CN116023784A - Antibacterial silicone rubber, silicone rubber product and method thereof, wearing product and antibacterial material - Google Patents
Antibacterial silicone rubber, silicone rubber product and method thereof, wearing product and antibacterial material Download PDFInfo
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- CN116023784A CN116023784A CN202111240476.9A CN202111240476A CN116023784A CN 116023784 A CN116023784 A CN 116023784A CN 202111240476 A CN202111240476 A CN 202111240476A CN 116023784 A CN116023784 A CN 116023784A
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- silicone rubber
- antibacterial
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- oil layer
- antimicrobial
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention provides antibacterial silicone rubber and a method thereof, a silicone rubber product and a method thereof, a wearing product and an antibacterial material. The method for preparing the antibacterial silicone rubber comprises a mixing stage and a vulcanization stage, wherein at least raw rubber and auxiliary forming components are mixed in the mixing stage to obtain mixed rubber; in the vulcanization stage, the mixed rubber is mixed with a vulcanizing agent and vulcanized to obtain vulcanized silicone rubber, and an antibacterial agent is added in the mixing stage and/or the vulcanization stage, wherein the antibacterial agent comprises a porous carrier and an antibacterial substance, and the antibacterial substance is loaded on the porous carrier. Therefore, the silicone rubber with the antibacterial function can be prepared simply and conveniently, and the antibacterial performance of rubber products is improved.
Description
Technical Field
The invention relates to the field of electronic equipment, in particular to antibacterial silicone rubber and a method thereof, a silicone rubber product and a method thereof, a wearing product and an antibacterial material.
Background
With the high-speed development of intelligent wearable equipment, headphones are important, and widely paid attention to people is obtained, so that the earphone has huge market potential. The antibacterial effect of materials has been of interest in the industry, particularly in the direct contact of earcaps, watchbands, etc. with human skin, which is an important factor affecting the consumer's use experience.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent.
In one aspect of the present invention, the present invention provides a method of preparing an antimicrobial silicone rubber comprising: a mixing stage and a vulcanization stage, wherein at least the raw rubber and the auxiliary forming components are mixed in the mixing stage to obtain a mixed rubber; and in the vulcanization stage, mixing the mixed rubber with a vulcanizing agent, and then vulcanizing to obtain vulcanized silicone rubber, wherein an antibacterial agent is added in the mixing stage and/or the vulcanization stage, the antibacterial agent comprises a porous carrier and an antibacterial substance, and the antibacterial substance is loaded on the porous carrier. Therefore, the silicon rubber with the antibacterial function can be prepared simply and conveniently, and the silicon rubber has lasting antibacterial performance.
In yet another aspect of the present invention, the present invention provides an antimicrobial silicone rubber, which is prepared by the aforementioned method. Thus, the antibacterial silicone rubber has durable antibacterial performance.
In yet another aspect of the present invention, the present invention provides a silicone rubber article comprising: the silicone rubber product comprises a silicone rubber product body, wherein the silicone rubber product body comprises an antibacterial agent, the antibacterial agent comprises a porous carrier and an antibacterial substance, and the antibacterial substance is loaded on the porous carrier; and the hand feeling oil layer is provided with penetrating air holes and/or non-penetrating air holes, and is formed on the surface of the silicone rubber product body. Therefore, the use experience and lasting antibacterial performance of the silicone rubber product can be improved through the arrangement of the hand feeling oil layer.
In yet another aspect of the present invention, the present invention provides a method of making the silicone rubber article described previously, comprising: providing a silicone rubber product body; and after the hand feeling oil is applied to the silicone rubber product body, treating the formed hand feeling oil layer so as to form penetrating air holes and/or non-penetrating air holes in the hand feeling oil layer. Therefore, the silicone rubber product with better hand feeling and lasting antibacterial property can be simply and conveniently prepared.
In still another aspect of the present invention, the present invention provides a wearing article prepared from the silicone rubber product described above. Thus, a wearing article having the aforementioned silicone rubber article can be obtained, and thus the wearing article has all the features and advantages of the aforementioned silicone rubber article, and will not be described herein.
In yet another aspect of the present invention, an antimicrobial material is provided that includes an oil-handling layer having through pores and/or non-through pores and a body formed on a surface of the body, the body containing an antimicrobial agent. Therefore, the antibacterial material can better release antibacterial substances and has a long-acting antibacterial function.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 shows a schematic flow chart of a method of preparing an antimicrobial silicone rubber in accordance with one embodiment of the invention;
FIG. 2 shows a schematic structural view of an antimicrobial agent according to one embodiment of the present invention;
FIG. 3 shows a schematic flow chart of a method of preparing an antimicrobial silicone rubber in accordance with yet another embodiment of the invention;
FIG. 4 shows a schematic flow chart of preparing a silicone rubber article according to one embodiment of the invention;
FIG. 5 shows a schematic flow chart of a process for preparing a silicone rubber article according to yet another embodiment of the present invention;
FIG. 6 shows a scanning electron microscope image of a silicone rubber article that has not been subjected to ultraviolet radiation in accordance with one embodiment of the present invention;
FIG. 7 shows a scanning electron microscope image of a silicone rubber article according to one embodiment of the present invention.
Reference numerals illustrate:
100: a silicone rubber article body; 110: an antibacterial substance; 120: a porous support; 200: a hand feel oil layer; 210: air bubbles; 220: a crack; 310: a first heat source; 320: and a second heat source.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
In one aspect of the invention, the invention provides a method for preparing the antibacterial silicone rubber, which comprises the steps of adding an antibacterial agent in the preparation process of the silicone rubber, wherein the antibacterial agent comprises a porous carrier and an antibacterial substance, and the antibacterial substance is loaded on the porous carrier, so that the antibacterial silicone rubber with lasting antibacterial performance is obtained.
For easy understanding, the principle that the method for preparing the antibacterial silicone rubber can achieve the above-mentioned beneficial effects is briefly described below:
the antibacterial process in the related art generally adopts a surface antibacterial coating and other forms, such as a shell component manufactured by using thermoplastic polyurethane elastomer and inorganic antibacterial particles through doping injection molding, or a rubber product is formed by mixing and vulcanizing fluororubber and inorganic antibacterial particles, so that the product has an antibacterial function. At present, the antibacterial effect on the silica gel earcaps in the related art is mainly realized by performing antibacterial treatment on silicone rubber or hand feeling oil. The inventors found that: the processing method in the related art has the following disadvantages: firstly, the antibacterial substance is doped into the hand-feeling oil layer to realize the antibacterial effect, the hand-feeling oil is worn along with the use of consumers, so that the antibacterial effect is reduced, and secondly, if the antibacterial agent is simultaneously added into the silicone rubber and the hand-feeling oil layer to realize the better antibacterial effect, the preparation cost is relatively high, and the large-scale batch production is not facilitated. In addition, the antibacterial substances can only be added uniformly, and when the antibacterial substances are unevenly distributed, the antibacterial substances are easy to agglomerate, so that poor appearance is caused, and the antibacterial effect is greatly influenced. In addition, most of antibacterial modification of the silicone rubber body in the related art is an empirical process operation, no quantifiable standard is used for guiding the antibacterial modification of the silicone rubber body, and after the antibacterial modification of the silicone rubber body, other substances cannot be coated on the surface of the silicone rubber body, otherwise, release of the antibacterial substances is affected, so that the actual antibacterial effect is greatly reduced.
