CN113322538A

CN113322538A - White copper-based antibacterial fiber and preparation method thereof

Info

Publication number: CN113322538A
Application number: CN202110553654.7A
Authority: CN
Inventors: 郑晓頔; 盛平厚; 李睿; 韩朝阳; 张雷
Original assignee: China Textile Academy
Current assignee: China Textile Academy
Priority date: 2021-05-20
Filing date: 2021-05-20
Publication date: 2021-08-31

Abstract

The invention discloses a white copper-based antibacterial fiber and a preparation method thereof, wherein the raw materials of the antibacterial fiber comprise 0.4-15% of a white copper-based alloy nano-powder antibacterial agent, 0.2-1.5% of a lubricant, 0.2-1.5% of an antioxidant, 0.2-1.5% of a dispersing agent and the balance of matrix resin, wherein the average particle size of the white copper-based alloy nano-powder antibacterial agent is 200-700 nm. The white copper-based antibacterial fiber provided by the invention has the characteristics of good antibacterial broad spectrum, good uniformity and consistency of color, wide dyeable range, low color matching difficulty and cost and good washing resistance.

Description

White copper-based antibacterial fiber and preparation method thereof

Technical Field

The invention belongs to the field of composite material engineering, and particularly relates to a white copper-based antibacterial fiber and a preparation method thereof.

Background

The antibacterial fiber has high application value in the fields of preparing functional antibacterial textiles, functional medical dressings and the like. Copper can inhibit the growth of bacteria, viruses and fungi at the same time, and has good antibacterial broad spectrum; meanwhile, copper is one of trace elements required by human bodies, is safe and non-toxic, and is environment-friendly. The copper-based antibacterial fiber can improve the added value of textiles and meet the requirements of people on safety, health and environmental protection, so that the copper-based antibacterial fiber is more and more emphasized and has huge market potential.

At present, raw materials of copper selected from the existing copper-based antibacterial fibers in the market comprise copper oxide, cuprous oxide, submicron metal copper powder and various copper salts. The copper powder is reddish brown or brownish yellow due to different particle sizes and oxidation degrees, copper oxide is black, copper ions are blue, and basic copper carbonate is likely to be generated and is green under different preparation modes of the fiber. The colored substances can not only make the antibacterial fiber have color, so that the application range of the fiber is narrowed; in the processes of high-temperature melting granulation, spinning and cooling, the raw material copper can further react with water and oxygen, so that when the product is applied at the rear end, the color is changeable and uneven, the valence state and the existing state of the copper are different, and the color difference is larger.

Therefore, the development of a fiber formula and a preparation method which use a white copper source as a base material and have good color uniformity and consistency are urgently needed for copper-based antibacterial fibers.

The present invention has been made in view of this situation.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide the white copper-based antibacterial fiber, which adopts the white copper-based alloy nano powder antibacterial agent as the raw material, effectively improves the uniformity of the fiber color while keeping the antibacterial property of the fiber, widens the dyeable range of the fiber, reduces the color matching difficulty and cost, and enlarges the application range of the fiber.

In order to solve the technical problems, the invention adopts the technical scheme that: a white copper-based antibacterial fiber comprises the following components:

a cupronickel alloy nano powder antibacterial agent, matrix resin, a lubricant, an antioxidant and a dispersant.

Furthermore, the cupronickel alloy nano powder antibacterial agent accounts for 0.4-15% of the total weight of the antibacterial fiber, and preferably accounts for 1-3%.

Further, the average particle size of the cupronickel alloy nano powder antibacterial agent is 200 to 700nm, preferably 300 to 600 nm.

The cupronickel alloy nano powder antibacterial agent with the content and the average particle size range can ensure the preparation and the antibacterial effect of the fiber and simultaneously give consideration to the preparation rate and the preparation cost of the fiber.

Furthermore, the lubricant, the antioxidant and the dispersant respectively account for 0.2-1.5%, 0.2-1.5% of the total weight of the antibacterial fiber, and the balance is matrix resin.

Preferably, the lubricant, the antioxidant and the dispersant respectively account for 0.3-1.2%, 0.3-1.2% and 0.3-1.2% of the total weight of the antibacterial fiber.

Furthermore, the lubricant, the antioxidant and the dispersant do not contain ions which have chemical reaction with the cupronickel alloy nano powder antibacterial agent.

