Composite sustained-release material as well as preparation method and application thereof

Abstract

The invention provides a composite sustained-release material as well as a preparation method and application thereof. The composite slow-release material comprises a porous metal framework and an organic phase, and pores of the porous metal framework are filled with the organic phase; the porous metal framework comprises self-degradable metal and sterilization elements; the organic phase comprises a water-soluble polymer and an organic functional substance. The composite slow-release material provided by the invention can realize differential synchronous release of inorganic sterilization elements and organic functional substances, and can be used in the washing device, so that the compounding of sterilization and other functions is realized, or the synergistic cooperation of various antibacterial substances is realized to improve the antibacterial effect.

Description

Technical Field

[0001] The present invention relates to the technical field of sustained-release materials, and particularly relates to a composite sustained-release material, a preparation method thereof, and an application thereof. Background Art

[0002] The existing antibacterial sustained-release technologies mainly include pure inorganic sustained-release systems or pure organic sustained-release systems.

[0003] A typical inorganic sustained-release system uses phosphate or silicate glass as a carrier to release silver ions. The characteristics of this system are that the bactericidal active substance is metal ions, the minimum inhibitory concentration is low, the required release amount is low, and it can withstand a relatively high processing temperature. However, the matrix has a slow release rate and a high processing sintering temperature, which matches the usage conditions.

[0004] A typical organic system includes a complex-phase water-soluble polymer sustained-release system, in which the insoluble phase controls the structural strength and release rate, and the soluble phase loads functional substances to achieve sustained release. The functional substances used in this system are mainly organic functional substances, such as quaternary ammonium salts, guanidine salts, active enzymes, etc. Its characteristics are that a relatively large release amount is required and it cannot be processed at high temperatures.

[0005] However, a single antibacterial sustained-release system has a single function. And if a metal bactericide is added to an organic release system, problems such as the migration of the metal bactericide to the surface interface will occur, resulting in uneven release rates and rapid failure in the later stage. Summary of the Invention

[0006] In order to solve the above technical problems, the present invention provides a composite sustained-release material, a preparation method thereof, and an application thereof. The composite sustained-release material can achieve differential synchronous release of inorganic bactericidal elements and organic functional substances, thereby realizing the combination of sterilization and other functions, or realizing the synergistic cooperation of multiple antibacterial substances to improve the antibacterial effect.

[0007] In a first aspect, the present invention provides a composite sustained-release material, which includes a porous metal framework and an organic phase, and the organic phase is filled in the pores of the porous metal framework;

[0008] The porous metal framework includes a self-degrading metal and a bactericidal element;

[0009] The organic phase includes a water-soluble polymer and an organic functional substance.

[0010] In some embodiments of the present invention, the porosity of the porous metal framework is 25-50%.

[0011] In some embodiments of the present invention, the self-degrading metal is magnesium, magnesium-aluminum alloy, magnesium-strontium alloy or magnesium-aluminum-strontium alloy.

[0012] In some embodiments of the present invention, the bactericidal element is selected from one or more of silver, zinc, and copper.

[0013] In some embodiments of the present invention, the content of the bactericidal element in the porous metal framework is 8-15 wt%.

[0014] In some embodiments of the present invention, the water-soluble polymer is polyethylene oxide and / or polyvinyl alcohol.

[0015] In some embodiments of the present invention, the weight-average molecular weight of the water-soluble polymer is 500,000-3,000,000, preferably 800,000-1,200,000.

[0016] In some embodiments of the present invention, the organic functional substance is selected from one or more of laundry enzymes, surfactants, and organic antibacterial agents.

[0017] In some embodiments of the present invention, the organic antibacterial agent is selected from one or more of guanidine salts, quaternary ammonium salts, and D-amino acids.

[0018] In some embodiments of the present invention, the content of the organic antibacterial agent in the organic phase is 40-60 wt%.

[0019] In a second aspect, the present invention provides a method for preparing the composite sustained-release material as described in the first aspect, and the preparation method includes the following steps:

[0020] (1) Mix the raw material powder of the porous metal framework with hollow particles and / or foaming agents, heat and melt, and form a porous metal framework after cooling;

[0021] (2) Mix the water-soluble polymer and the organic functional substance and heat and melt, then pour them into the pores of the porous metal framework, and form the composite sustained-release material after cooling.

