TWI626943B - Antibacterial powder, antibacterial masterbatch and antibacterial structure - Google Patents

Abstract

The invention provides an antibacterial powder, which has a core-shell structure. The core-shell structure includes a core layer and a shell layer covering the surface of the core layer. The core layer is zinc oxide particles and the shell layer includes zinc sulfide. The shell layer is prepared by surface modification of the core layer zinc oxide particles.

Description

Antibacterial powder, antibacterial masterbatch and antibacterial structure

The present invention relates to an antibacterial powder, in particular to a zinc oxide particle which can be prevented from dissolving out in an acid-base environment during the dyeing and finishing process, and further the zinc ion loses its antibacterial property after being chelated with the dye. The antibacterial powder is not limited to the substrate, and can be made into fibers, membranes, and boards by different methods, and these different appearance structures also have antibacterial effects.

In the current technology, in order to make clothes have antibacterial ability, antibacterial additives are generally directly added to the manufacturing process of clothes fiber to achieve antibacterial effect. However, common antibacterial additives have the disadvantage of not being resistant to acid and alkali. During the dyeing and finishing of fibers, metal ions will dissolve and chelate with the dye to lose the antibacterial effect. On the other hand, because silver ions are not easy to dissolve during dyeing, the industry has also developed silver ions as antibacterial additives in clothing fibers. However, the disadvantages of using silver ions as an antibacterial additive are that silver ions are expensive, and the precipitation of silver ions will be absorbed by the human body under long-term use. At present, no research can prove whether metallic silver ions can be metabolized by the human body. Furthermore, another common antibacterial treatment on the market is to add a post-treatment additive after it is made into colored fibers or clothing, but such post-treatment additives may cause the antibacterial ability to fail due to repeated washing of the clothes. From the above, it is known that the industry urgently needs to continue to develop antibacterial fibers or antibacterial additives with low resistance to dyeing and low cost.

The object of the present invention is to provide an antibacterial powder, an antibacterial masterbatch, and an antibacterial structure, so as to solve the problems and defects of the prior art.

The invention provides an antibacterial powder. The powder has a core-shell structure. The core-shell structure includes a core layer and a shell layer covering the surface of the core layer. The core layer is zinc oxide particles. The shell layer includes zinc sulfide. The layer system is obtained by modifying the surface of the core layer of zinc oxide particles.

In an embodiment of the antibacterial powder according to the present invention, the shell layer is obtained by reacting zinc oxide fine particles with a modifier, and the modifier includes mercaptan or sodium sulfide.

In one embodiment of the antibacterial powder of the present invention, the thiol used as a modifier is selected from n-dodecanethiol, 1,3-propanedithiol and ethylthiol.

In an embodiment of the antibacterial powder of the present invention, the particle size of the zinc oxide particles in the core layer is about 10 nanometers (nm) to about 800 nanometers (nm).

In an embodiment of the antibacterial powder of the present invention, the thickness of the shell layer is about 1 nm to about 100 nm.

The antibacterial masterbatch of the present invention includes a first polymer matrix and one embodiment of the above-mentioned antibacterial powder, and the antibacterial powder is uniformly dispersed in the first polymer matrix.

In an embodiment of the antibacterial masterbatch of the present invention, the first polymer matrix includes polyester, polyamide, polypropylene, polyethylene, or a combination thereof.

In an embodiment of the antibacterial masterbatch of the present invention, the weight percentage of the antibacterial powder in the antibacterial masterbatch is about 0.1% to about 30%.

The antibacterial structure of the present invention is made of the above-mentioned antibacterial masterbatch, and the antibacterial structure is a fiber, a film, or a board.

In an embodiment of the antibacterial structure of the present invention, the antibacterial structure is prepared by mixing one embodiment of the above-mentioned antibacterial masterbatch with a second polymer matrix. If the weight of the antibacterial structure is used as a basis, the antibacterial contained in the antibacterial structure is The content of the powder is about 0.1% by weight to about 29.9% by weight, wherein the first polymer matrix includes polyester, polyamine, polypropylene, polyethylene, or a combination thereof, and the second polymer matrix includes polyester and polyfluorene. Amine, polypropylene, polyethylene, polyurethane, or a combination thereof.