In the application, the inventor can realize the uniform distribution of the antibacterial agent in the silicone rubber by adding the antibacterial agent in the mixing stage for preparing the silicone rubber or in the vulcanizing stage for preparing the silicone rubber or in both the mixing stage and the vulcanizing stage for preparing the silicone rubber, and the method for preparing the antibacterial silicone rubber with durable antibacterial performance can be simply and conveniently obtained.
In particular, in the present application, the antibacterial agent may be added only in the kneading stage for producing the silicone rubber, only in the vulcanization stage for producing the silicone rubber, or both of the kneading stage and the vulcanization stage for producing the silicone rubber. The following explanation will be made by adding the antimicrobial agent in both the kneading stage and the vulcanization stage of the preparation of the silicone rubber, and those skilled in the art can select according to the actual situation, determine which stage of the kneading stage and the vulcanization stage of the preparation of the silicone rubber is to be added with the antimicrobial agent, or perform the addition of the antimicrobial agent in both stages.
Specifically, referring to fig. 1, the method of preparing the antibacterial silicone rubber includes:
S100: in the mixing stage, at least the raw rubber and the auxiliary forming components are mixed
According to some embodiments of the invention, the secondary molding composition includes a filler, an accelerator, a catalyst, an antioxidant, a coupling agent, and a mold release agent.
According to some embodiments of the invention, the raw materials are mixed at this step to obtain a mix, and when the antimicrobial agent is not added during the mixing stage, the raw rubber, filler, accelerator, catalyst, antioxidant, coupling agent and release agent are mixed to obtain a mix, and when the antimicrobial agent is added during the mixing stage, it is necessary to add an antimicrobial agent in addition to the above-mentioned raw materials to obtain antimicrobial properties to the silicone rubber during the mixing stage.
When the antibacterial agent is added in the mixing step, the antibacterial agent is dispersed for a plurality of times and is fully stirred until no obvious foaming, agglomerated white spots and uneven turbidity are seen.
According to some embodiments of the present invention, the method of preparing raw rubber is not particularly limited, for example, the method of preparing raw rubber may include the steps of: the macromolecule raw rubber is prepared by heating or pressurizing the siloxane micromolecules to cause the siloxane micromolecules to generate polymerization reaction. The macromolecule raw rubber is put into a dehydration kettle for intermittent dehydration, then is mixed with a platinum catalyst in a batching kettle, is continuously polymerized by a static mixer, and finally is continuously subjected to low molecular weight substance removal by a flash evaporator to prepare the raw rubber, and the special requirement is that the antibacterial agent is not directly added in the raw rubber preparation process because the mechanical strength of the raw rubber is low at this time, the mixing property of the antibacterial agent and the raw rubber is poor, the material property of the raw rubber is deteriorated, the antibacterial agent is not suitable for being added in the mixing process, and the antibacterial agent can be added in the subsequent mixing stage and the vulcanization stage. The inventor finds that after the antibacterial agent is added in the mixing stage and the vulcanizing stage, the physical and chemical properties of the finally prepared antibacterial silicone rubber material are not greatly different from those of the silicone rubber without the antibacterial agent, which indicates that the antibacterial agent added in the mixing stage and the vulcanizing stage does not destroy the original macromolecular chains in microcosmic scale, and the antibacterial agent is uniformly dispersed around the macromolecular chains in a porous carrier coating mode and is mutually bonded through weak molecular bonds, so that the antibacterial silicone rubber material has certain deformability.
According to some embodiments of the invention, the proportions of the substances of the mixing stage are not particularly limited, for example, the mass ratio of raw rubber, filler, accelerator, catalyst, antioxidant, coupling agent and release agent may be 100: (6-20): (0.05-0.12): (1-3): (2-4): (1.5-6): (0.2-0.6). When the proportion of the raw materials for preparing the rubber compound is within the above range, the antibacterial agent is better in miscibility with other substances when the antibacterial agent is added in this step, and the rubber compound in which the antibacterial agent is uniformly dispersed can be prepared.
According to some embodiments of the present invention, the type of filler is not particularly limited, and for example, the filler may be at least one of montmorillonite (i.e., silicate), zinc oxide whisker, bisphenol a type polycarbonate micropowder, and white carbon black, and when the filler is of the above type, the interaction between Si-O-Si in the silicone rubber can be effectively enhanced, thereby improving the mechanical properties of the raw rubber.
According to some embodiments of the present invention, the type of accelerator is not particularly limited, and for example, the accelerator may be at least one of a thiazole accelerator or a thiuram accelerator, and a small amount of accelerator is added in the mixing stage, so that the reaction between the silicone rubber and the vulcanizing agent (cross-linking agent) in the subsequent vulcanization stage can be greatly promoted, the vulcanization reaction speed is accelerated, the vulcanization time is shortened, the vulcanization reaction temperature is reduced, the amount of vulcanizing agent is reduced, and the productivity of the antibacterial silicone rubber is improved.
According to some embodiments of the present invention, the kind of the antioxidant is not particularly limited, and for example, the antioxidant may be cerium oxide, and the antioxidant property of the rubber may be improved by adding the antioxidant.
According to some embodiments of the present invention, the kind of the coupling agent is not particularly limited, and for example, the coupling agent may be mixed with trimethylethoxysilane, methanol and water, and the dispersibility and adhesiveness of the compound may be improved and the uniform distribution of the antibacterial substance may be improved by adding the coupling agent.
According to some embodiments of the present invention, the kind of the release agent is not particularly limited, and for example, the release agent may be an emulsion of silicone oil and water in "oil-in-water" type of silicone oil emulsified and ground. The addition of the release agent can prevent the adhesion force between the raw rubber and the mold from being too strong, so that the mold cannot be removed.
According to some embodiments of the present invention, when the antibacterial agent is added in the mixing stage or the vulcanization stage, the addition amount of the antibacterial agent is not particularly limited, and for example, the addition amount of the antibacterial agent is 0.4 to 1 part by weight based on 100 parts by weight of raw rubber. When the addition amount of the antibacterial agent is less than 0.4 parts by weight based on 100 parts by weight of the raw rubber, the antibacterial agent in the silicone rubber is too small, and the antibacterial effect of the silicone rubber is poor; when the addition amount of the antibacterial agent is more than 1 part by weight, the antibacterial effect of the silicone rubber is far more than the actual use requirement, and the manufacturing cost of the silicone rubber is obviously improved due to the fact that the cost of the antibacterial agent is high, so that the silicone rubber is not beneficial to popularization and application.
According to some embodiments of the present invention, referring to fig. 2, the antibacterial agent includes a porous carrier 120 and an antibacterial substance 110, and the antibacterial substance 110 is supported on the porous carrier 120. Therefore, the antibacterial substances can be loaded in the porous carrier by utilizing the porous structure of the porous carrier, so that the antibacterial agents are uniformly distributed in the silicone rubber, the occurrence of the agglomeration phenomenon of the antibacterial substances is reduced, and the problems of poor appearance, lower antibacterial effect and the like caused by the agglomeration of the antibacterial substances are effectively solved. In addition, the release rate of the antibacterial substance to the surface of the product should be controlled so as to make the antibacterial property of the product more durable, so that the porous carrier is selected, the release rate of the antibacterial substance is controlled by forming pores to be coated with the antibacterial substance by a permeation method, the external environment interference resistance of the antibacterial substance is improved, and the antibacterial activity of the surface of the product is prolonged.
According to some embodiments of the present invention, the number of spaces on the porous carrier is not particularly limited, and for example, the number of cells on the porous carrier may be 50 to 100 based on a porous carrier of 100 μm×100 μm. Based on a porous carrier of 100 micrometers multiplied by 100 micrometers, when the number of cells on the porous carrier is less than 50, the number of cells is too small, the concentration of active ingredients of antibacterial substances is too low, and the antibacterial effect of the silicone rubber is affected; when the number of cells on the porous support is more than 100, the number of cells per unit area is excessive, and the volume of individual cells is compressed, resulting in difficulty in migration of the antibacterial substance, thereby affecting the antibacterial effect of the silicone rubber.
According to some embodiments of the invention, it is known from the above that the concentration of the antimicrobial substance in the antimicrobial agent is related to the number of cells of the porous carrier. The concentration of the antibacterial substance in the antibacterial agent is not particularly limited, and for example, when the number of cells on the porous carrier is 50 to 100 based on a porous carrier of 100 micrometers×100 micrometers, the concentration of the antibacterial substance in the antibacterial agent may range from 0.2 to 1.5wt%. When the concentration of the antibacterial substance in the antibacterial agent is too low, the antibacterial effect of the antibacterial silicone rubber is not durable; when the concentration of the antibacterial substance in the antibacterial agent is too high, the migration of the antibacterial substance is difficult, and the manufacturing cost is increased.
According to some embodiments of the present invention, the kind of the porous carrier is not particularly limited as long as the number of cells per unit area thereof can satisfy the above-mentioned requirements and the inside thereof can be coated with an antibacterial substance, for example, the porous carrier includes at least one of glass beads, hydroxyapatite, silica, silicate, phosphate, and zeolite.
According to some embodiments of the present invention, the kind of the antibacterial substance is not particularly limited, and for example, the antibacterial substance may include at least one of zinc ion, silver ion, iron ion, and copper ion. Zinc ions, silver ions, copper ions and iron ions can block biochemical reaction by contacting with cell walls of bacteria to destroy biological enzyme activity of the bacteria, so that the effect of killing the bacteria is achieved. When the copper ion itself has a color, it can be used for producing a dark-colored silicone rubber product, and when the copper ion is used as an antibacterial substance for producing a light-colored silicone rubber, it may negatively affect the appearance, and at this time, the copper ion may be replaced with another antibacterial substance having no color, which may be selected by those skilled in the art according to the actual situation.
According to some embodiments of the present invention, due to the poor stability of silver ions, a reduction reaction occurs under the conditions of light irradiation and moisture contact to generate a black silver simple substance, and oxidation occurs again to generate a yellow and dark oxide, and when the silver simple substance is applied to silicone rubber as an antibacterial substance, the instability of the silver simple substance affects the appearance of the silicone rubber, and excessive migration and consumption of silver ions also causes great reduction of the antibacterial capability of the silicone rubber. In the present application, the inventors found that when silver ions are used as the antibacterial substance in the antibacterial agent, an anti-reducing agent and an antioxidant may be additionally added while the antibacterial agent is added, thereby delaying the progress of the process and improving the appearance and antibacterial performance of the antibacterial silicone rubber.
According to some embodiments of the present invention, when the antibacterial substance in the antibacterial agent is silver ions, an anti-reducing agent may be added in the mixing stage to prevent the formation of elemental silver, an antioxidant may be added to prevent oxidation of elemental silver, and at the same time, the antioxidant may also have a retarding effect on oxidation of other components in the silicone rubber, specifically, the amount of the anti-reducing agent may be 0.2 to 0.3 parts by weight and the amount of the antioxidant may be 0.5 to 0.7 parts by weight based on 1 part by weight of the antibacterial agent.
According to some embodiments of the present invention, the kind of the anti-reducing agent is not particularly limited, and for example, the anti-reducing agent may be a thiol group-containing compound, and in particular, the anti-reducing agent may be at least one of n-dodecyl mercaptan, t-dodecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan.
According to some embodiments of the present invention, the kind of the antioxidant is not particularly limited, and for example, the antioxidant may be at least one of sodium citrate, hydrazine hydrate, dithiol dihydroxyacetic acid, methylene dithioacetic acid.
S200: in the vulcanization stage, the mixed rubber and the vulcanizing agent are mixed and vulcanized
According to some embodiments of the invention, by vulcanizing the compound to obtain a vulcanized silicone rubber, when the antimicrobial agent is not added during the compounding stage, the antimicrobial agent may be added during the vulcanization at this stage; when the antibacterial agent is added in the kneading stage, the antibacterial agent may be added in the vulcanization treatment in this step, and the total amount of the antibacterial agent may be sufficient, or the antibacterial agent may not be added in the vulcanization treatment in this step, and the antibacterial agent may be selected by those skilled in the art according to the actual situation.
According to some embodiments of the present invention, the amount of the vulcanizing agent added in the vulcanization stage is not particularly limited, and for example, the vulcanizing agent may be added in an amount of 0.1 to 0.2% based on 1kg of the rubber compound. Based on 1kg of the rubber compound, when the addition amount of the vulcanizing agent is less than 0.1%, the antibacterial silicone rubber is difficult to mold; when the addition amount of the vulcanizing agent is more than 0.2%, the antibacterial silicone rubber is easy to cause brittle fracture, and is unfavorable for use.
According to some embodiments of the present invention, the kind of the vulcanizing agent is not particularly limited, and for example, the vulcanizing agent may be at least one of elemental sulfur, a peroxide, sulfur monochloride, a sulfur-containing accelerator, an organic peroxide, a quinone oxime compound, a polysulfide polymer, ethyl carbamate, an amine compound, a resin-based compound, a metal oxide, and an isocyanate, and specifically, the vulcanizing agent may be sulfur, an accelerator TMTD, benzoyl peroxide, or the like.
