CN210733488U

CN210733488U - Sandwich rubber product with antimicrobial effect

Info

Publication number: CN210733488U
Application number: CN201921164982.2U
Authority: CN
Inventors: 钱远强
Original assignee: Individual
Current assignee: Silver Microelectronics Ltd
Priority date: 2019-07-23
Filing date: 2019-07-23
Publication date: 2020-06-12
Anticipated expiration: 2029-07-23

Abstract

The present application relates to an antimicrobial sandwich-type rubber article comprising: an uppermost upper surface layer; a lower skin layer located lowermost; one or more antimicrobial layers positioned between the upper and lower skin layers; wherein the antimicrobial layer comprises silver microparticles having a uniformly distributed particle diameter of 5 to 40 μm, and the upper and lower surface layers each have a thickness of 5 to 50 μm.

Description

Sandwich rubber product with antimicrobial effect

Technical Field

The present application relates to the field of antimicrobial, in particular, to sandwich rubber articles having antimicrobial efficacy.

Background

In recent decades, free-release nano-silver or silver ions have become the most commonly used material in antimicrobial products. However, increasing research has shown that extensive use of nano-silver or silver ions can pose serious risks to human health and the environment. A recent study reviewed the current evidence of toxicity of nanoparticles or silver ions worldwide and suggested that free-released silver nanoparticles or silver ions may be harmful to the environment. In addition, when the nano silver or silver ions are used in an article in direct contact with a human body, the freely released nano silver or silver ions may permeate into the skin of the human body, thereby causing direct damage to the human body.

The permeation of nanosilver or silver ions into the skin becomes particularly severe in articles that come into close contact with human body parts or body fluids, and particularly in rubber articles that come into close contact with human body fluids, articles coated with nanosilver or silver ion coatings on their surfaces have begun to be avoided. This is because complex components (e.g., lipids, amino acids, urea, etc.) contained in human body fluids may attack or accelerate the aging of the surface of the rubber article coated with nano silver or silver ions, thereby promoting the release of nano silver.

In this regard, the present application provides a class of antimicrobial sandwich rubber articles that address one or more technical problems in the art by creating antimicrobial efficacy in a non-contact manner and without substantially releasing silver during use.

SUMMERY OF THE UTILITY MODEL

In one aspect of the present application, there is provided an antimicrobial sandwich-type rubber article comprising: an uppermost upper surface layer; a lower skin layer located lowermost; one or more antimicrobial layers positioned between the upper and lower skin layers; wherein the antimicrobial layer comprises silver microparticles having a uniformly distributed particle diameter of 5 to 40 μm, and the upper and lower surface layers each have a thickness of 5 to 50 μm.

In one embodiment, the thickness of the antimicrobial layer is equal to the particle size of the silver particles. In another embodiment, the antimicrobial layer comprises 5 to 30 weight percent of the silver particles and the balance rubber material, weight percent based on the weight of the antimicrobial layer. In yet another embodiment, if multiple antimicrobial layers are present, an intermediate layer is present between the antimicrobial layers, the intermediate layer having a thickness of from 5 μm to 35 μm.

In one embodiment, the sandwich-type rubber article is a condom, a contraceptive ring, a medical glove, a finger glove, a toe glove, or a wig liner. In another embodiment, the sandwich-type rubber article is a condom, wherein the silver particles have a particle size of 5 to 35 μm, the upper and lower skin layers have a thickness of 5 to 40 μm, and only one of the antimicrobial layers is present. In a further embodiment, the sandwich-type rubber article is a condom, wherein the silver particles have a particle size of 10 to 30 μm, or 15 to 25 μm, the upper and lower skin layers have a thickness of 10 to 35 μm, or 15 to 30 μm, and the antimicrobial layer comprises 15 wt% of the silver particles and the balance rubber material.

In yet another embodiment, the sandwich-type rubber article is a medical glove, wherein the silver particles have a particle size of 10 to 40 μm, and the upper and lower skin layers have a thickness of 20 to 50 μm. In another embodiment, the sandwich-type rubber article is a finger or toe sleeve, wherein the silver particles have a particle size of 15 to 40 μm, and the upper and lower surface layers have a thickness of 20 to 50 μm. In a further embodiment, the sandwich-type rubber article is a medical glove, finger glove or toe glove comprising two antimicrobial layers, and there is an intermediate layer between the two antimicrobial layers having a thickness of 20 μm to 35 μm.