The lubricant, the antioxidant and the dispersant can well coat the antibacterial agent, so that the cupronickel alloy nano-powder antibacterial agent is uniformly dispersed in the matrix resin, the cupronickel alloy nano-powder antibacterial agent is effectively prevented from being oxidized and denatured, and the uniformity and the consistency of fiber color are improved.

Further, the cupronickel alloy nano powder antibacterial agent comprises one or more of a nano copper-nickel alloy antibacterial agent, a nano iron-copper-nickel alloy antibacterial agent, a nano zinc-copper-nickel alloy antibacterial agent, a nano manganese-copper-nickel alloy antibacterial agent and a nano aluminum-copper-nickel alloy antibacterial agent.

The main component of the cupronickel alloy nano powder antibacterial agent is copper, the copper can simultaneously inhibit the growth of bacteria, viruses and fungi, has good antibacterial broad-spectrum property, is one of trace elements required by human bodies, is safe and non-toxic, is environment-friendly, and has lower price.

Copper ingots and nickel ingots are synthesized in a gas phase to prepare nano white copper alloy powder, and elements such as zinc, iron, manganese, aluminum and the like which can be dissolved with copper and nickel can be added to prepare complex white copper such as iron-copper-nickel alloy, zinc-copper-nickel alloy, manganese-copper-nickel alloy, aluminum-copper-nickel alloy and the like, so that the prepared fibers are white, the dyeable range is widened, the color matching difficulty and cost are reduced, and the application range of the fibers is enlarged while the antibacterial property of copper is ensured.

Further, the cupronickel alloy nano powder antibacterial agent is subjected to dispersion treatment coated by a dispersing agent.

Preferably, the dispersant comprises one or more of benzotriazole, organic acid and coupling agent.

Preferably, the organic acid comprises one or more of oleic acid, ascorbic acid, alkylamine, fatty acid, citric acid, salicylic acid.

Preferably, the coupling agent comprises one or more of a silane coupling agent and a phthalate coupling agent.

The coating and dispersing treatment of the cupronickel alloy nano powder antibacterial agent by using the dispersing agent enables the cupronickel alloy nano powder antibacterial agent to be uniformly dispersed in the master batch, reduces easy agglomeration of the cupronickel alloy nano powder antibacterial agent caused by small particle size, improves uniformity and consistency of fiber color, and has a certain antioxidation effect when the cupronickel alloy nano powder antibacterial agent is coated.

Further, the lubricant comprises one or more of low molecular wax, modified low molecular polyethylene, silicate ester, phosphate ester, white oil, turpentine oil, mineral oil, silicone oil, hydroxyl silicone oil, isopropanol, stearic acid and salt thereof, and amide polymer.

The antioxidant comprises one or more of antioxidant 1010, antioxidant 1024, antioxidant 1076, antioxidant 1098, antioxidant 168 and antioxidant DNP.

Further, the matrix resin comprises one or more of PP, PET, PA6, PA66, PBT and PLA.

A preparation method of a white copper-based antibacterial fiber comprises the following steps:

(1) grinding: adding the matrix resin slices into a pulverizer and grinding into matrix resin powder;

(2) weighing: weighing the cupronickel alloy nano powder antibacterial agent, the matrix resin powder, the lubricant, the antioxidant and the dispersant according to the weight parts;

(3) mixing: adding the cupronickel alloy nano powder antibacterial agent, matrix resin powder, a lubricant, an antioxidant and a dispersant into a high-speed mixer for high-speed and low-speed mixing;

(4) extruding: adding the mixed raw materials into a screw extruder for extrusion, and cooling and solidifying the extruded filaments;

(5) and (3) granulation: drying the solidified strands and cutting into granules to obtain master batches;

(6) and (3) drying: drying the master batch in a vacuum drying oven for 12-48 h;

(7) spinning: adding the dried master batch into a spinning machine, extruding at high temperature through a screw to form uniform melt, conveying the measured melt to a spinning assembly, spraying the melt through a spinneret plate to form strands, cooling, oiling, and finally winding to obtain pre-oriented fibers;

(8) elasticizing: false twist texturing is carried out on a texturing machine to obtain the white copper-based antibacterial fiber with draw texturing.

Wherein, the high-low speed mixing in the step (3) comprises the following steps:

at least one low speed mixing, said low speed mixing being mixing at a low rotational speed for a period of time.