According to some embodiments of the present invention, the vulcanizing agent is added in both the kneading stage and the vulcanizing agent stage, and the addition amount of the vulcanizing agent in the vulcanizing stage is not particularly limited, and for example, the addition amount of the antibacterial agent may be 0.05 to 0.15 parts by weight based on 1 part by weight of the vulcanizing agent. When the addition amount of the antibacterial agent is less than 0.05 parts by weight based on 1 part by weight of the vulcanizing agent, the antibacterial ability of the finally obtained antibacterial silicone rubber is poor; when the amount of the antibacterial agent added is more than 0.15 parts by weight, the content of the antibacterial agent is too large, which may affect the vulcanizing effect of the vulcanizing agent, and even may cause a catalytic poisoning. And the addition amount of the antibacterial agent in the mixing stage is the residual content.
According to some embodiments of the present invention, the antibacterial agent added in the vulcanization stage may be the same as the antibacterial agent added in the kneading stage described above, for example, referring to fig. 2, the antibacterial agent includes a porous carrier 120 and an antibacterial substance 110, and the antibacterial substance 110 is supported on the porous carrier 120. Specifically, the kind of the antibacterial substance and the kind and structure of the porous carrier may be the same as those described above, and will not be described again here. It should be noted that, when silver ions are selected as the antibacterial substance in the antibacterial agent, an anti-reducing agent and an antioxidant are added in the vulcanization stage, and the types and amounts of the anti-reducing agent and the antioxidant may be the same as those described above, and are not described here.
According to some embodiments of the present invention, in order to improve the use stability of the antibacterial silicone rubber, an oxide layer may be formed on the surface thereof, so that the preparation of a silicone rubber product may be performed directly using the antibacterial silicone rubber without applying a hand oil.
Specifically, referring to fig. 3, the step of forming an oxide layer includes:
s300: hot press molding and ultraviolet treatment are carried out on the vulcanized silicone rubber
According to some embodiments of the invention, the hot pressing treatment is first continued on the vulcanized silicone rubber at this step, in particular, the hot pressing treatment includes: the vulcanized silicone rubber is cut into a specific shape and then put into a mold, and hot press molding is carried out according to preset technological parameters, or the vulcanized silicone rubber can be directly injected into a mold cavity through an injection molding machine, and then hot press molding treatment is carried out.
According to some embodiments of the present invention, after the vulcanized silicone rubber is subjected to the hot pressing treatment, the vulcanized silicone rubber may be subjected to ultraviolet irradiation treatment, for example, irradiation is performed by an ultraviolet lamp, and the high energy of ultraviolet rays is utilized to destroy the small molecular chains on the surface of the vulcanized antibacterial silicone rubber, so that a slight oxidation layer is formed on the surface layer of the antibacterial silicone rubber.
According to some embodiments of the present invention, the irradiation band of the ultraviolet treatment is not particularly limited, and for example, the irradiation band of the ultraviolet treatment may be 263 to 270nm. When the irradiation wave band of ultraviolet treatment is less than 263nm, the energy of ultraviolet light is too high, so that the silicon rubber surface layer material can be burnt; when the irradiation wave band of ultraviolet treatment is larger than 270nm, the energy of ultraviolet light is lower, the penetrability is poor, and the formed oxide layer has poor hand feeling.
According to some embodiments of the present invention, the irradiation time of the ultraviolet treatment is not particularly limited, and for example, the irradiation time of the ultraviolet treatment may be 0.5 to 2 minutes. When the irradiation time of ultraviolet treatment is less than 0.5min, the irradiation time is too short to play a role in cleaning the surface of the silicone rubber, and the effect of optimizing the hand feeling cannot be obtained; when the irradiation time of the ultraviolet treatment is longer than 2min, the irradiation time of the ultraviolet treatment is too long, the ultraviolet energy is accumulated, and the surface of the silicone rubber is seriously aged.
According to some embodiments of the present invention, the thickness of the oxide layer formed on the surface of the silicone rubber by ultraviolet irradiation is not particularly limited, for example, the thickness of the oxide layer may range from 30 to 100nm, and when the thickness of the oxide layer is less than 30nm, the oxide layer is too thin, and the feel of the silicone rubber is poor; when the thickness of the oxide layer is more than 100nm, the oxide layer is too thick, so that the difficulty in migrating antibacterial substances in the antibacterial agent is increased, and the antibacterial activity of the antibacterial silicone rubber is reduced.
In yet another aspect of the invention, the invention provides an antimicrobial silicone rubber made by the method described above. Thus, the antibacterial silicone rubber prepared by the foregoing method can be obtained, and thus has all the features and advantages of the foregoing method, which are not described in detail herein. In general, the antibacterial silicone rubber has a durable antibacterial property and an excellent touch feeling, and its outer surface is not yellowing, is not foaming, and has an excellent antibacterial durability under severe environments.
In yet another aspect of the present invention, the present invention provides a silicone rubber article, referring to (c) in fig. 2, 4 and (c) in fig. 5, comprising: a silicone rubber article body 100 including an antibacterial agent including a porous carrier 120 and an antibacterial substance 110, the antibacterial substance 110 being supported on the porous carrier 120; and a hand feel oil layer 200, wherein the hand feel oil layer 200 has through air holes and/or non-through air holes, and the hand feel oil layer 200 is formed on the surface of the silicone rubber product body 100 (the antibacterial silicone rubber is not subjected to ultraviolet irradiation after being subjected to hot press molding in the preparation process, i.e. an oxidation layer is not formed on the surface of the antibacterial silicone rubber). The side of the hand feeling oil layer far away from the silicone rubber product body is the side contacted with a user, and the hand feeling of the silicone rubber product is improved and the silicone rubber product body can be protected through the arrangement of the hand feeling oil layer. Because the antibacterial agent is arranged in the body of the silicone rubber product in the silicone rubber product, the antibacterial agent comprises a porous carrier and antibacterial substances, and the antibacterial substances are loaded on the porous carrier, so that the antibacterial substances can be loaded in the porous carrier by utilizing the porous structure of the porous carrier, the antibacterial agents are uniformly distributed in the silicone rubber, the occurrence of the agglomeration phenomenon of the antibacterial substances is reduced, and the problems of poor appearance, lower antibacterial effect and the like caused by the agglomeration of the antibacterial substances are effectively alleviated. In addition, the release rate of the antibacterial substance to the surface of the product should be controlled so as to make the antibacterial property of the product more durable, so that the porous carrier is selected, the release rate of the antibacterial substance is controlled by forming pores to be coated with the antibacterial substance through a penetration method, the external environment interference resistance of the antibacterial substance is improved, and the antibacterial activity of the surface of the product is prolonged. Therefore, the silicone rubber product body has good antibacterial performance, and the hand feeling oil layer is provided with through air holes and/or non-through air holes, so that when the skin of a human body contacts, antibacterial substances in the silicone rubber product body can migrate along with the through air holes (as shown by paths shown by broken lines in (c) in fig. 4 and (c) in fig. 5), thereby exerting antibacterial effects. It will be appreciated that the silicone rubber article body 100 may also be made from the antimicrobial silicone rubber described above.
