4% of gelatin, 0.1% of glutaraldehyde as a cross-linking agent, 0.02% of xanthan gum, 0.02% of konjak gum and the balance of deionized water.

Comparative example 19 differs from example 23 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Ca-P zeolite (average particle size is 12 μm), 2% of chitosan, 0.02% of xanthan gum, 0.02% of konjac gum and the balance of deionized water.

Comparative example 20 differs from example 23 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Ca-P zeolite (average particle size is 12 mu m), 2% of oxidized starch, 0.02% of xanthan gum, 0.02% of konjac gum and the balance of deionized water.

Comparative example 21 differs from example 23 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Ca-P zeolite (average particle size is 12 μm), 2% of PVA1788, 0.02% of xanthan gum, 0.02% of konjac gum and the balance of deionized water.

Comparative example 22 differs from example 23 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Ca-P zeolite (average particle size is 12 mu m), 2% of sodium carboxymethyl cellulose, 0.02% of xanthan gum, 0.02% of konjac gum and the balance of deionized water.

Comparative example 23 differs from example 23 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% of inorganic mineral styptic powder-Ca-P zeolite (average particle size is 12 mu m), 2% of sodium alginate, 0.02% of xanthan gum, 0.02% of konjac gum and the balance of deionized water.

Comparative example 24 differs from example 23 in that: the slurry for coating the hemostatic gauze is prepared from the following raw materials in percentage by mass: 8% inorganic mineral styptic powder-Ca-P zeolite (average particle size 12 μm) and the balance deionized water.

Comparative example 25 was obtained by purchasing Quikshot control+produced by Z-media Co., ltd

Hemostatic dressing. The gauge was 12 inches by 12 inches, folded into 4 inch square pieces of gauze. The product is composed of three layers of hemostatic gauze, and the substrate of the gauze is non-woven fabric. The first layer and the third layer are oriented in the same warp and weft directions. The warp and weft direction orientation of the middle second layer is perpendicular to the first layer and the second layer. The test shows that the bending length of the first layer of hemostatic gauze in the warp direction is 8.50 cm, the bending length of the first layer of hemostatic gauze in the weft direction is 2.20 cm, and the average bending length is 5.35 cm; the bending length of the second layer of hemostatic gauze in the warp direction is 8.75 cm, the bending length of the second layer of hemostatic gauze in the weft direction is 1.85 cm, and the average bending length of the second layer of hemostatic gauze is 5.30 cm; the third layer of hemostatic gauze had a warp length of 8.45 cm, a weft length of 2.0 cm and an average warp length of 5.20 cm. If three pieces of gauze are of the same variety, the overall average bending length is 5.30 cm. The hemostatic material has high stiffness and is not suitable for being stuffed into an elongated wound which is penetrated by a gunshot wound and the like. The three-layer material has the falling rate of 0.33%,0.18% and 0.47% respectively according to the method for testing the falling rate of the oscillating powder in water.

Performance test

Detection method/test method

Softness of a fabric can be characterized by an index of the fabric's bending length.

The bending length of the fabric refers to the length of the fabric strip extending when the fabric strip is bent downwards to 7.1 degrees under the action of dead weight when one end of the fabric strip is suspended (GB/T18318.1-2009, section 1 of determination of the bending Property of textiles: inclined plane method).

In the application, the bending length test method is used for testing the bending performance of the textile according to GB/T18318.1-2009, section 1: slope method test.

The average warp length is obtained by dividing the sum of the warp length plus the weft length by 2.

The calculation method of the average bending length refers to the data processing method adopted in HG/T5254-2017 'determination of stiffening effect of textile dyeing and finishing auxiliary stiffening finishing agent'.

The smaller the bend length values obtained by the test, the better the softness of the fabric, i.e. the less stiff the fabric. The greater the bending length, the less soft the fabric, i.e., the higher the stiffness of the fabric.

Three methods were employed in this application to evaluate the severity of shedding of inorganic zeolite particles from a material.