In an embodiment of the antibacterial structure of the present invention, the antibacterial structure is made by directly processing an example of the above-mentioned antibacterial masterbatch. If the weight of the antibacterial structure is used as a basis, the content of the antibacterial powder contained in the antibacterial structure is about 0.1 to about 30 weight percent.

The zinc oxide microparticles of the core layer of the antibacterial powder of the present invention are coated with a layer of zinc sulfide as a shell layer, so the zinc oxide microparticles can be protected from the chelation reaction caused by the dissolution of zinc ions during the dyeing and finishing process, so the zinc oxide can be retained Antibacterial effect of particles. Since the zinc oxide particles have good antibacterial effect, stable source and low price, the method for modifying the surface of the zinc oxide particles to make the zinc sulfide sacrificial layer can provide an antibacterial powder with simple process, low cost and excellent antibacterial effect. On the other hand, the antibacterial masterbatch and antibacterial structure of the present invention can be prepared by adding the antibacterial powder of the present invention, and then made into an antibacterial product with good antibacterial ability.

In the following, in order to describe a specific numerical range, the term "a certain value to another value" is used, which should be interpreted to cover any value within the value range and the comparison between the values defined by any value within the value range. The small numerical range is the same as the arbitrary numerical value and the smaller numerical range explicitly described in the specification.

According to an embodiment of the present invention, an antibacterial powder is provided. The powder is composed of a core shell structure, wherein the core shell structure includes a core layer and a shell layer covering a surface of the core layer, and the core layer is oxidized. Zinc particles, the shell layer includes zinc sulfide, and the shell layer is prepared by modifying the surface of the core layer zinc oxide particles. In other words, the shell zinc sulfide layer on the surface of the zinc oxide particles is obtained by modifying the surface of the zinc oxide particles. The manufacturing method of the antibacterial powder of the present invention is described as follows, but the following method is only an exemplary illustration and is not intended to limit the manufacturing method of the antibacterial powder of the present invention.

The preparation method of the antibacterial powder of the present invention includes firstly adding zinc oxide particles into an organic solvent and stirring them uniformly, and then adding a thiol to the organic solvent to form a solution A. Thiol is used as a modifier of zinc oxide fine particles. In the practice of the present invention, the thiol used is selected from n-dodecanethiol, 1,3-propanedithiol or ethylthiol, and the organic solvent may be It is methanol, ethanol or toluene, but the invention is not limited thereto. The weight percentage of zinc oxide particles in the solution A is about 1% to about 40%, and the weight percentage of the thiol in the solution A is about 0.1% to about 10%. The others are organic solvents, such as organic solvents in the solution. The weight percentage in A is from about 55% to about 98%.

After the solution A is formed, the solution A is further stirred for 2 hours. Then, the solution A is spray-dried to form the antibacterial powder of the present invention.

In addition, the present specification also provides a method for manufacturing the antibacterial powder of the present invention. First, zinc oxide particles are added to a sodium sulfide solution and stirred to form a solution B, where sodium sulfide is used as a modifier of zinc oxide particles. Thereafter, the solution B is placed in a reaction device (such as an autoclave) for several hours to react, the temperature is 160 ° C., and the time is 8 hours, so that the surface of the zinc oxide fine particles is modified to form a zinc sulfide layer.

Please refer to FIG. 1. FIG. 1 is a schematic structural diagram of an antibacterial powder according to the present invention. In FIG. 1, only one powder is shown as a schematic diagram. As mentioned above, the antibacterial powder 100 of the present invention has a core-shell structure, which includes a core layer and a shell layer covering the surface of the core layer, wherein the core layer is zinc oxide particles 110 and the shell layer contains zinc sulfide, that is, the first The zinc sulfide layer 120 shown in FIG. 1 is obtained by modifying the surface of the zinc oxide particles 110 of the core layer. In order to make the antibacterial powder 100 have a better structural stability after being made into a structure such as a fiber, a film, or a plate, the particle diameter D of the zinc oxide particles 110 in the core layer is preferably about 10 nm (nm) to about 800 nm. It is suitable for drawing fine denier yarns (for example, DTY: 75/72), and the particle diameter D of the zinc oxide particles 110 is preferably less than 300 nanometers, so that finer denier yarns can be produced. The thickness W of the zinc sulfide layer 120 is preferably about 1 nm to about 100 nm, but the particle diameter D and the thickness W are not limited thereto. In the present invention, the core zinc oxide particles 110 in the antibacterial powder 100 have an antibacterial effect on Staphylococcus aureus, and the zinc sulfide layer 120 can protect the zinc oxide particles 110 and prevent the zinc oxide particles 110 from being present in the antibacterial powder 100. Dissolved during the application process (such as the dyeing process applied to clothing), resulting in reduced antibacterial effect.