According to some embodiments of the present invention, the structure of the air holes is not particularly limited, and for example, referring to (c) of fig. 4, the air holes in the feel oil layer 200 may be formed by a plurality of air bubbles 210, wherein the plurality of air bubbles extend along a direction perpendicular to the body of the silicone rubber product, are arranged to form an air hole penetrating the feel oil layer, and the feel oil layer may have a plurality of air holes formed by the air bubbles thereon.
According to some embodiments of the present invention, for example, referring to (c) of fig. 5, the feel oil layer 200 may have a plurality of micro-cracks 220 penetrating the feel oil layer, the micro-cracks extending in a direction perpendicular to the body of the silicone rubber article, so that penetrating pores are formed in the feel oil layer.
It is understood that the hand feel oil layer may have through air holes and/or non-through air holes, and when the hand feel oil layer has through air holes, the antibacterial agent in the silicone rubber product body may release antibacterial substances through the through air holes; when the hand feeling oil layer is provided with non-penetrating pores, the antibacterial agent in the silicone rubber product body can release antibacterial substances through the non-penetrating pores. The release of the antimicrobial substance is relatively slow when the layer of feel has non-penetrating pores compared to when the layer of feel has penetrating pores. Thus, the air holes which penetrate and/or do not penetrate can be selected according to the antibacterial requirement of the antibacterial silicone rubber.
According to some embodiments of the present invention, the diameter of the pores on the feel oil layer is not particularly limited, and for example, the diameter of the pores may be 15 to 100 μm. When the diameter of the air hole on the hand feel oil layer is smaller than 15 microns, the diameter of the air hole is too small, and antibacterial substances in the silicone rubber product body cannot migrate well to the surface of one side of the hand feel oil layer far away from the silicone rubber product body, so that the antibacterial effect is not realized; when the diameter of the air hole on the hand feeling oil layer is larger than 100 micrometers, the antibacterial substance migrates too fast, long-acting antibacterial is not facilitated, and large cracks visible to naked eyes exist on the silicone rubber product, so that the overall appearance is poor and the touch feeling is poor. If the air holes are formed of a plurality of air bubbles 210, the diameter of the air holes is preferably 50 to 100 μm, and if the air holes are cracks, the diameter of the air holes is preferably 15 to 30 μm.
In yet another aspect of the present invention, the present invention provides a method of making the aforementioned silicone rubber article comprising: providing a silicone rubber product body; and after the hand feeling oil is applied to the body of the silicone rubber product, the formed hand feeling oil layer is treated so as to form through air holes and/or non-through air holes in the hand feeling oil layer. Therefore, the silicone rubber product with good human touch feeling and lasting antibacterial effect can be obtained simply and conveniently by the method. The selection of the through-going air holes and/or the non-through-going air holes can be made by a person skilled in the art according to the actual situation.
According to some embodiments of the present invention, a method of forming through pores and/or non-through pores in the feel oil layer is not particularly limited, for example, referring to (a) of fig. 4, a certain amount of a foaming agent is added to the feel oil, i.e., a large amount of gas can be generated under a certain condition, thereby forming a large amount of continuous or discontinuous bubbles 210 in the feel oil layer 200, specifically, the feel oil forming the feel oil layer may include a solvent, a resin, a filler, a foaming agent and an auxiliary agent, and specifically, the method of forming the feel oil includes: mixing the solvent, the resin, the filler, the foaming agent and the auxiliary agent at normal temperature, and then rapidly stirring until bubbles are uniformly dispersed.
According to some embodiments of the present invention, the stirring speed when stirring the raw materials forming the hand oil is not particularly limited, for example, the stirring speed may be 1000 to 4000r/min, and when the stirring speed is within the above range, the foaming agent may form fine and small foam, and the bubble diameter is between 10 and 50 μm; when the stirring speed is higher than 4000r/min, the requirement on a foaming equipment machine is higher; when the stirring speed is less than 1000r/min, the generated bubbles are larger when the stirring speed is too low, and the formed hand feeling oil layer is easy to break.
According to some embodiments of the present invention, the mass ratio of the solvent, the resin, and the filler in the feel oil is not particularly limited, for example, the mass ratio of the solvent, the resin, and the filler in the feel oil may be (25 to 45): (35-45): (7-15).
According to some embodiments of the present invention, the amount of the foaming agent added to the feel oil is not particularly limited, for example, the amount of the foaming agent added is 0.05 to 0.3 parts by weight based on 1 part by weight of the feel oil. When the addition amount of the foaming agent is less than 0.05 parts by weight based on 1 part by weight of the hand feeling oil, the foaming agent content is too small to be favorable for the formation of bubbles; when the addition amount of the foaming agent is more than 0.3 weight part, the content of the foaming agent is excessive, the initial bubble shape is not well controlled, bubbles with oversized size are easily formed, the size of the bubbles is smaller than the thickness of the hand feel oil layer, and finally the formed bubbles are nonuniform in size, so that penetrating air holes are not formed, and non-penetrating air holes are formed.
According to some embodiments of the present invention, in order to ensure that the silicone rubber product body is not affected by temperature variation, a low-temperature foaming agent is selected during the preparation of the hand oil, and the boiling point of the foaming agent is not particularly limited, for example, the boiling point of the foaming agent may be 25 to 75 ℃.
According to some embodiments of the present invention, the kind of the foaming agent in the hand oil is not particularly limited as long as the boiling point thereof is low, and for example, the foaming agent may be at least one of lower aliphatic hydrocarbon, halogenated hydrocarbon, low boiling point alcohol, low boiling point ether, low boiling point ketone and low boiling point aromatic hydrocarbon.
According to some embodiments of the present invention, the kind of the solvent in the hand oil is not particularly limited, for example, the solvent in the hand oil may be one or more of white oil, aviation kerosene, and cyclohexane.
According to some embodiments of the present invention, the kind of resin in the feel oil is not particularly limited, for example, the resin in the feel oil may be vinyl-terminated polymethylsiloxane.
According to some embodiments of the present invention, the kind of filler in the feel oil is not particularly limited, for example, the filler in the feel oil may be a mixture of MQ resin and silica, and specifically, the mass ratio of MQ resin and silica in the filler may be (6-12): (1-6).
According to some embodiments of the present invention, the kind of auxiliary agent in the feel oil is not particularly limited, for example, the auxiliary agent in the feel oil may be an inhibitor and a hydrogen-containing silicone oil.
According to some embodiments of the present invention, referring to fig. 4, the treatment of the formed hand feel oil layer after applying the hand feel oil to the silicone rubber article body is performed according to the following steps:
Referring to (a) of fig. 4, a feel oil is applied on the silicone rubber article body 100 to form a feel oil layer 200.
Referring to (b) of fig. 4, a first temperature is applied to a side of the silicone rubber product body 100 far from the hand feeling oil layer 200, a second temperature is applied to a side near to the hand feeling oil layer 200, a temperature difference exists between the first temperature and the second temperature, bubbles are caused to flow over along a low temperature direction due to the existence of temperature difference convection, and a vertical dendrite-shaped bubble can be formed to form an internal passage by controlling a temperature gradient direction. Referring to (c) of fig. 4, bubbles 210 penetrate through the feel oil layer 200, thereby forming penetrating and/or non-penetrating pores in the feel oil layer 200. The selection of the through air holes and/or the non-through air holes can be performed by those skilled in the art according to the actual situation.
According to some embodiments of the present invention, the temperature ranges of the first temperature and the second temperature are not particularly limited as long as there is a temperature difference between the first temperature and the second temperature, for example, the first temperature may be-40 to 0 ℃, and the second temperature may be 100 to 200 ℃.
The manner of applying the first temperature and the second temperature according to some embodiments of the present invention is not particularly limited, and for example, referring to (b) of fig. 4, the first temperature may be applied through the first heat source 310, the second temperature may be applied through the second heat source 320, or the second temperature may be applied through the first heat source 310, and the first temperature may be applied through the second heat source 320. Specifically, the first person may be a mixture of liquid nitrogen and absolute ethanol, and the second heat source may be a heating plate. Those skilled in the art will choose from the actual situation.
According to some embodiments of the present invention, the method of forming the through pores in the feel oil layer may be, for example, a method of forming the through pores by ultraviolet irradiation of the feel oil layer having no bubbles therein without incorporating a foaming agent into the feel oil. The hand feeling oil forming the hand feeling oil layer only comprises solvent, resin, filler and auxiliary agent, wherein the types and the addition amounts of the solvent, the resin, the filler and the auxiliary agent can be kept consistent with those of the hand feeling oil added with the foaming agent, and are not repeated here.
Specifically, after the hand feeling oil is applied to the silicone rubber product body, ultraviolet irradiation is carried out on the formed hand feeling oil layer, and the method comprises the following steps of:
referring to (a) of fig. 5, a feel oil is applied on the silicone rubber article body 100 to form a feel oil layer 200.
Referring to (b) of fig. 5, UV ultraviolet irradiation is performed on the feel oil layer 200 from the side of the feel oil layer 200 away from the silicone rubber product body 100, and referring to (c) of fig. 5, a penetrating micro-crack 220 is finally formed on the feel oil layer 200. In particular, since the surface of the silicone rubber product body has the feel oil layer, and the feel oil layer has the function of protecting the silicone rubber product body, when the feel oil layer is irradiated with ultraviolet rays from the side of the feel oil layer away from the silicone rubber product body, the effect on the silicone rubber product body is not caused, and the oxide layer is not formed on the surface of the side of the silicone rubber product body close to the feel oil layer. Specifically, referring to fig. 6, it can be seen that the surface of the silicone rubber product not irradiated by ultraviolet rays has a large number of particles with a diameter of 30-60 micrometers, the particles are raised to make the surface smooth, but the hand feeling oil layer also serves as a sealing layer to prevent the migration of antibacterial substances, so that the antibacterial performance is seriously affected, referring to fig. 7 (7 a), it can be seen that the number of particles on the surface of the hand feeling oil layer is obviously reduced after the treatment by ultraviolet rays, referring to fig. 7 (7 b) and (7 b) show the partial enlarged view of the scanning electron microscope block of the silicone rubber product in the embodiment (7 a), and a large number of micro cracks are generated at the position pointed by arrows, and the cracks can be used as migration channels of the antibacterial substances of the silicone rubber product, so that the antibacterial capability of the body of the silicone rubber product can be fully exerted while the silicone rubber product has better hand feeling, and meanwhile, the problem that the antibacterial performance is lost along with the abrasion of the layer in the use process is not limited in the related technology, instead, the phenomenon that the hand feeling oil layer is worn out more fully occurs.
According to some embodiments of the present invention, the shape of the crack is not particularly limited, for example, the ratio of the length of the crack perpendicular to the surface of the silicone rubber article body to the width of the crack parallel to the surface of the silicone rubber article body may be greater than 50:1, thereby ensuring that the width of the crack is small, and providing an antimicrobial substance migration path while not affecting the feel of the silicone rubber article.
According to some embodiments of the present invention, the wavelength and time of the ultraviolet irradiation are not particularly limited, as long as the depth of the crack on the hand oil layer after the ultraviolet irradiation is greater than the thickness of the hand oil layer, for example, the depth of the crack may be 15-30 micrometers, so as to ensure that one end of the crack contacts the silicone rubber product body and the other end may contact the surface of the hand oil layer, for example, the wavelength of the ultraviolet irradiation may be 200-350 nm and the irradiation time may be 30-120S.
In still another aspect of the present invention, the present invention provides a wearing article, which is prepared from the aforementioned silicone rubber product. Therefore, the wearing product has all the characteristics and advantages of the silicone rubber product and is not repeated here.
According to some embodiments of the present invention, the kind of wearing product is not particularly limited, and for example, the wearing product may include an earcap, a case of an earphone, a watchband, or a key.
In still another aspect of the present invention, an antimicrobial material is provided, the antimicrobial material comprising a layer of a feel oil and a body, the layer of feel oil having through pores and/or non-through pores, the layer of feel oil being formed on a surface of the body, the body containing an antimicrobial agent. When the hand feeling oil layer is provided with through air holes, the antibacterial agent in the body can release antibacterial substances through the through air holes; when the hand feel layer has non-penetrating pores, the antimicrobial agent in the body can also release the antimicrobial substance through the non-penetrating pores, but only relatively slowly. Thus, the through and/or non-through air holes may be provided according to the antimicrobial requirements of the antimicrobial material.
According to some embodiments of the invention, the antimicrobial agent comprises a porous carrier and an antimicrobial substance, wherein the antimicrobial substance is supported on the porous carrier.
According to some embodiments of the invention, the antimicrobial material may comprise a silicone rubber material.
It should be noted that, the preparation method of the antibacterial material may refer to some or all steps in the preparation method, the relevant parameters of the air hole, the silicone rubber body and the antibacterial agent may refer to some or all technical features in the foregoing embodiment, and the undescribed portion of the antibacterial material embodiment may refer to the foregoing embodiment and the relevant drawings, which are not repeated herein.