At least one high speed mixing, said high speed mixing being mixing at a high rotational speed for a period of time.

The low-speed mixing and the high-speed mixing are carried out at intervals.

The raw materials are mixed by a high-speed and low-speed mixing mode, so that the mixing degree of the raw materials can be effectively improved, and the dispersibility of the raw materials is better.

By replacing the spinning assembly, the single-component pure antibacterial master batch can be spun, and the master batch can be used as a skin layer master batch and a base material core layer master batch without antibacterial agent to be subjected to composite spinning after being melted to obtain the skin-core structure white copper-based antibacterial fiber.

After adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:

the invention provides a white copper-based antibacterial fiber, which effectively improves the uniformity of fiber color while keeping the antibacterial property of the fiber by selecting a white copper-based alloy nano powder antibacterial agent as a raw material, widens the dyeable range of the fiber, reduces the color matching difficulty and cost, and enlarges the application range of the fiber.

The content and the average grain diameter of the cupronickel alloy nano powder antibacterial agent are limited, and the preparation rate and the preparation cost of the fiber are considered on the basis of ensuring the preparation and the antibacterial effect of the fiber.

The white copper-based antibacterial fiber provided by the invention has the characteristics of good antibacterial broad spectrum, excellent washing resistance, good uniformity and consistency of color, wide dyeable range, color matching difficulty and low cost.

The invention also provides a preparation method of the white copper-based antibacterial fiber, which has the characteristics of simple and convenient preparation process equipment, high efficiency, high repeatability and wide application prospect.

Detailed Description

To make the objects, technical solutions and advantages of the present invention clearer and more fully described below with reference to some examples, it will be understood by those skilled in the art that the following embodiments are only used for explaining the technical principles of the present invention and are not intended to limit the scope of the present invention. For example, although the present application describes the steps of the method of the invention in a particular order, these orders are not limiting, and one skilled in the art can perform the steps in a different order without departing from the underlying principles of the invention.

Example 1

A white copper-based antibacterial fiber comprises 0.4% of nano copper-nickel alloy antibacterial agent, 99% of PA6, 0.2% of low molecular wax, 0.2% of oleic acid and 0.2% of antioxidant 1010. Wherein the average grain diameter of the nano copper-nickel alloy antibacterial agent is 200nm, and the nano copper-nickel alloy antibacterial agent is subjected to dispersion treatment coated by oleic acid.

The preparation method of the white copper-based antibacterial fiber comprises the following steps:

(1) grinding: adding PA6 into a mill and grinding into PA6 powder;

(2) weighing: weighing nano copper-nickel alloy antibacterial agent, PA6 powder, low molecular wax, oleic acid and antioxidant 1010 in parts by weight;

(3) mixing: adding 0.4% of nano copper-nickel alloy antibacterial agent, 99% of PA6 powder, 0.2% of low molecular wax, 0.2% of oleic acid and 0.2% of antioxidant 1010 into a high-speed mixer for high-speed and low-speed mixing, wherein the low-speed mixing speed is 700 revolutions per minute, the mixing time is 2 minutes, the high-speed mixing speed is 1400 revolutions per minute, and the mixing time is 30 seconds; mixing at high and low speed at intervals, and mixing twice;

(4) extruding: adding the mixed raw materials into a screw extruder for extrusion, wherein the extrusion temperature is 255 ℃, and cooling and solidifying the extruded filaments by cooling water;

(5) and (3) granulation: drying the cured strand silk by a dryer, and cutting the cured strand silk into particles by a granulator to obtain master batches;

(6) and (3) drying: drying the master batch in a vacuum drying oven for 23 h;

(7) spinning: adding the dried master batch into a spinning machine, wherein the spinning temperature is 270 ℃, extruding the master batch at a high temperature through a screw to form a uniform melt, metering the uniform melt through a metering pump, conveying the melt to a spinning assembly, spraying the melt through a spinneret plate to form strands, cooling the strands under the action of a side blowing device, oiling the strands, and finally winding the strands to obtain pre-oriented fibers;

Example 2

A white copper-based antibacterial fiber comprises 1% of a nano iron-copper-nickel alloy antibacterial agent, 98.1% of PA6, 0.3% of a silane coupling agent KH560, 0.3% of fatty acid and 0.3% of an antioxidant 1098, wherein the average particle size of the nano iron-copper-nickel alloy antibacterial agent is 300nm, and the nano iron-copper-nickel alloy antibacterial agent is subjected to dispersion treatment coated by the fatty acid.

