CN113321868A

CN113321868A - White copper-based antibacterial master batch for fibers and preparation method thereof

Info

Publication number: CN113321868A
Application number: CN202110553652.8A
Authority: CN
Inventors: 郑晓頔; 盛平厚; 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 master batch for fibers and a preparation method thereof, wherein the raw materials of the antibacterial master batch 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 master batch for the fibers has the characteristics of good antibacterial broad spectrum, good uniformity and consistency of colors, wide dyeable range, low color matching difficulty and cost, simple and efficient preparation process equipment, high repeatability and wide application prospect.

Description

White copper-based antibacterial master batch for fibers 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 master batch for fibers 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, the raw material copper selected by the existing copper-based antibacterial master batch for the fiber on the market is cupric 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 master batch. 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 master batch formula and a preparation method which take a white copper source as a base material and have good color uniformity and consistency are urgently needed for copper-based antibacterial master batches for 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 master batch for the fiber, wherein the white copper-based alloy nano powder antibacterial agent is selected as the raw material to prepare the fiber master batch, so that the antibacterial property of the master batch is maintained, the uniformity and consistency of the color of the master batch are effectively improved, the dyeable range of the master batch is widened, the color matching difficulty and the cost are reduced, and the application range of the fiber is enlarged.

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

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

Further, the cupronickel alloy nano powder antibacterial agent accounts for 0.4-15% of the total weight of the master batch, 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 master batch, 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 master batch.

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 the color of master batches 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 master batch is white in fiber by preparing the white copper alloy while the antibacterial property of copper is ensured, the dyeable range is widened, the color matching difficulty and cost are reduced, and the application range of the fiber is enlarged.

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 the uniformity and consistency of the color of the master batch, and has a certain antioxidation effect when the cupronickel alloy nano powder antibacterial agent is coated.

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

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.

The preparation method of the white copper-based antibacterial master batch for the fibers 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: and drying the solidified strands, and cutting into granules to obtain the master batch.

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.

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

the invention provides a white copper series antibacterial master batch for fibers, which is prepared by selecting a white copper series alloy nano powder antibacterial agent as a raw material, so that the antibacterial property of the master batch is maintained, the uniformity and consistency of the color of the master batch are effectively improved, the dyeable range of the master batch is widened, the color matching difficulty and cost are reduced, and the application range of the fibers is enlarged.

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 master batch for the fibers has the characteristics of good antibacterial broad spectrum, excellent washing resistance, good uniformity and consistency of colors, wide dyeable range, and low color matching difficulty and cost.

The invention also provides a preparation method of the white copper-based antibacterial master batch for the fibers, which is characterized in that the raw materials are mixed in a high-speed and low-speed mixing mode, so that the mixing degree among the raw materials can be effectively improved, and the dispersibility among the raw materials is better.

The preparation method 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 master batch for fibers comprises 0.4% of a nano copper-nickel alloy antibacterial agent, 99% of PP, 0.2% of low molecular wax, 0.2% of oleic acid and 0.2% of an 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 antibacterial master batch comprises the following steps:

(1) grinding: adding PP into a grinder and grinding into PP powder;

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

(3) mixing: adding 0.4% of nano copper-nickel alloy antibacterial agent, 99% of PP 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; the high and low speed mixing are separated and mixed twice.

(4) Extruding: adding the mixed raw materials into a screw extruder for extrusion, wherein the extrusion temperature is 205 ℃, and cooling and solidifying the extruded filaments by cooling water;

(5) and (3) granulation: the solidified strand silk is dried by a dryer and then cut into particles by a granulator, namely master batches.

Example 2

A white copper series antibacterial master batch for fibers 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 fatty acid coating dispersion treatment. The extrusion temperature was 250 ℃ and the other preparation conditions and preparation method were the same as those of example 1.