The sandwich-type rubber article of the present application can effectively inhibit or kill (kill rate higher than 99%, and may even be as high as 99.997%) microorganisms on or around the surface layer even when the thickness of the upper and lower surface layers is as high as 50 μm, and substantially no silver particles or silver ions are released during use. In addition, the total thickness of the sandwich type rubber product is not too thick, and the normal use and texture of the rubber product can be ensured.

Drawings

The accompanying drawings are provided below to further describe embodiments of the present invention, but are only for the purpose of enabling those skilled in the art to better understand the disclosure of the present application, and are not intended to limit the scope of the present application.

FIG. 1 is a schematic cross-sectional view of a rubber article according to the present application after completion of construction of a first layer (e.g., a lower skin layer), wherein reference numeral 1 denotes the first layer made of rubber;

FIG. 2 is a schematic cross-sectional view of a rubber article according to the present application after completing the construction of a second layer (e.g., a sandwich layer, i.e., a layer of rubber doped with silver particles), wherein numeral 2 designates the second layer made of rubber doped with 15 wt% silver;

fig. 3 is a schematic cross-sectional view of a rubber article according to the present application after a third layer (e.g., upper skin) is completed, wherein reference numeral 3 refers to the third layer made of rubber.

Detailed Description

The following description includes certain specific details for a thorough understanding of the various disclosed embodiments. One skilled in the relevant art will recognize, however, that an embodiment may be practiced without one or more of the specific details, or with other methods, components, materials, and so forth.

Unless the context requires otherwise, in the following description and claims, the terms "comprise" and "comprise" should be interpreted in an open, inclusive sense, i.e., as "comprising (including, but not limited to").

Reference throughout the specification to "one embodiment," or "an embodiment," or "another embodiment," or "certain embodiments" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases "one embodiment," "an embodiment," "another embodiment," or "certain embodiments" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

It should be noted that all quantities of expressed ingredients, numerical values indicating reaction conditions, used in the specification and claims are to be understood as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present application. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of reported significant digits and ordinary rounding approaches.

Definition of

Unless expressly indicated to the contrary, the following terms used in the specification and appended claims have the following meanings:

as used herein, the term "antimicrobial", "antimicrobial efficacy" or "antimicrobial effect" refers to the generic term for the action of inhibiting or killing microorganisms (e.g., bacteria, viruses, fungi, etc.), the term "inhibiting microorganisms" refers to the action of inhibiting the growth and reproduction of microorganisms, and the term "killing microorganisms" refers to the action of killing microbial nutrients and propagules. In this context, microorganisms mainly refer to bacteria, viruses, fungi, etc.

The term "silver particles" as used herein refers to silver micro-sized particles that are round or round-like (e.g., oval or irregular round). Based on this, silver wire (or silver wire), silver flake (or silver foil), silver rod, and the like are not included in the scope of the "silver particles" as used herein. In addition, "silver particles" as used herein mainly refers to elemental silver particles, and does not contain nano silver or silver ions or silver compounds. Of course, the silver particles may also contain the requisite amount of non-silver impurities, or silver particles of other shapes or sizes (e.g., less than 1% by weight) during actual manufacture and application, as will be understood and appreciated by those skilled in the art.

The term "rubber article" as used herein refers to an article made from a rubber (e.g., natural latex, polybutadiene rubber, etc.) as the major constituent component, without excluding the inclusion of other adulterated components. In addition, if no specific description is given to the structure of the rubber article in the present application, the "rubber article" as referred to herein each means a rubber article having a sandwich-type structure in which a layer containing silver particles is sandwiched at an inner position, that is, neither an upper surface layer nor a lower surface layer contains any silver particles.

The term "substantially" as used herein means that the amount of change in the specified value is less than 5%, preferably 3%, more preferably 1% of the specified value. For example, "the content of the silver particles is substantially constant" means that the content of the silver particles varies by less than 3%, preferably 1%, more preferably 0.5% of the content of the silver particles. By "substantially no silver particles or silver ions are released" it is meant that the weight of the released silver particles (or silver ions) is less than 1%, preferably 0.5%, and even more preferably 0.1% of the weight of the original silver particles. Similarly, the term "substantially" should be interpreted as modifying other numerical values.

Antimicrobial mechanism without release of silver particles or silver ions

In the present application, metallic silver particles are hidden in a matrix (rubber material), microorganisms are inhibited or killed using a positive charge action of an ionic group of silver (e.g., electric field influence, etc.), and substantially no silver ions or silver particles are released from the matrix in the process of inhibiting or killing microorganisms, thereby preventing harm to a human body or pollution to the environment.

Detection method of trace silver or silver ions

1g of the sample was immersed in 100mL of a simulant (artificial sweat, pH 5.5), and after immersion at 40 ℃ for 1 hour, the silver content in the simulant was analyzed by ICP-OES.

Antimicrobial performance test method and antimicrobial effect

Antimicrobial effect

The antimicrobial effect of the antimicrobial article was obtained by measuring the value of the antimicrobial property by JISZ 2801: 2010.

Antimicrobial performance test method

1. Test bacteria

Staphylococcus aureus (Staphylococcus aureus, ATCC 6538P); candida albicans (Candidaalbicas, ATCC 10231).

2. Detection standard

JIS Z 2801:2010

The above test bacteria and tests were provided and conducted by Guangzhou division, general Standard technology services, Inc.

Exemplary embodiments

In a first aspect of the present application, there is provided an antimicrobial sandwich-type rubber article comprising: an uppermost upper surface layer; a lower skin layer located lowermost; one or more antimicrobial layers positioned between the upper and lower skin layers; wherein the antimicrobial layer comprises silver microparticles having a uniformly distributed particle diameter of 5 to 40 μm, and the upper and lower surface layers each have a thickness of 5 to 50 μm.

Here, when the particle diameter of the fine silver particles is larger than the above range, the cost of the rubber product is excessively high and the appearance, texture and use state of the final rubber product may be affected, thereby making the price and application of the final product uncompetitive. For example, too large silver particles can cause the user to feel "grainy" significantly, thereby causing an uncomfortable feeling during use. When the particle size of the silver particles is less than the above range, positive charge effects (such as an electric field, etc.) generated therefrom may be insufficient, and thus microorganisms may not be effectively killed or inhibited due to shielding of the cover (e.g., an upper surface layer or a lower surface layer).

The applicant has found through extensive experiments that when the particle size of the silver particles is within the above range, even when the silver particles are covered with a covering (e.g., a rubber layer) of 40 μm or more, even as high as 50 μm, the microorganisms on or around the surface of the covering can be effectively inhibited or killed (the killing rate is higher than 99%, and even as high as 99.997%), and the total thickness of the corresponding rubber article does not need to be excessively large, so that the normal texture of the rubber article can be ensured.

It is generally recognized in the art that large particle size silver particles can result in cost prohibitive for the final article and that silver nanoparticles or silver ions are not readily released from the article to kill microorganisms. However, based on the principle of non-contact sterilization of microorganisms of the present application, the silver particles can inhibit or kill microorganisms without contacting the microorganisms, thereby preventing harm to a human body or environmental pollution. In addition, the antimicrobial principle of the present application is not particularly limited to the specific material of the rubber covering (i.e., the surface layer) as long as the thickness thereof does not affect the silver particles to exert the antimicrobial effect. For example, the rubber covering may be a natural latex layer, a polybutadiene rubber layer, a styrene butadiene rubber layer, a neoprene rubber layer, or the like.

In one embodiment, the thickness of the antimicrobial layer is equal to the particle size of the silver particles. In another embodiment, the thickness of the antimicrobial layer is not particularly limited as long as it can immobilize and coat the silver particles, for example, the thickness of the antimicrobial layer may be slightly larger than (e.g., 10% or 15% larger than) or slightly smaller than (e.g., 10% or 15% smaller than) the particle size of the silver particles. Of course, in view of the actual industrial production, the silver particles need not be completely contained within the antimicrobial layer, but a small fraction of the volume of the silver particles (i.e., less than 20% of the total volume of the particles) may protrude from the antimicrobial surface, as long as the antimicrobial layer is capable of securely encasing the silver particles.

In this regard, one skilled in the art will appreciate that the upper skin layer, antimicrobial layer, and lower skin layer as used herein need not have a distinct physical boundary, i.e., the upper skin layer and lower skin layer may not have a distinct interface with the antimicrobial layer. For example, the silver particles may be considered as regularly distributed in the middle of an integral rubber layer. As another example, the upper surface layer may be integrally formed with the antimicrobial layer, whereby the silver particles may be considered to be distributed on the bottom of the upper surface layer, while the lower surface layer may present a distinct physical interface with the upper surface layer comprising silver particles on the bottom. Conversely, the lower skin layer may be integrally formed with the antimicrobial layer, whereby the silver particles may be considered to be distributed on top of the lower skin layer, while the upper skin layer may present a distinct physical interface with the lower skin layer comprising silver particles on top.

In one embodiment, the antimicrobial layer comprises 5 to 30 weight percent silver particles and the balance rubber material, wherein weight percent is based on the weight of the antimicrobial layer. In another embodiment, the antimicrobial layer comprises 5, 10, 15, 20, 25, or 30 weight percent silver particles and the balance rubber material, wherein weight percent is based on the weight of the antimicrobial layer. Of course, any value within the above range may be selected according to the actual use, as long as the silver particles can exert the effect of killing microorganisms.

In one embodiment, if multiple antimicrobial layers are present, an intermediate layer is present between the antimicrobial layers. In another embodiment, if multiple antimicrobial layers are present, there is no intermediate layer between the antimicrobial layers. In yet another embodiment, the thickness of the intermediate layer is from 5 μm to 35 μm, such as 10 μm, 15 μm, 20 μm, 25 μm or 30 μm. In further embodiments, the presence or absence of an intermediate layer can be arbitrarily set according to the antimicrobial requirements and texture requirements of the rubber article.

In one embodiment, the sandwich-type rubber article may be a condom, a contraceptive ring, a medical glove, a finger glove, a toe sleeve, a wig liner, or the like. In this regard, since the silver particles are firmly enclosed inside, the content of the silver particles is substantially unchanged, i.e., no silver particles are released, even after undergoing a plurality of water washes. For example, when the rubber article of the present application is a finger glove, the content of silver particles is substantially unchanged after being subjected to the water washing 50 times test, for example, the content of silver particles varies by less than 0.1%, 0.05%, 0.01%, or less. Of course, for disposable articles such as condoms, there is also no release of silver particles.

In one embodiment, the sandwich-type rubber article is a condom, wherein the silver particles have a particle size of 5 to 35 μm, the upper and lower skin layers have a thickness of 5 to 40 μm, and only one antimicrobial layer is present. In another embodiment, the sandwich-type rubber article is a condom, wherein the silver particles have a particle size of 10 to 30 μm, the upper and lower skin layers have a thickness of 10 to 35 μm, and the bio-layer comprises 15 wt% silver particles and the balance rubber material. In yet another embodiment, the sandwich-type rubber article is a condom, wherein the silver particles have a particle size of 15 to 25 μm, the upper and lower skin layers have a thickness of 15 to 30 μm, and the biolayer comprises 15 wt% of the silver particles and the balance rubber material. In yet another embodiment, the sandwich-type rubber article is a condom, wherein the silver particles have a particle size of 10 μm, 15 μm, 20 μm, 25 μm, 30 μm or 35 μm, the upper and lower skin layers have a thickness of 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm or 40 μm, respectively, and the bio-layer comprises 15 wt% silver particles and the balance rubber compound. It follows that such condoms comply with condom thickness regulations and, as shown in the examples below, are capable of significantly killing staphylococcus aureus and candida albicans. Although killing experimental data for viruses have not been obtained for a while, it is expected that such condoms will still have effective killing efficacy against viruses such as HIV.

In one embodiment, the sandwich-type rubber article is a medical glove, wherein the silver particles have a particle size of 10 μm to 40 μm, and the upper and lower skin layers have a thickness of 20 μm to 50 μm. In another embodiment, the sandwich-type rubber article is a medical glove wherein the silver particles have a particle size of 15 μm, 20 μm, 25 μm or 35 μm and the upper and lower skin layers have a thickness of 25 μm, 30 μm, 35 μm, 40 μm or 45 μm.

In one embodiment, the sandwich-type rubber article is a finger or toe sleeve, wherein the silver particles have a particle size of 15 to 40 μm, and the upper and lower surface layers have a thickness of 20 to 50 μm. In one embodiment, the sandwich-type rubber article is a finger or toe sleeve, wherein the silver particles have a particle size of 20 μm, 25 μm, 30 μm or 35 μm, and the upper and lower skin layers have a thickness of 25 μm, 30 μm, 35 μm, 40 μm or 45 μm.

In the above embodiments, the sandwich-type rubber article comprises two or more antimicrobial layers, and there is an intermediate layer having a thickness of 20 μm to 35 μm between the two or more antimicrobial layers. For example, a sandwich-type rubber article comprises two or three antimicrobial layers, and an intermediate layer having a thickness of 20 μm to 35 μm is present between the two or three antimicrobial layers.

Hereinafter, specific embodiments of the present disclosure will be explained in detail by examples listed below in order to better understand various aspects and advantages of the present disclosure. It should be understood, however, that the following examples are non-limiting and are intended to illustrate only certain embodiments of the present application.