Please refer to FIG. 2, which is a schematic diagram of the structure of the antibacterial masterbatch of the present invention. As shown in FIG. 2, the antibacterial powder 100 of the present invention can be directly added to the first polymer matrix 210 to form an antibacterial masterbatch 200. In a preferred case, the antibacterial powder 100 can be uniformly dispersed in the first polymer matrix 210. Inside. According to the embodiment of the present invention, the first polymer matrix 210 may be formed of a thermoplastic polymer material such as polyester, polyamide, polypropylene, polyethylene, or a combination thereof, and the antibacterial powder 100 in the antibacterial masterbatch 200 The weight percentage is from about 0.1% to about 30%, but is not limited thereto. The manufacturing method of the antibacterial masterbatch 200 of the present invention is exemplified as follows, but is not limited thereto. The preparation of the antibacterial masterbatch 200 of the present invention can be prepared by blending the antibacterial powder 100 of the present invention with the first polymer matrix 210, for example, by putting the antibacterial powder 100 and the first polymer matrix 210 into a biaxial extrusion process. Machine, blended at 280 ° C and extruded to obtain antibacterial polyester masterbatch. For example, in the above process, the first polymer matrix 210 may be (but not limited to) polyethylene terephthalate (PET).

Furthermore, the antibacterial masterbatch 200 can be further processed to form other products having an antibacterial structure. For example, after mixing and diluting the antibacterial masterbatch 200 with a second polymer matrix, the antibacterial masterbatch 200 can be processed into a fibrous form to form an antibacterial fiber; the antibacterial masterbatch 200 can also be processed into a fibrous, film, or plate shape. To form antibacterial fibers, films or plates, the fibers or films formed by the antibacterial masterbatch 200 of the present invention can be further made into cloth or clothing with antibacterial function. In the embodiment of the present invention, the second polymer matrix may include polyester, polyamide, polypropylene, polyethylene, polyurethane, or a combination thereof, and the antibacterial powder contained in the antibacterial structure is based on the weight of the antibacterial structure. The content of 100 is about 0.1% by weight to about 29.9% by weight, but the invention is not limited thereto. In other embodiments, the antibacterial masterbatch 200 can be directly processed into antibacterial structures such as fibers, films, or boards, and if the weight of the antibacterial structure is used as a basis, the content of the antibacterial powder 100 contained in the antibacterial structure is about 0.1 weight. Percent to about 30 weight percent.

The following is a description of the fabric manufacturing process, but it is not limited to this.

Fabrics can be woven into fibers through a knitting machine. In general fabric production, the fabric is dyed to the desired color through a dyeing and finishing process, which is beneficial to the subsequent production of various colored clothing and other textiles. Please refer to Fig. 3. Fig. 3 is a schematic diagram showing the change of the pH value of the fabric during each dyeing and finishing process. As shown in Figure 3, the dyeing and finishing process includes the following stages.

Stage <i>: In the dyeing stage, the cloth is dyed with a dye (pH of the dye is about 4).

Stage <ii>: The washing stage cleans the dyed cloth and restores the pH of the cloth to near neutral (pH value is about 7).

Stage <iii>: In the fixing treatment stage, the color stability of the fabric is improved through the fixing treatment in an alkaline environment (pH value is about 10).

Stage <iv>: In the re-washing stage, the cloth after the fixation treatment is washed, and the pH value of the cloth is returned to near neutral (pH value is about 7) to complete the dyeing and finishing process.

Generally, zinc oxide particles are not resistant to acidic environments, and will dissolve in acidic environments. Therefore, if ordinary zinc oxide particles with no zinc sulfide layer on the surface are used as antibacterial powder, the fabric produced will be used for dyeing and finishing During the dyeing stage, <i> will dissolve zinc ions, and zinc ions will chelate with the dye, causing the antibacterial effect of zinc oxide to be invalidated, resulting in the final dyed fabric having no antibacterial function.