Example 3

A white copper series antibacterial master batch for fibers comprises 3% of a nano zinc-copper-nickel alloy antibacterial agent, 95.5% of PA66, 0.5% of phthalate ester coupling agent, 0.5% of ascorbic acid and 0.5% of 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. The extrusion temperature was 275 ℃ and the other preparation conditions and preparation method were the same as those of example 1.

Example 4

A white copper series antibacterial master batch for fibers 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 coating and dispersion treatment. The extrusion temperature was 200 ℃ and the other preparation conditions and preparation method were the same as those of example 1.

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.

In this experimental example, the master batches prepared in example 1 and comparative examples 1 to 5 were tested for their properties, 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 master batch is in the range of 0.4% to 15%, the antibacterial rate of the master batch is increased to 99% with the increase of the antibacterial agent content, and the fiber can be prepared. The staphylococcus aureus and the escherichia coli are bacteria, the candida albicans is fungi, and the broad-spectrum advantage of the antibacterial master batch prepared by the invention is mainly reflected in that the antibacterial performance and the antifungal performance are excellent.

However, if the content of the antibacterial agent in the master batch exceeds the content range, as in comparative example 4, is 0.2%, the antibacterial rate of the master batch is obviously reduced and the antibacterial property is insufficient when the content of the antibacterial agent is too low; however, when the content of the antibacterial agent is too large, as the content of the antibacterial agent in comparative example 5 is 25%, since the antibacterial agent is the cupronickel alloy, the spinnability of the prepared master batch is reduced with the increase of the content of the cupronickel alloy, the mechanical property of the formed fiber is deteriorated, and even the fiber cannot be prepared under the conditions of filament floating, no winding and the like.

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.

The experimental example compares the master batches prepared in the example 2 and the comparative examples 6 to 10, and finds that when the average particle size of the cupronickel alloy nano powder antibacterial agent is within the range of 200-700 nm, the prepared master batches and the master batches have relatively high preparation rate of prepared fibers on the basis of controlling the preparation cost, and when the average particle size of the cupronickel alloy nano powder antibacterial agent is within the range of 300-600 nm, the comprehensive effect is better.

However, when the average particle size is less than this range, the production cost is greatly increased and the agglomeration is easily caused, as in comparative example 9 in which the average particle size is 50 nm; when the average particle size is larger than this range, the production yield of the master batch and the master batch into fibers can be greatly reduced when the average particle size is 1000nm as in comparative example 10.

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.

In this experimental example, the master batches prepared in the above example 3 and comparative examples 11 to 14 were tested for their properties, and the test results are shown in table 2:

TABLE 2 antimicrobial species control experiments

As can be seen from the test results of example 3, comparative example 11 to comparative example 14 described above, when the master batch raw material does not contain an antibacterial agent as in comparative example 11, although the fiber produced is white, it has no antibacterial property; in the comparative example 12, the cupronickel alloy nano powder antibacterial agent was replaced with antibacterial cuprous oxide, but the prepared master batch and fiber were mauve due to reddish brown copper oxide; 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.

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 master batch for the fibers is characterized by comprising the following components:

2. The white copper-based antibacterial master batch for the fiber according to claim 1, wherein the white copper-based alloy nano powder antibacterial agent accounts for 0.4-15% of the total weight of the master batch, and preferably accounts for 1-3%.

3. The white copper-based antibacterial masterbatch for 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 master batch for the fibers according to claim 1, wherein the lubricant, the antioxidant and the dispersant respectively account for 0.2-1.5%, 0.2-1.5% of the total weight of the master batch, and the balance is matrix resin;

5. The white copper-based antibacterial master batch for fibers 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 masterbatch for fiber according to any one of claims 1-5, 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 master batch for fibers 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 masterbatch for fiber according to claim 1 or 4, wherein the matrix resin comprises one or more of PP, PET, PA6, PA66, PBT, and PLA.

9. The white copper-based antibacterial master batch for fibers 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 salts thereof, and amide polymer;

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