The preparation method of the white copper-based antibacterial fiber is the same as that of example 1.

Example 3

A white copper-based antibacterial fiber comprises 3% of a nano zinc-copper-nickel alloy antibacterial agent, 95.5% of PA66, 0.5% of a phthalate coupling agent, 0.5% of ascorbic acid and 0.5% of an antioxidant 168, wherein the average particle size of the nano zinc-copper-nickel alloy antibacterial agent is 600nm, and the nano zinc-copper-nickel alloy antibacterial agent is subjected to dispersion treatment coated by the ascorbic acid.

Example 4

A white copper-based antibacterial fiber comprises 15% of a nano zinc-copper-nickel alloy antibacterial agent, 80.5% of PLA, 1.5% of isopropanol, 1.5% of salicylic acid and 1.5% of an antioxidant DNP, wherein the average particle size of the nano zinc-copper-nickel alloy antibacterial agent is 700nm, and the nano zinc-copper-nickel alloy antibacterial agent is subjected to salicylic acid-coated dispersion treatment.

Experimental example 1

Referring to the embodiment of example 1, only the content of the antibacterial agent was changed, and the other conditions were not changed, to obtain comparative examples 1 to 5.

This experimental example tests the performance of the antibacterial fibers prepared in example 1 and comparative examples 1 to 5, and the test results are shown in table 1:

TABLE 1 control experiment of antibacterial agent content

From the test results of the example 1 and the comparative examples 1 to 5, it can be seen that the antibacterial agent content in the raw material is in the range of 0.4% to 15%, the raw material can be prepared into fibers with the increase of the antibacterial agent content, and the bacteriostasis rate of the fibers is increased to 99%. The staphylococcus aureus and the escherichia coli are bacteria, the candida albicans is fungi, and the broad-spectrum advantage of the antibacterial fiber prepared by the invention is mainly reflected by excellent antibacterial performance and antifungal performance.

However, in the sample out of the content range, if the content of the antibacterial agent in the comparative example 4 is 0.2%, when the content of the antibacterial agent is too small, the antibacterial rate of the fiber is obviously reduced, and the antibacterial property is insufficient; however, when the content of the antibacterial agent was too large, as in comparative example 5, the content of the antibacterial agent was 25%, and the drawn textured fiber could not be produced in the case where the yarn drifted, the full lap failed, the yarn breakage was too large, and the like occurred.

With the increase of the content of the antibacterial agent, on the premise of controlling the fiber fineness to be approximately the same, the spinnability of the prepared master batch is reduced, the mechanical property of the formed fiber is deteriorated, the tensile strain is gradually reduced, but the correlation between the tensile strength and the polymer matrix material is larger, and the master batch is basically not influenced by the antibacterial agent.

Experimental example 2

Referring to the embodiment of example 2, other conditions were not changed, and only the average particle size of the antibacterial agent was changed to 200nm, 600nm, 700nm, 50nm, 1000nm, respectively, to obtain comparative examples 6 to 10.

This experimental example compares the antibacterial fibers prepared in example 2 and comparative examples 6 to 10, and the results are shown in table 2.

TABLE 2 antimicrobial particle size control experiment

Comparing the antibacterial fibers prepared in the example 2 and the comparative examples 6 to 10, it is found that when the average particle size of the cupronickel alloy nano powder antibacterial agent is in the range of 200 to 700nm, the preparation cost is controlled, and the preparation rate of the fibers is relatively high and is above 86%. However, when the average particle size is less than this range, the production cost is greatly increased and the agglomeration is liable to occur, which leads to a decrease in the production yield, as in comparative example 9 in which the average particle size is 50 nm; when it is higher than this average particle diameter range, the production yield of the fiber is greatly reduced as in comparative example 10, in which the average particle diameter is 1000 nm.

With the increase of the granularity of the antibacterial agent, the spinnability of the prepared master batch is reduced on the premise of controlling the fiber fineness to be approximately the same, the mechanical property of the formed fiber is deteriorated, the tensile strength and the tensile strain are gradually reduced, but when the particle size is less than 700nm, the mechanical property is not obviously reduced.

In summary, the overall effect is better when the average particle size of the cupronickel alloy nano powder antibacterial agent is within the range of 300 to 600 nm.