Examples

Example 1

The cleaned and dried condom mandrel is dipped into a first dip bath comprising natural latex (bath temperature 21 ℃) for 50 seconds and then pulled out slowly and dried and initially cured (i.e. not fully cured) at 116 ℃ and repeated a number of times until a first layer with a thickness of 15 μm is obtained.

The mold was further immersed in a second dipping bath (bath temperature 21 ℃) containing 15 wt% of silver particles having a particle size of 15 μm and 85 wt% of natural latex for 50 seconds, taking care to keep the silver particles uniformly dispersed in the second dipping bath by stirring or the like before dipping. The mold was slowly pulled out and dried at 116 ℃ and initially cured to give a second layer with a thickness of 15 μm.

The mold was again immersed in a third dipping bath (bath temperature 21 ℃) containing natural latex for 50 seconds and slowly pulled out, then dried at 116 ℃ and initially cured, repeated several times until a third layer with a thickness of 15 μm was obtained.

Finally, the three layers are completely cured and demolded, thus obtaining the sandwich type condom.

Example 2 detection of the amount of silver or silver ions released

A sample of 1g of the condom prepared in example 1 was soaked in 100mL of a simulant (artificial sweat, pH 5.5) and after soaking at 40 ℃ for 1 hour, the simulant was analyzed for silver content using ICP-OES. The test structures are shown in table 1.

Table 1: release test results

Test items	Unit of	Test results	Method detection limit
				Solubility in water	mg/L	Not detected out	1.0

Example 3 non-contact antimicrobial efficacy of silver particles

A sample of flakes was cut out of the condom prepared in example 1, irradiated on both sides for 20 minutes under uv light, and then a bacterial solution was inoculated on either surface of the sample. The control sample was a latex film without antimicrobial properties. Japanese Industrial Standard JIS Z2801: 2010 was used, and the experimental results are shown in Table 2 below.

Table 2: results of the antibacterial test

It can be seen that, for the sample of the present application, the silver particles exert high antibacterial efficacy (antibacterial rate > 99.99%, actually 99.997%) in a non-contact manner. This also provides further experimental support for the present application.

From the foregoing it will be appreciated that, although specific embodiments of the application have been described herein for purposes of illustration, various modifications or improvements may be made by those skilled in the art without departing from the spirit and scope of the application. Such variations and modifications are intended to fall within the scope of the appended claims.

Claims

1. An antimicrobial sandwich rubber article comprising:

an uppermost upper surface layer;

a lower skin layer located lowermost;

one or more antimicrobial layers positioned between the upper and lower skin layers;

wherein the antimicrobial layer comprises silver microparticles having a uniformly distributed particle diameter of 5 to 40 μm, and the upper and lower surface layers each have a thickness of 5 to 50 μm.

2. The sandwich-type rubber article of claim 1 wherein the antimicrobial layer has a thickness equal to the particle size of the silver microparticles.

3. The sandwich-type rubber article of claim 1 wherein if there are multiple layers of said antimicrobial layers, there is an intermediate layer between said antimicrobial layers, said intermediate layer having a thickness of from 5 μ ι η to 35 μ ι η.

4. A sandwich-type rubber article according to any one of claims 1 to 3 which is a condom, a contraceptive ring, a medical glove, a finger glove, a toe glove or a wig liner.

5. The sandwich-type rubber article of claim 4 which is a condom, wherein the silver particles have a particle size of 5 to 35 μm, the upper and lower skin layers have a thickness of 5 to 40 μm, and only one of the antimicrobial layers is present.

6. The sandwich-type rubber article of claim 5 wherein the silver microparticles have a particle size of 10 to 30 μm, or 15 to 25 μm, and the upper and lower skin layers have a thickness of 10 to 35 μm, or 15 to 30 μm.

7. The sandwich-type rubber article of claim 4 which is a medical glove wherein the silver particles have a particle size of 10 to 40 μm and the upper and lower skin layers have a thickness of 20 to 50 μm.

8. The sandwich-type rubber article of claim 4 which is a finger or toe sleeve, wherein the silver particles have a particle size of 15 to 40 μm, and the upper and lower surface layers have a thickness of 20 to 50 μm.

9. A sandwich-type rubber article according to claim 7 or 8 comprising two said antimicrobial layers and there is an intermediate layer between the two antimicrobial layers having a thickness of from 20 μm to 35 μm.