In contrast, the surface of the zinc oxide particles 110 of the antibacterial powder 100 (shown in FIG. 1) of the present invention is coated with a layer of zinc sulfide 120, and zinc sulfide will not dissolve in the acidic environment. Therefore, during the dyeing stage, In <i>, the zinc sulfide layer 120 can protect the zinc oxide fine particles 110 and prevent the zinc ions of the zinc oxide fine particles 110 from dissolving out during the dyeing process and a chelating reaction with the dye, thereby keeping the zinc oxide fine particles 110 having an antibacterial effect. That is, the cloth made by using the antibacterial powder 100 of the present invention can retain the complete zinc oxide particles 110 after the dyeing stage <i>. Next, in the stage of the dyeing and finishing process, <iii> the color fixing treatment, zinc sulfide will dissolve in the alkaline environment, so the zinc oxide particles 110 with antibacterial effect will come out of the zinc sulfide layer 120 and maintain its antibacterial ability, That is, after the dyeing and finishing process is completed, the surface of the zinc oxide particles 110 of the antibacterial powder 100 of the present invention in the cloth may not have the zinc sulfide layer 120, but the zinc oxide particles 110 are completely retained in the cloth, and the cloth can be continuously provided. Good antibacterial ability. Finally, after washing the fabric and completing the dyeing and finishing process, it can be made into various antibacterial fabrics with antibacterial function. From the above, it can be seen that the zinc sulfide layer 120 in the antibacterial powder 100 of the present invention is used as a sacrificial layer for protecting the zinc oxide fine particles 110.

According to this, by covering the surface of the zinc oxide fine particles 110 with the zinc sulfide layer 120, the zinc oxide fine particles 110 can be protected and sequestration of zinc ions with dyes or other compounds can be prevented, so the antibacterial effect of the zinc oxide fine particles 110 can be maintained. In addition, because zinc oxide has high safety characteristics, and metal zinc is also a metal with a high content in nature, it has the advantage of low price. Therefore, the antibacterial powder 100 made of zinc oxide particles 110 and its derivatives can be used. It has the advantages of high safety, low cost and long-lasting antibacterial.

In order to enable a person having ordinary knowledge in the art to implement the present invention, each embodiment of the antibacterial powder of the present invention and each comparative example will be described in further detail below, and an antibacterial test will be performed on each of the examples and each comparative example to The characteristics of the antibacterial powder of the present invention are further verified, and the test results are shown in Table 1. The antibacterial structure is taken as an example of the antibacterial fiber, and the antibacterial cloth or antibacterial dyed cloth made of the antibacterial fiber is used for the antibacterial test. It should be noted that the following examples are merely illustrative, and are not intended to limit the present invention. That is, the materials and materials used in the examples may be appropriately changed without exceeding the scope of the present invention. The amount and ratio and processing process.

Example 1

I. Description of the production method of antibacterial powder

First, zinc oxide particles (selected from FZO-50 of ISHIHARA SANGYO KAISHA, LTD .; particle size of 21 nm or less) are added to methanol and stirred well, and then n-dodecanethiol is added to the above solution to form A solution A in which n-dodecanethiol is used as a surface modifier of zinc oxide particles. The weight percentage of zinc oxide particles, n-dodecanethiol and methanol is 20: 2: 78. After the solution A was uniformly stirred for 2 hours, the zinc oxide fine particles were reacted with n-dodecanethiol to form a zinc sulfide layer on the surface of the zinc oxide fine particles. Thereafter, the solution A is spray-dried to form the antibacterial powder of the present invention after drying.

Second, the preparation of antibacterial masterbatch

The antibacterial powder and the first polymer matrix (using polyethylene terephthalate (PET) as an example) were put into a biaxial extruder and blended at a temperature of 280 ° C, and then extruded to obtain an antibacterial masterbatch. grain. The weight percentage of the antibacterial powder and the first polymer matrix polyester is 30:70, that is, based on the total weight of the antibacterial masterbatch, the content of the antibacterial powder is 30% by weight.

Third, the preparation of antibacterial fibers

The antibacterial masterbatch prepared above and the second polymer matrix (using polyethylene terephthalate (PET) as an example) were mixed at a weight ratio of 1 to 29 to obtain a mixture. The mixture was extruded at a temperature of ℃ to 290 ° C to obtain filaments; the coiler was wound at a winding speed of 3,000 meters / minute to obtain 120 denier / 48 filaments (120 denier / 48 filaments (120D / 48F) local alignment yarns are then made into 75D / 48F antibacterial fibers by a friction-type stretch nip twisting machine.