1. Water shedding rate: the testing method comprises the steps of immersing a certain amount of zeolite hemostatic gauze in water, oscillating for one hour on a rotary oscillator, fishing out the gauze, hanging the gauze above the immersion liquid until no liquid drops, filtering the immersion liquid, collecting the dropped particles, drying and weighing, and calculating the drop rate. The index evaluates how much particulate matter may be introduced into the liquid when the product is contacted with the liquid.

2. Dry state dust fall rate: the testing method is that a certain amount of zeolite hemostatic gauze is placed on a stainless steel screen, a rubber rod is used for beating the gauze for a certain time at a certain frequency, and after falling off from the stainless steel screen, the falling dust is carried by air flow to a glass fiber filter membrane to be trapped and collected, the weight of the trapped powder is weighed, and the falling rate is calculated. This index evaluates the zeolite dust on the product, i.e., the ratio of inorganic particulates that are not bound to the substrate by the binder.

3. Rub dust fall-off rate: placing a certain amount of zeolite hemostatic gauze on a stainless steel screen, rubbing for a certain number of times by using both hands, then beating the gauze for a certain time with a rubber rod at a certain frequency, and after falling off from the stainless steel screen, carrying the dust to a glass fiber filter membrane by airflow to be trapped and collected; repeating the above kneading process for 5 times; the weight of all the trapped powder is weighed, and the falling rate is calculated. This index evaluates the ratio of inorganic particulates that may fall off when the zeolite on the product is rubbed.

Slurry stability test: the test subjects were the slurries prepared in examples 1-9 and comparative examples 1-12. The testing method comprises the following steps: after the slurries were mixed well, 250mL of slurry was measured and poured into a 250mL graduated cylinder. Standing and settling for 4 hours. The top 25 ml of slurry and the bottom 25 ml of slurry in the measuring cylinder were then tested for solids content. The stability of the slurry was evaluated by taking the ratio of the difference between the two to the bottom solids content as the sedimentation ratio.

Determination of the solid content: test subjects the slurries prepared in examples 1-9 and comparative examples 1-12. The testing method comprises the following steps: 25 ml of the slurry was poured into a previously weighed aluminum foil dish and weighed. Then dried overnight in a 105 degree oven and weighed. The dry weight of the residual solids is calculated, divided by the initial weight of the slurry, and the calculated value is the solids content of the slurry. For example, after a sample is settled for 4 hours by standing, the solids content of the slurry of the top 25 ml and the bottom 25 ml is 5.78% and 9.79%, respectively, and the settlement ratio is (9.79% -5.78%)/9.79% = 40.96%. The smaller the number, the more stable the slurry, and the larger the number, the more severe the slurry settling.

When the slurry is unstable, several conditions may occur,

(1) The solid content in the slurry is gradually increased from top to bottom, and part of powder is settled to the bottom to form an obvious powder close-packed deposition layer;

(2) The slurry is split in phase, the solid content of the upper layer is extremely low, the slurry resembles a clear water sample, the solid content of the lower layer is higher, an obvious macroscopic boundary line exists between the two layers, but the solid content of the inner part of the lower layer is more uniform, and the bottom of the lower layer is not provided with an obvious close-packed deposition layer;

(3) The slurry powder and latex particles clearly form a flocculated structure, forming a bean-like deposit, resembling the morphology of salty soybean milk.

The three conditions are respectively marked as three states of close-packed deposition, double-layer phase separation and flocculation phase separation.

Samples with a sedimentation ratio of less than 5.0% and samples in which flocculation phase separation did not occur were judged as stable slurries.

Hemostatic gauze performance test prepared using the slurry for hemostatic gauze coating, test subjects: hemostatic gauze in example 2 was test set 1, hemostatic gauze a in example 3 was test set 2, hemostatic gauze a in example 4 was test set 3, hemostatic gauze a in example 9 was test set 4, hemostatic gauze B in example 9 was test set 5, hemostatic gauze B in example 3 was test set 6, hemostatic gauze a in example 7 was test set 7, hemostatic gauze B in example 4 was test set 8, and hemostatic gauze B in example 7 was test set 9. Test groups 1-9 tested in vitro clotting time, in-water shedding rate, dry shedding rate and rub shedding rate, average bending length.

Effect of slurry stability and pH: test subjects the slurries in examples 10-15 and comparative examples 13-15. The testing method comprises the following steps: see the slurry stability test described above, to determine the sedimentation ratio.

Influence of inorganic hemostatic mineral powder compounding on comprehensive performance: hemostatic gauze in test subject examples 16-22. Test methods refer to in vitro clotting time, shedding rate in water, dry shedding rate, average bending length and sedimentation ratio.

Test subjects the zeolite-nonwoven fabric composites of examples 23-31 and comparative examples 16-24 were tested for calcium ion exchange after zeolite coating. The testing method comprises the following steps: 0.8 g of the same zeolite powder and 7 g of a polyester nonwoven fabric were taken and immersed in 700 g of a sodium chloride aqueous solution (physiological saline) having a concentration of 0.9%. At this time, calcium ions in the zeolite are introduced from the zeolite into the sodium chloride aqueous solution through ion exchange reaction, and sodium ions are exchanged into the zeolite. In the soaking process, the calcium ion concentration in the solution is tested on line in real time by using the calcium ion selective electrode until the ion exchange reaches the balance, and the calcium ion concentration is not changed any more. Because of the high concentration and large volume of sodium chloride solution, almost all the freely movable calcium ions in the zeolite are exchanged. Thus, the total number of freely movable calcium ions in the zeolite can be estimated in terms of the amount of calcium ions exchanged out. Then referring to the above procedure, the composite material coated with the slurry containing the same amount of zeolite was also immersed in an aqueous solution of sodium chloride having a concentration of 0.9% which was also 700 g, and the concentration of calcium ions eluted from the composite material into the sodium chloride solution by ion exchange was tested on line in real time using a calcium ion selective electrode until the ion exchange reached equilibrium, and the calcium ion concentration was no longer changed.

Data analysis

Table 2 shows the stability test parameters of the slurries prepared in examples 1-9 and comparative examples 1-12

It can be seen in combination with examples 1-9 and comparative examples 1-12 and with Table 2 that stable slurries can be obtained with only the compounded forms of xanthan gum-konjac gum and xanthan gum-locust bean gum when the suspending agent concentration is below 0.1%. The formulation of stable slurries cannot be achieved either alone or in the alternative.

It should be noted that, in the screening experiment, it is found that stable slurry can be obtained with more complex forms when the total concentration of the suspending agent is greatly increased to be more than or equal to 0.5%. However, the suspending agent itself is a polymer having a high glass transition temperature, and when the amount of the suspending agent is too large, the softness of the product is also affected. Therefore, in the present application, xanthan gum-konjac gum and xanthan gum-locust bean gum systems that can achieve good suspension effect at ultra-low concentration (< 0.1%) are preferred.

Table 3 is a data table of the in vitro clotting time, in-water shedding rate, dry shedding rate, rub shedding rate, and average bending length of test groups 1 to 9

From the test results of test groups 1-9, the in vitro coagulation time of the product obtained by coating the slurry in the application is less than 3 minutes in the in vitro coagulation test of the product, which indicates that the product in the application has obvious procoagulant efficacy; the bending length of the product in the application is less than 3.0 cm, which indicates that the product has higher softness; the water shedding rate, the dry dust shedding rate and the rubbing dust shedding rate are far lower than those of the product coated by the solution type binder, which shows that the product of the application has the obvious advantage of low shedding rate.

Table 4 is a table of sedimentation ratio parameters of the slurries in examples 10 to 15 and comparative examples 13 to 15

Test object	Sedimentation proportion%
		Example 10	2.5
Example 11	1.1
		Example 12	1.4
Example 13	0.8
		Example 14	3.6
Example 15	1.2
		Comparative example 13	96
Comparative example 14	45
		Comparative example 15	89

As can be seen from the combination of examples 10-15 and comparative examples 13-15 and Table 4, the pH of the slurries in the present application was controlled to be 6-10, and the resulting slurries were relatively good in suspension and relatively stable in storage for coating processes to produce hemostatic gauze products. Preferably, the pH value of the slurry is controlled to be 7.0-9.0, and the slurry is matched with a mixture of xanthan gum and konjak gum or a mixture of xanthan gum and locust bean gum to be used as a suspending agent.

Table 5 is a table of performance test parameters of blood-stopping gauze of examples 16 to 22

As can be seen by combining examples 16-22 with Table 5, the slurries prepared in this application are very stable, with a sedimentation ratio of less than 1%. After being coated on the terylene spunlaced non-woven fabric, the obtained hemostatic material has the average bending length of less than 3.0 cm, the water and dry falling rate of less than 0.2 percent, and the in vitro coagulation time of less than 180 seconds.

It can be seen from the combination of examples 16-22 and Table 5 that the in vitro coagulation index is further improved when the clay mineral is mixed in the X and Y zeolite, and the in vitro coagulation time is shortened, which is related to the stronger activation ability of the clay material to the surface factor (XII factor). It should be noted that the in vitro clotting time is not completely proportional to the blood stopping speed of the animal and human experiments. The in vitro clotting time of zeolite materials is often slightly longer than that of clay-based materials, however, in practical human experiments, procoagulant properties are exhibited that are not inferior to those of clay-based materials. This may be related to the greater diversity of the role of zeolites, which, in addition to activating surface factors (factor XII), can also provide calcium ions (factor IV) involved in the activation and stabilization of procoagulant fibrinogen (factor V) and autologous prothrombin C (factor X).

Table 6 shows the detection parameters of examples 23 to 31 and comparative examples 16 to 24

As can be seen from the combination of examples 23 to 31 and comparative examples 16 to 24 and Table 6, when 0.8g of the unbound zeolite powder was immersed in 700g of physiological saline, the equilibrium concentration of dissolved calcium ions was 0.77mmol/L. In contrast, when 0.8g of zeolite was adhered to the nonwoven fabric substrate with the binder, the equilibrium concentration of dissolved calcium ions was less than 0.77mmol/L, and therefore, it was revealed that a part of zeolite was coated with the binder, and no longer contacted with physiological saline, and no participation in the ion exchange reaction was possible.

As can be seen from the combination of examples 23 to 31 and comparative examples 16 to 24 and Table 6, when styrene-butadiene latex was used as the binder, the concentration was 2.0%,3.0% and 4.0%, respectively, and the equilibrium concentration of calcium ions was 0.74, 0.75 and 0.73mmol/L, respectively, which dissolved calcium ions in amounts of 3.9%, 2.6% and 5.2% less than the soluble amount of zeolite powder itself, thus indicating that almost no zeolite was completely coated with styrene-butadiene latex.

As can be seen from the combination of examples 23 to 31 and comparative examples 16 to 24 and Table 6, when the polychloroprene latex, the carboxylated styrene-butadiene latex, the pure acrylic latex, the styrene-acrylic latex, the polyurethane latex and the polyacrylate latex were all used as binders, the soluble calcium ions were 1.3%,2.6%,1.3%,3.9%,3.9% and 2.6% less, and the values were not large. When gelatin (added with 0.1% glutaraldehyde as a cross-linking agent) was used as a binder, the equilibrium concentration of calcium ions was greatly reduced to 0.61, 0.57 and 0.53mmol/L at concentrations of 2%,3% and 4%, indicating that about 20.8%, 26.0% and 31.2% of calcium ions were enclosed by the binder within the zeolite and no more involved in ion exchange, indicating that more zeolite was fully covered with gelatin binder and surface embedded.

In combination with examples 23-31 and comparative examples 16-24 and with Table 6, it can be seen that when 2% concentration of chitosan, starch, PVA1788 and sodium carboxymethylcellulose were used as binders, 32.5%, 24.7%, 22.1% and 31.2% of calcium ions, respectively, were embedded by the binders and were no longer able to participate in the ion exchange reaction. The concentration of sodium alginate of 2% as binder is particularly high, 72.7% of the calcium ion concentration is reduced, possibly related to the fact that sodium alginate is easily combined with calcium ions to form insoluble calcium alginate, which consumes part of the calcium ions.

In addition to the calcium ion concentrations after reaction equilibrium was reached, the initial dissolution rate of calcium ions was used as an indicator to distinguish between the water-soluble binder and the latex binder as seen in the combination of examples 23-31 and comparative examples 16-24 and in Table 6. The dissolution data of the first 30 seconds were selected, and the rate constant was calculated according to the kinetic model of the first order reaction, and the results are shown in Table 6. As can be seen from Table 6, the dissolution rate constant of calcium ions was 47.2X10 when pure zeolite powder was not covered with any binder on the surface ^-3 s ^-1 The dissolution rate of zeolite is slightly reduced to 25.8-33.5X10 after zeolite is coated on the non-woven substrate by using 2% styrene-butadiene latex, neoprene latex, carboxylated styrene-butadiene latex, pure propylene latex, styrene-acrylic latex, polyurethane latex and polyacrylate as binders ^-3 s ^-1 Therefore, it is explained that part of the surface is covered with the latex binder, and the dissolution rate of calcium ions is slowed down.

As can be seen from the combination of examples 23 to 31 and comparative examples 16 to 24 and the combination of Table 6, the calcium ion elution rate was increased from 26.9X10 when the styrene-butadiene latex concentration was increased from 2.0% to 3.0% and 4.0% ^-3 s ^-1 Reduced to 23.3X10 ^-3 s ^-1 And 19.1X10 ^-3 s ^-1 When gelatin and shell polymer with concentration of 2% are usedWhen sugar, starch oxide, PVA1788 and sodium carboxymethylcellulose are used as binder, the dissolution rate constant of calcium ions is reduced to 12.4X10 ^-3 s ^-1 、6.9×10 ^-3 s ^-1 、11.5×10 ^-3 s ^-1 、14.0×10 ^-3 s ^-1 And 9.8X10 ^-3 s ^-1 The numerical value is obviously smaller than that of the latex type binder, which indicates that the surface coating of the zeolite is serious, and the hemostatic effect of the prepared hemostatic material is affected. Therefore, the polymer colloid emulsion provided in the application can reduce the coating ratio of the sizing agent on the surface of the zeolite coated by the binder, so that the hemostatic material prepared by the application is guaranteed to have a better hemostatic effect, and meanwhile, the hemostatic material has better safety and flexibility.

It should be noted that the pores within the zeolite are in three-dimensional communication and that calcium ions can diffuse between different regions within the zeolite. Thus, when the zeolite surface portion is embedded, calcium ions in the embedded region can still be ion exchanged with the external liquid by diffusing internally to other open regions not embedded. This is also why the ion exchange rate index is more affected by the binder than the exchangeable calcium ion index in the above results. For example, in the comparative example, after coating the soluble polymer, the soluble calcium ion is reduced by 20-30%, but the initial exchange rate is reduced by 70% -85%, the latter value is closer to the ratio of the surface covered by the binder.

In conclusion, the preparation method of the sizing agent for coating the hemostatic gauze has the advantages of simpler route process, short production period, high yield of the hemostatic gauze prepared by the sizing agent, and capability of greatly reducing the production cost of the hemostatic gauze. The hemostatic gauze prepared from the slurry for coating the hemostatic gauze has the advantages of high surface exposure proportion of inorganic components, good hemostatic effect, low powder falling rate, good safety, good flexibility of composite materials and good hand feeling, and solves three problems in the related technology.

The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims

1. A slurry for coating hemostatic gauze, which is characterized in that: the slurry mainly comprises a dispersing agent, inorganic mineral hemostatic powder, a high molecular colloid emulsion and a suspending agent; the mass of the binder component in the high polymer colloid emulsion accounts for 0.2-3% of the total content of the slurry; the mass of the suspending agent accounts for 0.01% -0.1% of the total content of the slurry; the inorganic mineral hemostatic powder accounts for 1% -15% of the total content of the slurry; the pH value of the slurry is controlled to be 6-10; the dispersing agent is water or a mixed dispersing agent formed by water and volatile organic solvent.

2. A slurry for hemostatic gauze coating according to claim 1 wherein: the polymer colloid emulsion consists of a dispersing solvent and colloid particles dispersed in the solvent; the surface of the colloid particles in the high polymer colloid emulsion is provided with negative charges or nonionic surfactant components; glass transition temperature T of the polymer colloid emulsion _g Below 25 ℃.

3. A slurry for hemostatic gauze coating according to claim 1 or 2 wherein: the high polymer colloid emulsion is one or a combination of a plurality of neoprene rubber latex, styrene-butadiene rubber latex, carboxyl styrene-butadiene rubber latex, polyurethane latex, pure propylene rubber latex, styrene-acrylic rubber latex, polyacrylate latex, oxidized polyethylene latex and polytetrafluoroethylene emulsion; the diameter of colloid particles in the polymer colloid emulsion is between 50 and 500 and nm; glass transition temperature T of the polymer colloid emulsion _g Below 0 ℃.

4. A slurry for hemostatic gauze coating according to claim 1 or 2 wherein: the inorganic mineral hemostatic powder comprises zeolite hemostatic powder and clay hemostatic powder, wherein the zeolite hemostatic powder is at least one of A-type zeolite, X-type zeolite, Y-type zeolite, P-type zeolite, clinoptilolite, mordenite, chabazite and ZSM-5 zeolite; the clay styptic powder is at least one of kaolin, montmorillonite, bentonite, attapulgite, diatomite, illite and halloysite; the average particle size of the inorganic mineral hemostatic powder is 50 nm-50 mu m.

5. A slurry for hemostatic gauze coating according to claim 4 wherein: the average particle size of the inorganic mineral hemostatic powder is 100 nm-20 mu m.

6. A slurry for hemostatic gauze coating according to claim 5 wherein: the average particle size of the inorganic mineral hemostatic powder is 400 nm-4 mu m.

7. A slurry for hemostatic gauze coating according to claim 1 wherein: the pH value of the slurry is controlled to be 7.0-9.0; the suspending agent is at least one of xanthan gum, locust bean gum and konjac gum.

8. A hemostatic gauze coating slurry according to claim 7 wherein: the suspending agent is a mixture of xanthan gum and konjak gum or a mixture of xanthan gum and locust bean gum, and the mass of the suspending agent accounts for 0.01-0.1% of the total content of the slurry; when the suspending agent is a mixture of xanthan gum and konjac gum, the mass ratio of the xanthan gum to the konjac gum is (9:1) - (3:7); when the suspending agent is a mixture of xanthan gum and locust bean gum, the mass ratio of the xanthan gum to the locust bean gum is (7:3) - (2:8).

9. A hemostatic gauze prepared from a slurry for hemostatic gauze coating according to any one of claims 1 to 8, characterized in that: comprises a flexible substrate and an inorganic mineral powder coating, wherein the inorganic mineral powder coating is prepared from the slurry for coating the hemostatic gauze in the claims 1-8; the average bending length of the hemostatic gauze prepared by the slurry for coating the hemostatic gauze is less than 3.0 cm, the falling rate in water is less than 0.2%, and the in-vitro coagulation time is less than three minutes.

10. A hemostatic gauze prepared from a slurry for hemostatic gauze coating according to claim 9 wherein: the flexible substrate is one of absorbent cotton gauze, all-cotton non-woven fabric, polyester-viscose blended non-woven fabric, polyurethane sponge sheet, melamine resin sponge sheet and sponge strip.