Therefore, the antibacterial material has the advantages that through and/or non-through air holes are formed in the hand feeling oil layer, so that the antibacterial agent in the body can better release antibacterial substances, the comfort of material touch is realized, and the antibacterial property of the material is realized.
The following description of the present application is made by way of specific examples, which are provided to illustrate the present application and should not be construed to limit the scope of the present application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products available commercially without the manufacturer's attention.
Example 1:
1. mixing raw rubber, a filler, an accelerator, a catalyst, an antioxidant, a coupling agent and a release agent, wherein the filler can be montmorillonite, the accelerator is a thiuram accelerator, the antioxidant is cerium oxide, the coupling agent is a mixture of trimethylethoxysilane, methanol and water, and the mass ratio of the raw rubber to the filler to the accelerator to the catalyst to the antioxidant to the coupling agent to the release agent can be 100:13:0.08:2:3:3:0.5; the porous carrier in the antibacterial agent is glass beads, the antibacterial substance is zinc ions, based on 100 weight parts of raw rubber, the addition amount of the antibacterial agent is 0.6 weight parts, and finally the rubber compound is obtained,
2. And mixing the mixed rubber with a vulcanizing agent, and vulcanizing, wherein the vulcanizing agent is sulfur, and the adding amount of the vulcanizing agent is 0.1% based on 1kg of the mixed rubber, so as to finally obtain the vulcanized silicone rubber.
3. The method comprises the steps that a hand feel oil layer is arranged on the surface of vulcanized silicone rubber, the hand feel oil for forming the hand feel oil layer comprises a solvent, resin, filler and an auxiliary agent, wherein the solvent is aviation kerosene, the resin is vinyl-terminated polymethylsiloxane, and the filler is prepared from the following components in percentage by mass: 5, the mixture of MQ resin and silicon dioxide, the auxiliary agent is hydrogen-containing silicone oil, and the mass ratio of solvent, resin and filler in the hand feeling oil is 30:40:10.
4. and (3) carrying out ultraviolet irradiation on the formed hand feel oil layer, wherein the wavelength of the ultraviolet irradiation is 300nm, and the irradiation time is 60S.
Comparative example 1:
comparative example 1 was prepared in the same manner as in example 1 except that no antibacterial agent was added in the step of preparing the compound, and the remainder remained the same.
The test results were as follows:
TABLE 1
TABLE 2
| Test conditions | Example 1 (antibacterial Activity value n) | Comparative example 1 (antibacterial Activity value n) |
| Not tested | 3.4 | 1.5 |
| High temperature and high humidity | 6.9 | 0.8 |
| Cosmetic-olive essential oil | 6.9 | 0.7 |
| Cosmetic-lipstick | 6.9 | 0.7 |
| Artificial sweat | 6.9 | 0.6 |
| Ultraviolet ray | 6.9 | 0.6 |
The results show that, referring to table 1, after the addition of the antibacterial agent in the mixing stage, the physical and chemical properties of the finally prepared antibacterial silicone rubber material are not greatly different from those of the silicone rubber without the antibacterial agent, which shows that the antibacterial agent added in the mixing stage does not destroy the original macromolecular chains in microcosmic scale, and is uniformly dispersed around the macromolecular chains in a porous carrier coating form, and is bonded with each other through weak molecular bonds, so that the antibacterial silicone rubber material has certain deformability. It can be seen that the addition of the antimicrobial agent does not adversely affect the physicochemical properties of the silicone rubber itself.
Referring to table 2, according to the antibacterial test standard of ISO22196, the antibacterial activity value of the antibacterial silicone rubber after the addition of the antibacterial agent reaches 6.9, which is much higher than the antibacterial activity value of 2.6 of the silicone rubber without the antibacterial agent, compared with the silicone rubber without the antibacterial agent. Moreover, after complex environmental tests such as artificial sweat, ultraviolet light, high temperature and high humidity treatment and the like are carried out, the antibacterial activity value can still be maintained at a very high level, and the antibacterial activity value is far greater than that of silicone rubber which is subjected to the same complex environmental test and is not added with antibacterial agents, so that the porous structure of the porous carrier can effectively control the migration of antibacterial substances, and the antibacterial activity still has excellent performance after various complex use environments.
It should be noted that the relationship between the antimicrobial activity value n and the antimicrobial ratio R is as follows: r= (1-10) -n ) As shown by x 100%, when n is greater than 2, R may be greater than 99%, indicating that the ratio of the number of colonies surviving after 24 hours to the initial concentration of colonies on the surface of the unit antimicrobial product is less than 1%, i.e., the greater n, the greater R, the greater antimicrobial.
In the description of the present invention, the azimuth or positional relationship indicated by the terms "upper", "lower", etc. are based on the azimuth or positional relationship shown in the drawings, and are merely for convenience of describing the present invention and do not require that the present invention must be constructed and operated in a specific azimuth, and thus should not be construed as limiting the present invention.
In the description of the present application, "a and/or B" may include any of the cases of a alone, B alone, a and B, wherein A, B is merely for example, which may be any technical feature of the present application using "and/or" connection.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in the present specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (30)
1. A method of preparing an antimicrobial silicone rubber comprising: a mixing stage and a vulcanization stage, wherein,
at least mixing the raw rubber and auxiliary forming components in the mixing stage to obtain a mixed rubber;
in the vulcanization stage, the mixed rubber and a vulcanizing agent are mixed and vulcanized to obtain vulcanized silicone rubber,
and adding an antibacterial agent in the mixing stage and/or the vulcanizing stage, wherein the antibacterial agent comprises a porous carrier and an antibacterial substance, and the antibacterial substance is loaded on the porous carrier.
2. The method according to claim 1, wherein the auxiliary molding component comprises a filler, a promoter, a catalyst, an antioxidant, a coupling agent, and a mold release agent, and the mass ratio of the raw rubber, the filler, the promoter, the catalyst, the antioxidant, the coupling agent, and the mold release agent is 100: (6-20): (0.05-0.12): (1-3): (2-4): (1.5-6): (0.2-0.6).
3. The method according to claim 1, wherein the antibacterial agent is added in an amount of 0.4 to 1 part by weight based on 100 parts by weight of the raw rubber in the kneading stage or the vulcanizing stage.
4. A method according to claim 1 or 3, characterized in that the number of cells on the porous support is 50-100 based on 100 micrometers x 100 micrometers of the porous support.
5. The method of claim 4, wherein the porous support comprises at least one of glass beads, hydroxyapatite, silica, silicate, phosphate, and zeolite.
6. A method according to claim 1 or 3, wherein the antimicrobial substance comprises at least one of zinc ions, silver ions, iron ions and copper ions.
7. The method according to claim 6, wherein the antimicrobial substance is silver ions and the antimicrobial agent, the anti-reducing agent and the antioxidant are added during the mixing and/or the vulcanization stage.
8. The method according to claim 7, wherein the anti-reducing agent is added in an amount of 0.2 to 0.3 parts by weight and the antioxidant is added in an amount of 0.5 to 0.7 parts by weight based on 1 part by weight of the antibacterial agent.
9. A method according to claim 3, wherein the concentration of the antimicrobial substance in the antimicrobial agent is 0.2 to 1.5wt%.
10. A method according to claim 1, wherein the antimicrobial agent is added in both the mixing stage and the vulcanization stage, and wherein the vulcanizing agent is added in an amount of 0.1 to 0.2% based on 1kg of the rubber compound in the vulcanization stage.
11. The method according to claim 10, wherein the antibacterial agent is added in an amount of 0.05 to 0.15 parts by weight based on 1 part by weight of the vulcanizing agent.
12. The method as recited in claim 1, further comprising: and carrying out hot press molding and ultraviolet treatment on the vulcanized silicone rubber.
13. The method according to claim 12, wherein the irradiation wavelength band of the ultraviolet treatment is 263 to 270nm and the irradiation time is 0.5 to 2min.
14. An antimicrobial silicone rubber, characterized in that it is prepared by the method of any one of claims 1-13.
15. A silicone rubber article, comprising:
the silicone rubber product comprises a silicone rubber product body, wherein the silicone rubber product body comprises an antibacterial agent, the antibacterial agent comprises a porous carrier and an antibacterial substance, and the antibacterial substance is loaded on the porous carrier;
and the hand feeling oil layer is provided with penetrating air holes and/or non-penetrating air holes, and is formed on the surface of the silicone rubber product body.
16. The silicone rubber article according to claim 15, wherein the air holes in the hand feel oil layer extend in a direction perpendicular to the body of the silicone rubber article.
17. The silicone rubber article according to claim 15 or 16, wherein the pores have a diameter of 15 to 100 μm.
18. A method of making the silicone rubber article of any one of claims 15-17, comprising:
providing a silicone rubber product body;
and after the hand feeling oil is applied to the silicone rubber product body, treating the formed hand feeling oil layer so as to form penetrating air holes and/or non-penetrating air holes in the hand feeling oil layer.
19. The method of claim 18, wherein the hand oil comprises a solvent, a resin, a filler, a foaming agent, and an adjuvant.
20. The method according to claim 19, wherein the mass ratio of the solvent, the resin and the filler is (25 to 45): (35-45): (7-15).
21. A method according to claim 19 or 20, wherein the blowing agent has a boiling point of 25 to 75 ℃.
22. The method of claim 19, wherein the step of treating the formed feel oil layer after applying the feel oil to the silicone rubber article body is performed by:
applying a hand feel oil to the silicone rubber article body;
And applying a first temperature to one side, far away from the hand feeling oil layer, of the silicone rubber product body, applying a second temperature to one side, close to the hand feeling oil layer, wherein a temperature difference exists between the first temperature and the second temperature, and bubbles in the hand feeling oil layer are communicated under the action of temperature difference convection, so that penetrating air holes and/or non-penetrating air holes are formed in the hand feeling oil layer.
23. The method of claim 22, wherein the first temperature is-40 to 0 ℃ and the second temperature is 100 to 200 ℃.
24. The method of claim 18, wherein the hand oil comprises a solvent, a resin, a filler, and an adjuvant.
25. The method of claim 24, wherein the step of treating the formed feel oil layer after applying the feel oil to the silicone rubber article body is performed by:
applying a hand feel oil to the silicone rubber article body;
and irradiating ultraviolet rays on the hand feel oil layer so as to form penetrating microscopic cracks on the hand feel oil layer.
26. The method of claim 25, wherein the ultraviolet radiation has a wavelength of 200-350 nm and a radiation time of 30-120S.
27. A wearing article, wherein the wearing article is produced using the silicone rubber article according to any one of claims 15 to 17.
28. The wearable product of claim 27, wherein the wearable product comprises an earcap, a headset case, a wristband, or a key.
29. The antibacterial material is characterized by comprising a hand feeling oil layer and a body, wherein the hand feeling oil layer is provided with through air holes and/or non-through air holes, the hand feeling oil layer is formed on the surface of the body, and the body contains an antibacterial agent.
30. The antimicrobial material of claim 29, wherein the antimicrobial agent comprises a porous carrier and an antimicrobial substance, the antimicrobial substance being supported on the porous carrier, the antimicrobial material comprising a silicone rubber material.
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| CN202111240476.9A CN116023784A (en) | 2021-10-25 | 2021-10-25 | Antibacterial silicone rubber, silicone rubber product and method thereof, wearing product and antibacterial material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238056A (en) * | 2015-10-09 | 2016-01-13 | 昆明理工大学 | Preparation method of antibiosis high temperature silicone rubber |
| CN111019359A (en) * | 2019-12-30 | 2020-04-17 | 广东聚合科技股份有限公司 | High-temperature-resistant antibacterial silicone rubber and preparation method thereof |
| CN112011186A (en) * | 2020-09-04 | 2020-12-01 | 陕西省石油化工研究设计院 | Efficient mould-resistant silicon rubber material and preparation method thereof |
| CN112063177A (en) * | 2020-09-10 | 2020-12-11 | 江苏天辰新材料股份有限公司 | Antibacterial and mildew-proof high-temperature vulcanized silicone rubber and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011008204A1 (en) * | 2009-07-15 | 2011-01-20 | Technical Textiles | Ionized performance fabric with antimicrobial/antibacterial/antifungal properties |
| CN102898945B (en) * | 2011-07-28 | 2016-03-02 | 比亚迪股份有限公司 | Silica gel feel oil and preparation method thereof and silica gel product and preparation method thereof |
| CN109320967A (en) * | 2018-09-03 | 2019-02-12 | 广州市瑞合新材料科技有限公司 | A kind of antibiotic property add-on type liquid silicon rubber and preparation method thereof |
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- 2021-10-25 CN CN202111240476.9A patent/CN116023784A/en not_active Withdrawn
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238056A (en) * | 2015-10-09 | 2016-01-13 | 昆明理工大学 | Preparation method of antibiosis high temperature silicone rubber |
| CN111019359A (en) * | 2019-12-30 | 2020-04-17 | 广东聚合科技股份有限公司 | High-temperature-resistant antibacterial silicone rubber and preparation method thereof |
| CN112011186A (en) * | 2020-09-04 | 2020-12-01 | 陕西省石油化工研究设计院 | Efficient mould-resistant silicon rubber material and preparation method thereof |
| CN112063177A (en) * | 2020-09-10 | 2020-12-11 | 江苏天辰新材料股份有限公司 | Antibacterial and mildew-proof high-temperature vulcanized silicone rubber and preparation method thereof |
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