Fourth, the preparation of antibacterial cloth

The antibacterial fiber was woven into an antibacterial cloth with a knitting machine.

Fifth, the process of dyeing and finishing of antibacterial cloth

In this embodiment, the antibacterial cloth can be dyed into an antibacterial dyed cloth through a dyeing and finishing process. The dyeing and finishing process first uses a black dye (selected from Dianix's Black XF) in an acidic environment with a pH of about 4.8. After dyeing the antibacterial cloth to black, after dyeing and washing, the color stability of the antibacterial cloth will be improved by the color fixing treatment in an alkaline environment with a pH value of about 10. Finally, the antibacterial cloth will be washed to complete the dyeing and finishing process. . In this example, the antibacterial effect was tested with the dyed antibacterial cloth.

Six, antibacterial test instructions

The antibacterial test in this case was carried out according to the method of AATCC 100. The test strain was common Staphylococcus aureus.

Example 2

I. Description of the production method of antibacterial powder

The manufacturing method of the antibacterial powder of Example 2 is to first add zinc oxide particles (selected from FZO-50 of ISHIHARA SANGYO KAISHA, LTD .; the particle size is 21 nm or less) to the sodium sulfide solution and stir to form a solution. B, wherein sodium sulfide is used as a surface modifier of zinc oxide particles, the weight percentage of zinc oxide particles in solution B is about 0.1% to about 10%, and the weight percentage of sodium sulfide in solution B is about 1% to about 5%. After that, the solution B is placed in a pressure kettle equipment and reacted at 160 degrees Celsius for 8 hours to obtain the antibacterial powder of the present invention.

Second, the preparation of antibacterial masterbatch

The method for producing the antibacterial masterbatch is the same as in Example 1.

Third, the preparation of antibacterial fibers

The method for producing the antibacterial masterbatch is the same as in Example 1.

Fourth, the preparation of antibacterial cloth

The manufacturing method of an antibacterial cloth is the same as that of Example 1.

Fifth, the process of dyeing and finishing of antibacterial cloth

The dyeing and finishing process of the antibacterial cloth is the same as in Example 1.

Six, antibacterial test instructions

The antibacterial test was the same as in Example 1.

Example 3

I. Description of the production method of antibacterial powder

First add zinc oxide particles (selected from Zongyang Technology Co., Ltd .; particle size is 300 nm) to methanol and stir well, then add n-dodecanethiol to the above solution to form a solution A, of which n-decane Dialkyl mercaptan is a surface modifier for zinc oxide particles. The weight percentage of zinc oxide particles, n-dodecanethiol and methanol is 20: 2: 78. After the solution A was uniformly stirred for 2 hours, the zinc oxide fine particles were reacted with n-dodecanethiol to form a zinc sulfide layer on the surface of the zinc oxide fine particles. Thereafter, the solution A is spray-dried to form the antibacterial powder of the present invention after drying.

Second, the preparation of antibacterial masterbatch

The method for producing the antibacterial masterbatch is the same as in Example 1.

Third, the preparation of antibacterial fibers

The method for producing the antibacterial masterbatch is the same as in Example 1.

Fourth, the preparation of antibacterial cloth

The manufacturing method of an antibacterial cloth is the same as that of Example 1.

Fifth, the process of dyeing and finishing of antibacterial cloth

The dyeing and finishing process of the antibacterial cloth is the same as in Example 1.

Six, antibacterial test instructions

The antibacterial test was the same as in Example 1.

Example 4

I. Description of the production method of antibacterial powder

First add zinc oxide particles (selected from Sigma-Aldrich; particle size is 800 nm) to methanol and stir well, then add n-dodecanethiol to the above solution to form a solution A, where n-dodecane Thiols are used as surface modifiers for zinc oxide particles. The weight percentage of zinc oxide particles, n-dodecanethiol and methanol is 20: 2: 78. After the solution A was uniformly stirred for 2 hours, the zinc oxide fine particles were reacted with n-dodecanethiol to form a zinc sulfide layer on the surface of the zinc oxide fine particles. Thereafter, the solution A is spray-dried to form the antibacterial powder of the present invention after drying.

Second, the preparation of antibacterial masterbatch

The method for producing the antibacterial masterbatch is the same as in Example 1.

Third, the preparation of antibacterial fibers

The method for producing the antibacterial masterbatch is the same as in Example 1.

Fourth, the preparation of antibacterial cloth

The manufacturing method of an antibacterial cloth is the same as that of Example 1.

Fifth, the process of dyeing and finishing of antibacterial cloth

The dyeing and finishing process of the antibacterial cloth is the same as in Example 1.

Six, antibacterial test instructions

The antibacterial test was the same as in Example 1.

Comparative Example 1

I. Description of the production method of antibacterial powder

The antibacterial powder uses zinc oxide fine particles (selected from FZO-50 of ISHIHARA SANGYO KAISHA, LTD .; the particle size is 21 nm or less) and used directly without surface modification.

Second, the preparation of antibacterial masterbatch

The method for producing the antibacterial masterbatch is the same as in Example 1.

Third, the preparation of antibacterial fibers

The method for producing the antibacterial masterbatch is the same as in Example 1.

Fourth, the preparation of antibacterial cloth

The manufacturing method of an antibacterial cloth is the same as that of Example 1.

Fifth, the process of dyeing and finishing of antibacterial cloth

The antibacterial cloth of Comparative Example 1 was directly tested for its antibacterial effect in an undyed state, that is, the antibacterial cloth of Comparative Example 1 was not subjected to a dyeing and finishing process.

Six, antibacterial test instructions

The antibacterial test was the same as in Example 1.

Comparative Example 2

I. Description of the production method of antibacterial powder

The preparation method of the antibacterial powder is the same as that of Comparative Example 1.

Second, the preparation of antibacterial masterbatch

The method for producing the antibacterial masterbatch is the same as that of Comparative Example 1.

Third, the preparation of antibacterial fibers

The method for producing the antibacterial masterbatch is the same as that of Comparative Example 1.

Fourth, the preparation of antibacterial cloth

The manufacturing method of an antibacterial cloth is the same as that of the comparative example 1.

Fifth, the process of dyeing and finishing of antibacterial cloth

The dyeing and finishing process of the antibacterial cloth is the same as in Example 1.

Six, antibacterial test instructions

The antibacterial test was the same as in Example 1, and the antibacterial test was performed after dyeing.

Please refer to Table 1. Table 1 is a comparison table of the results of the antibacterial test performed on the antibacterial cloths formed in Example 1 and Example 2 and Example 3 and Comparative Examples 1 to 2 of the present invention. The antibacterial test is based on the AATCC-100: 2012 specification for the ATCC 6538 Staphylococcus aureus test.

Table 1 Comparison table of the results of the antibacterial test of antibacterial cloth         <TABLE border = "1" borderColor = "# 000000" width = "85%"> <TBODY> <tr> <td> </ td> <td> Example 1 </ td> <td> Example 2 < / td> <td> Example 3 </ td> <td> Example 4 </ td> <td> Comparative Example 1 </ td> <td> Comparative Example 2 </ td> </ tr> <tr> <td> Antibacterial powder material </ td> <td> Zinc oxide particles coated with zinc sulfide layer on the surface </ td> <td> Zinc oxide particles coated with zinc sulfide layer on the surface </ td> <td> Surface coating Zinc oxide particles covered with zinc sulfide layer </ td> <td> Zinc oxide particles covered with zinc sulfide layer </ td> <td> Zinc oxide particles </ td> <td> Zinc oxide particles </ td> < / tr> <tr> <td> Modifier </ td> <td> n-dodecanethiol </ td> <td> sodium sulfide </ td> <td> n-dodecanethiol </ td > <td> n-dodecanethiol </ td> <td> None </ td> <td> None </ td> </ tr> <tr> <td> Primary particle size </ td> <td> 21nm </ td> <td> 21nm </ td> <td> 300nm </ td> <td> 800nm </ td> <td> 21nm </ td> <td> 21nm </ td> </ tr> < tr> <td> Whether to dye </ td> <td> Yes </ td> <td> Yes </ td> <td> Yes </ td> <td> Yes </ td> <td> No </ td > <td> Yes </ td> </ tr> <tr> <td> Antibacterial effect of Staphylococcus aureus </ td> <td> 96.30% </ td> <td> 94.80% </ td> <td> 93 .30% </ td> <td> 93.00% </ td> <td> ＞ 99.9% </ td> <td> 0% </ td> </ tr> </ TBODY> </ TABLE>

According to the test results in Table 1, because the antibacterial cloth of Comparative Example 2 has undergone a dyeing process, the zinc ions in zinc oxide have been chelated with the dye during the dyeing and finishing process, so compared to the undyed Comparative Example 1, the comparative example The antibacterial fabric of 2 has lost its antibacterial ability. In contrast, in Example 1, Example 2, Example 3 and Example 4 of the present invention, no matter the particle diameter of the zinc oxide particles is tens of micrometers or hundreds of micrometers, the zinc oxide particles of the core layer are used as shells. The zinc sulfide layer of the layer is protected, so the zinc ions in zinc oxide will not chelate with the dye during the dyeing and finishing process, and retain the antibacterial effect of the zinc oxide particles, so the antibacterial fabric made still has good antibacterial properties. ability.

In summary, the zinc oxide particles of the antibacterial powder of the present invention are coated with a zinc sulfide layer on the surface, so the zinc oxide particles can be protected from the chelation reaction caused by the dissolution of zinc ions during the dyeing and finishing process, so the oxidation can be maintained. Antibacterial effect of zinc particles. Since the zinc oxide particles have good antibacterial effect, stable source and low price, the method for modifying the surface of the zinc oxide particles to make the zinc sulfide sacrificial layer can provide an antibacterial powder with simple process, low cost and excellent antibacterial effect. Furthermore, the antibacterial masterbatch and antibacterial structure of the present invention can be prepared by adding the antibacterial powder of the present invention, and then made into an antibacterial product with good antibacterial ability, such as antibacterial fiber, cloth or clothing. The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the scope of patent application of the present invention shall fall within the scope of the present invention.

100‧‧‧ antibacterial powder

110‧‧‧zinc oxide particles

120‧‧‧Zinc sulfide layer

200‧‧‧Antibacterial masterbatch

210‧‧‧The first polymer matrix

D‧‧‧ particle size

W‧‧‧ thickness

<I>, <ii>, <iii>, <iv> ‧‧‧ stages

FIG. 1 is a schematic diagram showing the structure of the antibacterial powder of the present invention. FIG. 2 is a schematic diagram showing the structure of the antibacterial masterbatch of the present invention. Fig. 3 is a schematic diagram showing the change of the pH value of the cloth in the dyeing and finishing process.

Claims (9)

An antibacterial masterbatch includes: a first polymer matrix including polyester, polyamide, polypropylene, polyethylene, or a combination thereof; and a plurality of antibacterial powders uniformly dispersed in the first polymer matrix, each The antibacterial powder has a core-shell structure, which includes a core layer and a shell layer covering a surface of the core layer, wherein the core layer is zinc oxide particles, the shell layer includes zinc sulfide, and the The shell layer is obtained by modifying the surface of the zinc oxide particles of the core layer. The antibacterial masterbatch according to claim 1, wherein the shell layer is obtained by reacting zinc oxide fine particles with a modifier, and the modifier includes a mercaptan or sodium sulfide. The antibacterial masterbatch according to claim 2, wherein the thiol is selected from the group consisting of n-dodecanethiol, 1,3-propanedithiol, and ethylthiol. The antibacterial masterbatch according to claim 1, wherein the particle size of the zinc oxide particles of the core layer is about 10 nanometers (nm) to about 800 nanometers. The antibacterial masterbatch according to claim 1, wherein the thickness of the shell layer is about 1 nm to about 100 nm. The antibacterial masterbatch according to claim 1, wherein the weight percentage of the antibacterial powder in the antibacterial masterbatch is about 0.1% to about 30%. An antibacterial structure is prepared from the antibacterial masterbatch according to claim 1, wherein the antibacterial structure is a fiber, a film, or a board. The antibacterial structure according to claim 7 is prepared by mixing the antibacterial masterbatch described in claim 1 with a second polymer matrix. If the weight of the antibacterial structure is used as the basis, The content of the antibacterial powder is about 0.1% by weight to about 29.9% by weight, wherein the second polymer matrix type includes polyester, polyamide, polypropylene, polyethylene, polyurethane, or a combination thereof. The antibacterial structure described in claim 7 is made by directly processing the antibacterial masterbatch described in claim 1. If the weight of the antibacterial structure is used as a basis, the content of the antibacterial powder contained in the antibacterial structure is about 0.1 to about 30 weight percent.