[0022] In some embodiments of the present invention, the foaming agent is an inorganic foaming agent and / or an organic foaming agent.

[0023] In some embodiments of the present invention, the inorganic foaming agent is selected from one or more of ammonium bicarbonate, sodium bicarbonate, and ammonium chloride.

[0024] In some embodiments of the present invention, the organic foaming agent is selected from one or more of polyvinyl alcohol, polystyrene, and polyurethane.

[0025] In some embodiments of the present invention, in step (2), after the pouring, it is kept warm for more than 5 min, and then cooled to below 40°C at a rate of ≤2°C / min.

[0026] In a third aspect, the present invention provides an application of the composite sustained-release material as described in the first aspect in antibacterial.

[0027] In a fourth aspect, the present invention provides a washing device, and the washing device includes the composite sustained-release material as described in the first aspect.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The composite sustained-release material provided by the present invention has a dual-phase composite structure of a metal phase and an organic phase, wherein the metal phase is loaded with a bactericidal element, and the organic phase is loaded with an organic functional substance, and the inorganic bactericidal element and the organic functional substance can be released at different rates and synchronously in water. This composite sustained-release material can be used in a washing device, so as to realize the combination of sterilization and other functions, or realize the synergistic cooperation of multiple antibacterial substances to improve the antibacterial effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The drawings here are incorporated into the specification and form a part of this specification, showing embodiments consistent with the present invention and used together with the specification to explain the principles of the present invention.

[0031] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without creative efforts.

[0032] Figure 1 It is a schematic structural diagram of a porous metal skeleton. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] In order to be able to more clearly understand the above objects, features and advantages of the present invention, the following will further describe the solutions of the present invention. It should be noted that, without conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other.

[0034] Many specific details are set forth in the following description in order to fully understand the present invention, but the present invention can also be implemented in other ways different from those described herein; obviously, the embodiments in the specification are only a part of the embodiments of the present invention, rather than all of the embodiments.

[0035] In a first aspect, an embodiment of the present invention provides a composite sustained-release material, and the composite sustained-release material includes a porous metal skeleton and an organic phase, and the organic phase is filled in the pores of the porous metal skeleton;

[0036] The porous metal skeleton includes a self-degrading metal and a bactericidal element;

[0037] The organic phase includes a water-soluble polymer and an organic functional substance.

[0038] The composite sustained-release material provided by the present invention has a dual-phase composite structure of a metal phase and an organic phase. The metal phase is loaded with a bactericidal element, and the self-degrading metal has a slow degradation characteristic, which can match the release rate of the bactericidal element, realize the sustained release of the bactericidal substance and ensure the overall mechanical properties of the material. The organic phase is loaded with an organic functional substance, and in water, the differential release (i.e., the organic functional substance is released relatively quickly while the bactericidal element is released relatively slowly) of the inorganic bactericidal element and the organic functional substance can be realized, so as to realize the combination of sterilization and other functions (when the organic functional substance is not an antibacterial agent), or realize the synergistic cooperation of multiple antibacterial substances (when the organic functional substance is an antibacterial agent) to improve the antibacterial effect.

[0039] In some embodiments of the present invention, the porosity of the porous metal framework is 25-50%; for example, it can be 25%, 26%, 28%, 30%, 32%, 33%, 35%, 36%, 38%, 40%, 42%, 43%, 45%, 46%, 48% or 50%, etc.

[0040] In some embodiments of the present invention, the self-degrading metal is magnesium, magnesium-aluminum alloy, magnesium-strontium alloy or magnesium-aluminum-strontium alloy.

[0041] Magnesium metal has excellent mechanical properties and self-degrading characteristics. The porous metal framework prepared therefrom has good mechanical properties and can realize the sustained release of the bactericidal element. Aluminum and strontium elements can accelerate the degradation rate of magnesium. Using their alloy with magnesium as the metal carrier can adjust the sustained release rate of the bactericidal element. In the present invention, the contents of aluminum and strontium are not particularly limited, and those skilled in the art can select according to the required sustained release rate of the bactericidal element.

[0042] In some embodiments of the present invention, the bactericidal element is selected from one or more of silver, zinc and copper.

[0043] In some embodiments of the present invention, the content of the bactericidal element in the porous metal framework is 8-15 wt%; for example, it can be 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt% or 15 wt%, etc.

[0044] In the present invention, if the content of the bactericidal element in the porous metal framework is too low, it is likely to result in too low a concentration of the released bactericidal element or even fail to reach the effective concentration, and the bactericidal effect is poor; if the content of the bactericidal element in the porous metal framework is too high, on the one hand, it will lead to poor mechanical properties of the porous metal framework, and on the other hand, it will accelerate the degradation of magnesium, resulting in a relatively fast release rate of the bactericidal element and the rapid failure of the composite sustained-release material.

[0045] In some embodiments of the present invention, the water-soluble polymer is polyethylene oxide (PEO) and / or polyvinyl alcohol (PVA).

[0046] In some embodiments of the present invention, the weight-average molecular weight of the water-soluble polymer is 500,000 - 3,000,000, for example, it can be 500,000, 600,000, 700,000, 800,000, 850,000, 900,000, 950,000, 1,000,000, 1,050,000, 1,100,000, 1,150,000, 1,200,000, 1,300,000, 1,500,000, 1,600,000, 1,800,000, 2,000,000, 2,200,000, 2,300,000, 2,500,000, 2,600,000 or 2,800,000, etc.; preferably 800,000 - 1,200,000.

[0047] In the present invention, if the molecular weight of the water-soluble polymer is too small, its dissolution rate is too fast, which will lead to too fast release rate of the organic functional substance; if the molecular weight of the water-soluble polymer is too large, on the one hand, its dissolution rate is too slow, which is likely to result in too slow release rate of the organic functional substance, and the concentration of the released organic functional substance is relatively low or even fails to reach the effective concentration. On the other hand, its melt viscosity is relatively large, making it difficult to enter the pores of the porous metal framework, which is not conducive to the preparation of the composite sustained-release material.

[0048] In some embodiments of the present invention, the organic functional substance is selected from one or more of laundry enzymes, surfactants, and organic antibacterial agents.

[0049] In some embodiments of the present invention, the organic antibacterial agent is selected from one or more of guanidine salts, quaternary ammonium salts, and D-amino acids.

[0050] Among them, D-amino acids have the property of inhibiting biofilms, thus realizing the antibacterial function. The present invention does not impose special restrictions on the types of the D-amino acids. Exemplarily, it can be one or more of D-leucine, D-phenylalanine, D-valine, and D-tyrosine.

[0051] In some embodiments of the present invention, the content of the organic antibacterial agent in the organic phase is 40 - 60 wt%; for example, it can be 40 wt%, 42 wt%, 43 wt%, 45 wt%, 46 wt%, 48 wt%, 50 wt%, 52 wt%, 53 wt%, 55 wt%, 56 wt%, 58 wt% or 60 wt%, etc.

[0052] It should be noted that in the present invention, the type, molecular weight of the water-soluble polymer, and the content of the organic functional substance in the organic phase will affect the release rate of the organic functional substance, and the effective concentrations of different organic functional substances are different. Therefore, those skilled in the art can select appropriate types of water-soluble polymers, molecular weights, and contents of organic functional substances according to actual needs.

[0053] As a preferred embodiment, the water-soluble polymer is polyethylene oxide and / or polyvinyl alcohol, and its weight-average molecular weight is 800,000-1,200,000; the organic functional substance is an organic antibacterial agent, and the organic antibacterial agent is selected from one or more of guanidine salts, quaternary ammonium salts, and D-type amino acids; the content of the organic antibacterial agent in the organic phase is 40-60 wt%. This solution can ensure that the above-mentioned organic antibacterial agent has an appropriate release rate and cooperates synergistically with the bactericidal elements released by the metal phase, thereby achieving a good antibacterial effect.

[0054] In a second aspect, the present invention provides a method for preparing a composite sustained-release material as described in the first aspect, and the preparation method includes the following steps:

[0055] (1) Mix the raw material powder of the porous metal skeleton with hollow particles or a foaming agent, heat and melt, and form a porous metal skeleton after cooling;

[0056] (2) Mix the water-soluble polymer and the organic functional substance and heat and melt, and then pour them into the pores of the porous metal skeleton, and form the composite sustained-release material after cooling.

[0057] In the present invention, the raw materials of the porous metal skeleton refer to self-degradable metals and bactericidal elements, which can be added in the form of simple substances respectively or in the form of intermediate alloys. After mixing the raw material powder of the porous metal skeleton with hollow particles and / or a foaming agent and heating and melting, the hollow particles are retained in the metal phase, or the foaming agent decomposes to generate bubbles, so that the metal phase forms a porous structure.

[0058] In some embodiments of the present invention, the foaming agent is an inorganic foaming agent and / or an organic foaming agent.

[0059] In some embodiments of the present invention, the inorganic foaming agent is selected from one or more of ammonium bicarbonate, sodium bicarbonate, and ammonium chloride.

[0060] In some embodiments of the present invention, the organic foaming agent is selected from one or more of polyvinyl alcohol, polystyrene, and polyurethane.

[0061] In the present invention, the dosages of the hollow particles and the foaming agent are not particularly limited. The lower the dosage, the lower the porosity of the porous metal skeleton, and the higher the dosage, the higher the porosity of the porous metal skeleton. Those skilled in the art can select appropriate dosages of the hollow particles and the foaming agent according to the required porosity of the porous metal skeleton.

[0062] In some embodiments of the present invention, in step (2), after the casting, it is heat-insulated for more than 5 minutes, and then cooled at a rate of ≤2 °C / min to below 40 °C. Among them, the heat-insulation time can be, for example, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 12 minutes, 13 minutes, 15 minutes, 16 minutes, 18 minutes or 20 minutes, etc. The cooling rate can be 2 °C / min, 1.8 °C / min, 1.5 °C / min, 1.2 °C / min, 1 °C / min, 0.8 °C / min or 0.5 °C / min, etc.

[0063] It should be noted that the above "heat-insulation" refers to maintaining the melting temperature of the mixture of the water-soluble polymer and the organic functional substance. In the present invention, by heat-insulating for more than 5 minutes after casting and controlling the cooling rate ≤2 °C / min, it helps the melt of the water-soluble polymer and the organic functional substance to fully enter the pores of the porous metal skeleton.

[0064] In the third aspect, the present invention provides an application of the composite sustained-release material as described in the first aspect in antibacterial.

[0065] In the fourth aspect, the present invention provides a washing device, and the washing device includes the composite sustained-release material as described in the first aspect.

[0066] In some embodiments of the present invention, the washing device is a washing machine, and the composite sustained-release material is placed at the water inlet of the washing machine.

[0067] The technical solution of the present invention will be further described below through specific embodiments.

[0068] Example 1

[0069] This example provides a composite sustained-release material, which includes a porous metal skeleton and an organic phase, and the organic phase is filled in the pores of the porous metal skeleton;

[0070] The structural schematic diagram of the porous metal skeleton is as Figure 1 shown, its porosity is 38%, and the porous metal skeleton is composed of self-degradable metal Mg (90 wt%), bactericidal element Ag (6 wt%), and Cu (4 wt%);

[0071] The organic phase is composed of water-soluble polymer PEO (weight average molecular weight 1 million, 50 wt%) and organic functional substance D-leucine (50 wt%).

[0072] The preparation method of the composite sustained-release material in this example is as follows:

[0073] (1) Mix magnesium powder, copper powder, magnesium-silver alloy powder, and foaming agent ammonium bicarbonate evenly, heat it to 1100 °C at a rate of 15 °C / min, hold for 10 min, and then cool it naturally to room temperature to obtain a porous metal skeleton with a measured porosity of 38%;

[0074] (2) Mix PEO with a weight-average molecular weight of 1 million and D-leucine evenly, heat and melt it at 85 °C, then pour the melt into the pores of the porous metal skeleton, hold at 85 °C for 5 min, then cool it to 40 °C at a rate of 1.5 °C / min, and then cool it naturally to room temperature to obtain the composite sustained-release material.

[0075] Example 2

[0076] This example provides a composite sustained-release material, which includes a porous metal skeleton and an organic phase, and the organic phase is filled in the pores of the porous metal skeleton;

[0077] The structural schematic diagram of the porous metal skeleton is as Figure 1 shown, with a porosity of 25%. The porous metal skeleton is composed of self-degradable metal Mg (92 wt%), bactericidal element Ag (5 wt%), and Zn (3 wt%);

[0078] The organic phase is composed of water-soluble polymer PVA (weight-average molecular weight of 800,000, 40 wt%) and organic functional substance D-phenylalanine (60 wt%).

[0079] The preparation method of the composite sustained-release material in this example is as follows:

[0080] (1) Mix magnesium powder, magnesium-silver alloy powder, magnesium-zinc alloy powder, and foaming agent sodium bicarbonate evenly, heat it to 1100 °C at a rate of 15 °C / min, hold for 10 min, and then cool it naturally to room temperature to obtain a porous metal skeleton with a measured porosity of 25%;

[0081] (2) Mix PVA with a weight-average molecular weight of 800,000 and D-phenylalanine evenly, heat and melt it at 80 °C, then pour the melt into the pores of the porous metal skeleton, hold at 80 °C for 5 min, then cool it to 40 °C at a rate of 2 °C / min, and then cool it naturally to room temperature to obtain the composite sustained-release material.

[0082] Example 3

[0083] This example provides a composite sustained-release material, which includes a porous metal skeleton and an organic phase, and the organic phase is filled in the pores of the porous metal skeleton;

[0084] The structural schematic diagram of the porous metal skeleton is as Figure 1As shown, its porosity is 50%, and the porous metal skeleton is composed of self-degradable metal Mg (83 wt%), bactericidal elements Ag (10 wt%), and Cu (5 wt%);

[0085] The organic phase is composed of water-soluble polymer PEO (weight-average molecular weight of 1.2 million, 60 wt%), organic functional substance polyhexamethylene biguanide hydrochloride (20 wt%), and D-tyrosine (20 wt%).

[0086] The preparation method of the composite sustained-release material in this example is as follows:

[0087] (1) Mix magnesium powder, copper powder, magnesium-aluminum alloy powder, magnesium-silver alloy powder, and foaming agent ammonium chloride evenly, heat it to 1100 °C at a rate of 15 °C / min, keep it warm for 10 min, and then cool it to room temperature naturally to obtain a porous metal skeleton, and its porosity is measured to be 50%;

[0088] (2) Mix PEO with a weight-average molecular weight of 1.2 million, polyhexamethylene biguanide hydrochloride, and D-tyrosine evenly, heat and melt it at 90 °C, then pour the melt into the pores of the porous metal skeleton, keep it warm at 90 °C for 8 min, and then cool it to room temperature at a rate of 1 °C / min to obtain the composite sustained-release material.

[0089] Example 4

[0090] This example provides a composite sustained-release material, which includes a porous metal skeleton and an organic phase, and the organic phase is filled in the pores of the porous metal skeleton;

[0091] The structural schematic diagram of the porous metal skeleton is as Figure 1 As shown, its porosity is 42%, and the porous metal skeleton is composed of self-degradable metal Mg (88 wt%), bactericidal element Ag (4 wt%), and Cu (8 wt%);

[0092] The organic phase is composed of water-soluble polymer PEO (weight-average molecular weight of 1 million, 50 wt%) and organic functional substance benzalkonium chloride (50 wt%).

[0093] The preparation method of the composite sustained-release material in this example is as follows:

[0094] (1) Mix magnesium powder, copper powder, magnesium-silver alloy powder, and foaming agent polystyrene evenly, heat it to 1100 °C at a rate of 15 °C / min, keep it warm for 10 min, and then cool it to room temperature naturally to obtain a porous metal skeleton, and its porosity is measured to be 42%;

[0095] (2) Mix PEO with a weight-average molecular weight of 1 million and benzalkonium chloride evenly, heat and melt them at 85 °C, then pour the melt into the pores of the porous metal framework, keep it at 85 °C for 5 min, then cool it at a rate of 1.5 °C / min to 40 °C, and then naturally cool it to room temperature to obtain the composite sustained-release material.

[0096] Comparative Example 1

[0097] This comparative example provides a composite sustained-release material, the difference from Example 1 is only that the porous metal framework is composed of self-degradable metal Mg (94 wt%), bactericidal element Ag (1 wt%), and Cu (5 wt%).

[0098] Comparative Example 2

[0099] This comparative example provides a composite sustained-release material, the difference from Example 1 is only that the porous metal framework is all self-degradable metal Mg and does not contain bactericidal elements.

[0100] Comparative Example 3

[0101] This comparative example provides a composite sustained-release material, the difference from Example 1 is only that the organic phase is all water-soluble polymer PEO.

[0102] Performance Test

[0103] Respectively take 20 g of the composite sustained-release materials prepared in the above examples and comparative examples, place them in 1 L of deionized water at 25 °C for 5 seconds and then take them out to obtain the sustained-release liquid. Using this sustained-release liquid, select Staphylococcus aureus and Escherichia coli, and conduct the bacteriostatic rate and continuous interfacial antibacterial effect tests according to the regulations of the antibacterial and bacteriostatic effect evaluation method WS / T650-2019. The test results are shown in Table 1 below.

[0104] Table 1

[0105]

[0106] Among them, it is judged that there is a continuous antibacterial effect during this period when the bactericidal rate ≥ 90%.

[0107] It can be seen from the test results in Table 1 that the composite sustained-release material provided by the embodiment of the present invention has a bacteriostatic rate of more than 99% and a continuous interfacial antibacterial effect for 14 days. And the release time of the composite sustained-release material in the above performance test is only 5 seconds, which matches the water inlet flow rate of the washing machine. Therefore, the composite sustained-release material provided by the embodiment of the present invention can be used in the washing machine and placed at the water inlet to play a bactericidal role.

[0108] Among them, compared with Example 1, in Comparative Example 1, due to the too low content of the bactericidal element in the porous metal skeleton, the antibacterial rate and the continuous antibacterial time of the composite sustained-release material both decreased significantly. In Comparative Examples 2 and 3, due to the absence of the bactericidal element and the organic antibacterial agent respectively, the antibacterial rate of the composite sustained-release material decreased significantly, and there was no continuous antibacterial effect.

[0109] It should be noted that in this article, relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprise", "include" or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or further includes elements inherent to such process, method, article or device. Without further limitation, an element defined by the phrase "comprising an..." does not exclude the presence of additional identical elements in the process, method, article or device comprising the element.

[0110] The above are only specific embodiments of the present invention, enabling those skilled in the art to understand or implement the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments described herein, but rather to the broadest scope consistent with the principles and novel features invented herein.

Claims

1. A composite sustained-release material, characterized in that, The composite sustained-release material includes a porous metal framework and an organic phase, and the organic phase is filled in the pores of the porous metal framework; The porous metal framework includes a self-degrading metal and a bactericidal element; The organic phase includes a water-soluble polymer and an organic functional substance.

2. The composite sustained-release material according to claim 1, wherein The porosity of the porous metal framework is 25-50%; Preferably, the self-degrading metal is magnesium, magnesium-aluminum alloy, magnesium-strontium alloy or magnesium-aluminum-strontium alloy.

3. The composite sustained-release material according to claim 1 or 2, characterized in that The bactericidal element is selected from one or more of silver, zinc and copper; Preferably, the content of the bactericidal element in the porous metal framework is 8-15 wt%.

4. The composite sustained-release material according to any one of claims 1-3, characterized in that, The water-soluble polymer is polyethylene oxide and / or polyvinyl alcohol; Preferably, the weight-average molecular weight of the water-soluble polymer is 500,000-3,000,000, preferably 800,000-1,200,000.

5. The composite sustained-release material according to any one of claims 1-4, characterized in that, The organic functional substance is selected from one or more of washing enzymes, surfactants and organic antibacterial agents; Preferably, the organic antibacterial agent is selected from one or more of guanidine salts, quaternary ammonium salts and D-type amino acids; Preferably, the content of the organic antibacterial agent in the organic phase is 40-60 wt%.

6. A method for preparing a composite sustained-release material according to any one of claims 1-5, characterized in that, The preparation method includes the following steps: (1) Mix the raw material powder of the porous metal framework with hollow particles and / or a foaming agent, heat and melt, and form a porous metal framework after cooling; (2) Mix the water-soluble polymer and the organic functional substance and heat and melt, then pour them into the pores of the porous metal framework, and form the composite sustained-release material after cooling.

7. The preparation method according to claim 6, characterized in that, The foaming agent is an inorganic foaming agent and / or an organic foaming agent; Preferably, the inorganic foaming agent is selected from one or more of ammonium bicarbonate, sodium bicarbonate and ammonium chloride; Preferably, the organic foaming agent is selected from one or more of polyvinyl alcohol, polystyrene and polyurethane.

8. The preparation method according to claim 6 or 7, characterized in that, In step (2), after the pouring, keep it warm for more than 5 minutes, and then cool it at a rate of ≤2 °C / min to below 40 °C.

9. Application of the composite sustained-release material according to any one of claims 1-5 in antibacterial.

10. A washing device, characterized in that, The washing device includes the composite sustained-release material according to any one of claims 1-5.

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