Experimental example 3

Referring to the embodiment of example 3, the conditions were otherwise unchanged, only the type of the antibacterial agent was changed, and cuprous oxide powder, pure copper powder, and zinc oxide powder were selected and compared to obtain comparative examples 11 to 14.

This experimental example tests the performance of the antibacterial fibers prepared in the above example 3, comparative example 11 to comparative example 14, and the test results are shown in table 3:

TABLE 3 control experiment of antimicrobial species

As can be seen from the test results of example 3, comparative example 11 to comparative example 14 described above, when the raw material does not contain an antibacterial agent as in comparative example 11, although the fiber produced is white, it has no antibacterial property; the cupronickel alloy nano powder antibacterial agent was replaced with cuprous oxide having antibacterial property as in comparative example 12, but the prepared fiber was purple red since cupric oxide showed reddish brown; similarly, as in comparative example 13, the antibacterial agent of the cupronickel alloy nano powder is replaced by the antibacterial pure copper powder, and the prepared fiber is purple, so that the application range of the fiber is narrowed; in contrast, in comparative example 14, the antibacterial agent of the cupronickel alloy nano powder was replaced with the antibacterial zinc oxide powder, and although the prepared fiber was white, the antibacterial rate was significantly reduced.

Experimental example 4

An antibacterial fiber was prepared by subjecting a common fiber to chemical plating post-treatment to form a copper antibacterial plating layer on the fiber surface, to obtain comparative example 15.

This experimental example tests the properties of the fibers prepared in the above example 4 and comparative example 15, and the test results are shown in table 4:

TABLE 4 control experiment of the preparation method of antibacterial fiber

The fiber obtained by the preparation method has good washability, the copper content is not lost basically after 50 times of washing, and the bacteriostasis rate can be maintained at 99% before and after washing. After 50 times of washing, the antibacterial fiber obtained by the plating method has about a half-less loss of copper content and also has a reduced bacteriostasis rate.

Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1. The white copper-based antibacterial fiber is characterized by comprising the following components:

2. The white copper-based antibacterial fiber according to claim 1, wherein the amount of the cupronickel alloy nanopowder antibacterial agent is 0.4-15%, preferably 1-3% of the total weight of the antibacterial fiber.

3. The white copper-based antibacterial fiber according to claim 1 or 2, wherein the average particle size of the white copper-based alloy nano-powder antibacterial agent is 200 to 700nm, preferably 300 to 600 nm.

4. The white copper-based antibacterial fiber according to claim 1, wherein the lubricant, the antioxidant and the dispersant respectively account for 0.2-1.5%, 0.2-1.5% and the balance matrix resin of the total weight of the antibacterial fiber;

5. The white copper-based antibacterial fiber according to claim 4, wherein the lubricant, the antioxidant and the dispersant do not contain ions which chemically react with the cupronickel alloy nano powder antibacterial agent.

6. The white copper-based antibacterial fiber according to any one of claims 1 to 5, wherein the white copper-based alloy nano powder antibacterial agent comprises one or more of a nano copper-nickel alloy antibacterial agent, a nano iron-copper-nickel alloy antibacterial agent, a nano zinc-copper-nickel alloy antibacterial agent, a nano manganese-copper-nickel alloy antibacterial agent and a nano aluminum-copper-nickel alloy antibacterial agent.

7. The white copper-based antibacterial fiber according to claim 6, wherein the white copper-based alloy nano-powder antibacterial agent is subjected to dispersion treatment coated by a dispersing agent;

preferably, the dispersant comprises one or more of benzotriazole, organic acid and coupling agent;

preferably, the organic acid comprises one or more of oleic acid, ascorbic acid, alkylamine, fatty acid, citric acid and salicylic acid;

8. The white copper-based antibacterial fiber according to claim 1 or 5, wherein the lubricant comprises one or more of low molecular wax, modified low molecular polyethylene, silicate ester, phosphate ester, white oil, turpentine, mineral oil, silicone oil, hydroxyl silicone oil, isopropanol, stearic acid and its salt, amide polymer;

9. A white copper-based antibacterial fiber according to claim 1 or 4, characterized in that the matrix resin comprises one or more of PP, PET, PA6, PA66, PBT, PLA.

10. A method for preparing the white copper-based antibacterial fiber according to any one of claims 1 to 9, characterized by comprising the following steps: