CN102691129A - Antibacterial polyster fiber as well as production method and application thereof - Google Patents

Abstract

The invention relates to an antibacterial polyester fiber product, production method and application. The method comprises mixing antibacterial components and the like with polyester resin, melt-extruding to prepare antibacterial masterbatch, and melt-spinning the antibacterial masterbatch and polyester resin to produce antibacterial polyester fiber. The antibacterial polyester fiber of the present invention has a long spinning cycle and very good spinnability, and its antibacterial rate against E. More than 98%; non-irritating to the skin. Therefore, the antibacterial polyester fiber produced by the present invention using existing equipment has very good application prospects.

Description

A kind of antibacterial polyester fiber and its production method and its application

【Technical field】

The invention belongs to the field of textile technology. More specifically, the present invention relates to a polyester fiber product with antibacterial function, a production method of the antibacterial polyester fiber, and an application of the antibacterial polyester fiber. the

【Background technique】

There are various bacteria, fungi and other microorganisms in nature. These microorganisms grow and reproduce rapidly under suitable environmental conditions, and spread diseases through contact, affecting people's health. All kinds of textiles are a good living medium for these microorganisms, and they are worn by humans and move around, and they have also become an important source of disease transmission and pollution. the

Fiber can attach many microorganisms. If the temperature and humidity are suitable, these microorganisms will multiply rapidly and cause various harms to the human body. Therefore, in recent years, with the gradual improvement of human health awareness, the antibacterial properties of textiles have attracted more and more attention. Fibers and textiles with antibacterial effects have also become the focus of more and more people's attention. the

Antibacterial fiber belongs to functional fiber. There are three production methods for functional fiber. The first method is chemical modification method, that is, using chemical technology to graft antibacterial functional groups to the reactive groups of fiber substrates. For substances without reactive groups , it is necessary to introduce reactive groups to make the fibers have the conditions for chemical modification. Because this method involves a certain chemical reaction, the processing method is complicated and difficult. This method is rarely used. the

The second method is a physical modification method, that is, blending and adding antibacterial functional substances at different stages of fiber forming, for example, it can be added when spinning raw materials are polymerized; it can also be blended and added when spinning and extruding; for wet spinning Silk can also add functional materials to the spinning dope. Due to its convenient operation, low technical difficulty and wide applicability, physical modification has become the most important method for functional fiber manufacturing. the

The third method is the post-finishing method, which is a physical modification after the fiber is formed or made into a fabric, usually by surface coating method, resin finishing method or microcapsule method. After-finishing functional additives are generally distributed on the surface of fibers and fabrics, so their durability has always been one of the difficulties that people have been working on for a long time. Fibers or fabrics are made into clothing products, which need to be washed and reused continuously, and the functional materials bonded to the surface through finishing are easy to fall off during washing, which reduces its functionality, and in severe cases almost loses all functions, such as antibacterial The fibers no longer have antimicrobial properties. Its functionality decreases with the increase of washing frequency and usage time. The advantage of this method is that the operation is very simple and there are few influencing factors. The disadvantage is that the durability is not guaranteed. It is difficult to meet the requirement that the fabric be functional throughout the wear cycle. Therefore, it is only favored by some low-end or disposable products. the

For example, CN 01113772, the title of invention "Nano polyester staple fiber and its manufacturing method" discloses a method of mixing nano-scale powder with specific antibacterial and bactericidal functions with resin, extruding and spinning to manufacture antibacterial polyester staple fiber, and the invention was published in Adding 30% nano-kid stone ore to polyester resin, and adding such a high amount of inorganic powder to the spinning material, the spinnability is seriously threatened, and it is difficult to pass the normal spinning process. CN 200510012956, the invention name "Nano-composite antibacterial polyester POY blending high-speed spinning method" discloses the use of 20-60 nanometer silver, zinc, silicon-based oxide composite antibacterial powder to make polyester masterbatch, and then the masterbatch is 3- Add 7% to the spinning polyester resin for melt spinning to produce antibacterial polyester fibers. In this method, the composite antibacterial powder is directly added to polyester resin to obtain polyester masterbatch, but it is difficult to achieve good dispersion of antibacterial powder in polyester resin, and unevenly dispersed powder materials will increase the speed of spinning when spinning. The pressure will block the spinneret and affect the spinnability of the fiber; and the uneven dispersion of the antibacterial agent will further affect the antibacterial performance of the fiber. CN200510027688, the name of the invention "An antibacterial and moisture-conducting polyester fiber and its production method and application" and CN 200910184329, the name of the invention "An anti-ultraviolet, antibacterial, moisture-conducting polyester fiber and its production method and application" are all phosphoric acid Zirconium silver-loaded powder is used to make polyester antibacterial masterbatch. The disadvantage of this method is that the antibacterial powder is difficult to disperse evenly in polyester fibers, which may easily lead to poor spinnability and no guarantee of fiber antibacterial performance. the

On the basis of summarizing the prior art, the present inventor has optimized the antibacterial agent system suitable for spinning through a large number of experimental studies, and completed the present invention. the

【Content of invention】

[Technical problem to be solved]

The object of the present invention is to provide a polyester fiber with antibacterial function. the

Another object of the present invention is to provide a production method of the antibacterial polyester fiber. the

Another object of the present invention is to provide the application of the antibacterial polyester fiber. the

[Technical solutions]

The present invention is achieved through the following technical solutions. the

The invention relates to a production method of antibacterial polyester fiber. the

The steps of the production method are as follows:

A. Preparation of antibacterial masterbatch

In the mixer, use 0.015-2 parts by weight of anti-tarnish treatment agent to carry out surface anti-tarnish treatment to 1-20 parts by weight of zeolite silver-loaded zinc antibacterial agent and 1-20 parts by weight of zirconium phosphate-loaded silver antibacterial agent, and then add 0.3-1 Continue to process the coupling dispersant in parts by weight to obtain a mixture containing an antibacterial agent; then, mix the mixture with 75-90 parts by weight of polyester resin, and then use a twin-screw extruder at a heating temperature of 240-265°C , Melt extrusion under the conditions of host speed 200-230 rpm and feeding 18-24Hz to obtain an antibacterial masterbatch;

B. Preparation of antibacterial polyester fiber

Weigh 2-10 parts by weight of the antibacterial masterbatch prepared in step A) and 90-98 parts by weight of polyester resin, and spin by melt spinning to obtain the antibacterial polyester fiber;

The coupling dispersant is one or more coupling dispersants selected from silane series, aluminate series, titanate series or bimetallic composite coupling dispersants;

The anti-tarnish treatment agent is one or more selected from benzotriazole, tolyltriazole, potassium tolyltriazole, natural hydrotalcite, synthetic hydrotalcite, calcined alumina magnesium or silicon Anti-tarnish treatment agent for acid aluminum. the

According to a preferred embodiment of the present invention, the silane series coupling dispersant is a compound of the following formula:

R _n SiX _(4-n)

In the formula:

n=1~3;

R is a methyl, vinyl, amino, epoxy, mercapto or acryloxypropyl functional group;

X is an alkoxy, aryloxy, acyl or chloro group. the

According to another preferred embodiment of the present invention, the aluminate series is selected from distearoyloxyisopropyl aluminate, trimethyl aluminate, triisopropyl aluminate or tribenzyl aluminate. the

According to another preferred embodiment of the present invention, the titanate series is a compound of the following formula:

ROO _(4-n) Ti(OX-R'Y) _n

In the formula:

n=2 or 3;

RO is a hydrolyzable short-chain alkoxy functional group;

OX is a carboxyl, alkoxy, sulfonic or phosphoryl group. the

According to another preferred embodiment of the present invention, the bimetallic composite coupling agent is an aluminum-titanium composite coupling agent or an aluminum-zirconium composite coupling agent. the

According to another preferred embodiment of the present invention, the surface anti-discoloration treatment is carried out at the mixer speed of 2800-3000 rpm for 10-30 minutes. the

According to another preferred embodiment of the present invention, the treatment of the coupling dispersant is carried out at the speed of the mixer at 500-600 rpm for 3-5 minutes. the

According to another preferred embodiment of the present invention, the polyester resin is mixed for 3-5 minutes at a mixer speed of 500-600 rpm. the

The present invention also relates to the antibacterial polyester fiber produced by the method. the

The present invention also relates to the application of the antibacterial polyester fiber in resisting Escherichia coli, Staphylococcus aureus and Candida albicans. the

The present invention will be described in more detail below. the

The invention relates to a production method of antibacterial polyester fiber. the

The steps of the production method are as follows:

A. Preparation of antibacterial masterbatch

In the mixer, use 0.015-2 parts by weight of anti-tarnish treatment agent to carry out surface anti-tarnish treatment to 1-20 parts by weight of zeolite silver-loaded zinc antibacterial agent and 1-20 parts by weight of zirconium phosphate-loaded silver antibacterial agent, and then add 0.3-1 Continue to process the coupling dispersant in parts by weight to obtain a mixture containing an antibacterial agent; then, mix the mixture with 75-90 parts by weight of polyester resin, and then use a twin-screw extruder at a heating temperature of 240-265°C 1. Melt extrusion under the conditions of host speed 200-230 rpm and feeding 18-24Hz to obtain an antibacterial masterbatch. the

First, 0.015-2 parts by weight of the anti-tarnish treatment agent is used to perform surface anti-tarnish treatment on 1-20 parts by weight of the zeolite silver-carried zinc antibacterial agent and 1-20 parts by weight of the zirconium phosphate-carried silver antibacterial agent. The purpose of mixing is to allow the anti-tarnish treatment agent to cover its antibacterial agent, thereby effectively preventing the antibacterial agent from oxidative discoloration, affecting the antibacterial effect of its fibers, and changing the appearance of its fabric. the

The zeolite-loaded silver-zinc antibacterial agent is a silver-loaded zinc 4A zeolite with a silver content of 0.2-0.45% and a zinc content of 1-4% based on the total weight of the antibacterial agent. In the antibacterial agent, different silver and zinc contents not only affect the antibacterial performance of its products, but also affect the discoloration performance of its products. Preferably, the silver content of the zeolite silver-loaded zinc antibacterial agent is 0.28-0.35%, and the zinc content is 1.8-3.2%. The zeolite silver-loaded zinc antimicrobial agent used in the present invention can be the product sold by Beijing Chonggao Nano Technology Co., Ltd. under the trade name Andymei antimicrobial agent AM, or the product sold by Haier Kehua Company under the trade name antibacterial agent FS-ZN . the

The silver-loaded zirconium phosphate antibacterial agent is a layered silver-loaded zirconium phosphate product with a silver content of 1-3% based on the total weight of the antibacterial agent. In the antibacterial agent, different silver contents obviously affect the antibacterial performance and discoloration performance of the product. Preferably, the silver content of the silver-loaded zirconium phosphate antibacterial agent is 1.6-2.4%. Zirconium phosphate silver-loaded antibacterial agent used in the present invention, zeolite silver-loaded zinc antibacterial agent can be the sales product of Beijing Chonggao Nano Technology Co., Ltd. with the trade name Andymei AMR antibacterial agent, or can be sold by Shanghai Runhe Nano Co., Ltd. with the trade name antibacterial agent The product sold by RHA-1 may also be a product sold by Japan SR Trading Company under the brand name zeomic. the

The weight ratio of the zeolite-supported silver-zinc antibacterial agent to the zirconium phosphate-supported silver antibacterial agent is preferably 4-15:6-14; more preferably 8-10:10-12. the

The inventors have found that, compared with a single antibacterial agent, when the zeolite silver-loaded zinc antibacterial agent and the zirconium phosphate silver-loaded antibacterial agent are used in combination according to the above weight ratio, the product has a very obvious antibacterial effect and anti-discoloration increase. effect, specifically refer to the content of effect evaluation 1 in the technical solution of this specification. the

According to the present invention, the anti-tarnish treatment should be understood as a chemical substance that can prevent silver from reacting with sulfide in the air to generate silver sulfide, and produce a black or yellow film layer on its surface. Substances that do not affect antibacterial performance and fiber performance can be used in the present invention. the

The anti-tarnish treatment agent is preferably one or more selected from benzotriazole, tolyltriazole, tolyltriazole potassium, natural hydrotalcite, synthetic hydrotalcite, alumina magnesium calcined Or aluminum silicate anti-tarnish treatment agent. More preferably one or more anti-tarnish treatment agents selected from benzotriazole, tolyltriazole, natural hydrotalcite or aluminum silicate. the

These anti-tarnish treatment agents are all products currently on the market. For example, benzotriazole is CAS95-14-7; methylbenzotriazole is CAS 21412-99; the molecular formula of alumina magnesium calcined product is [Mg _0.7 Al _0.6 O _1.15 ]; synthetic hydrotalcite is [Mg ₄₅ Al _0.5 (OH) ₁₃ CO ₃ .3.5H ₂ O].

When the amount of the zeolite silver-loaded zinc antibacterial agent and the zirconium phosphate silver-loaded antibacterial agent is 1-20 parts by weight, if the amount of the anti-tarnish treatment agent is less than 0.015 parts by weight, the effect of preventing discoloration is not ideal, and there will be a slight yellow color. If the amount of the anti-tarnish treatment agent is greater than 2 parts by weight, it will affect the processing and antibacterial performance of the product, especially the spinning performance; therefore, the amount of the anti-tarnish treatment agent is 0.015 ~ 2 parts by weight. It is suitable. the

The mixer is a product currently on the market, such as a high-speed mixer produced by Zhangjiagang Chuangjia Machinery Co., Ltd., model SHR-5A/10A. the

The anti-discoloration treatment is carried out under the following conditions: the rotating speed of the mixer used is usually 2800-3000rpm, and the anti-discoloration treatment time is 10-30min. This mixing is conducive to the coating of the antibacterial agent and improves the anti-discoloration performance . Preferably, the speed of the mixer is 2850-2950 rpm, and the anti-discoloration treatment time is 16-25 minutes. At this time, the surface coating effect is the best, and the anti-discoloration performance is significantly improved. the

After the anti-discoloration treatment, 0.3-1 weight part of coupling dispersant is added to continue the treatment to obtain a mixture containing antibacterial agent. the

According to the present invention, the coupling dispersant should be understood as a substance that can improve the dispersibility of the antibacterial agent, reduce the surface viscosity of the melt, and reduce the torque and extrusion pressure of the extruder. the

The coupling dispersant is one or more coupling dispersants selected from silane series, aluminate series, titanate series or bimetallic composite coupling dispersants. the

Described silane series coupling dispersant is following formula compound:

R _n SiX _(4-n)

In the formula:

n=1~3;

R is a methyl, vinyl, amino, epoxy, mercapto or acryloxypropyl functional group;

X is an alkoxy, aryloxy, acyl or chloro group. the

The R group is a non-hydrolyzable organic functional group that can be combined with the polymer, and X is a hydrolyzable group, preferably methoxy and ethoxy. the

The silane series coupling dispersant is specifically, for example, γ-aminopropyltriethoxysilane (CAS919-30-2, EINECS 213-048-4), vinyltriethoxysilane (CAS 78-08- 0), N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (CAS73069-29-2), they are all products sold in the market. the

The aluminate series can be (C ₃ H ₇ O) _x Al(OCOR) _m (OCOR) _n (OAB) _y compound, such as distearin sold by Fuzhou Yuanke New Fine Materials Co., Ltd. Acyloxyisopropyl aluminate, trimethyl aluminate, triisopropyl aluminate, tribenzyl aluminate.

The titanate series are compounds of the following formula:

ROO _(4-n) Ti(OX-R'Y) _n

In the formula:

n=2 or 3;

RO is a hydrolyzable short-chain alkoxy functional group;

OX is a carboxyl, alkoxy, sulfonic or phosphoryl group. the

The short-chain alkoxy functional groups that can be hydrolyzed by RO can react with the hydroxyl groups on the surface of inorganic substances, so as to achieve the purpose of chemical coupling. the

The titanate series are specifically isopropyl tristearate titanate (CAS61417-49-0), tetraisopropyl bis(dioctylphosphite) titanate (CAS 65460-52 -8) or isopropyl tris(dioctylpyrophosphate acyloxy) titanate (CAS67691-13-8). the

The bimetallic composite coupling agent is an aluminum-titanium composite coupling agent and/or an aluminum-zirconium composite coupling agent, specifically such as the aluminum-titanium composite coupling agent OL-AT1618 sold by the Shanxi Chemical Research Institute; Hangzhou Jessica Aluminum-zirconium composite coupling agent HY-031 sold by Chemical Co., Ltd. the

The conditions for using coupling dispersant to process are as follows:

The treatment of the coupling dispersant is carried out for 3-5 minutes under the condition of the rotation speed of the mixer at 500-600 rpm. This processing time can ensure that the surface treatment of the material is relatively sufficient; if the processing time is less than 5 minutes, the surface treatment of the material is insufficient; not effectively. the

Then, mix the mixture of antibacterial agent and coupling dispersant with 75-90 parts by weight of polyester resin, and then use the twin-screw extruder at a heating temperature of 240-265 ° C and a main engine speed of 200-230 rpm. Melt extrusion is carried out under the condition of feeding 18-24Hz to obtain an antibacterial masterbatch. the

The polyester resin is a PET (polyethylene terephthalate) resin that can be used for spinning, and its intrinsic viscosity is 0.64-0.66g/dL, such as the spinning grade polyester chips sold by Sinopec Yizheng Chemical Fiber Co., Ltd. , PetroChina Liaoyang Petrochemical Co., Ltd. sells spinning-grade polyester chips. the

The antibacterial agent and the polyester resin of the surface anti-tarnishing treatment are mixed under the following conditions: mix for 3-5 minutes under the condition of mixer rotating speed 500-600rpm, this mixing time can ensure that the materials are mixed more fully; less than If this time is exceeded, the materials will not be mixed uniformly; if the time is longer than this time, the friction of the materials may generate heat and cause sticky lumps to agglomerate, which will cause uneven mixing and affect the production process and product quality. the

The twin-screw extruder used in the present invention is a product currently on the market, such as the TE-65 co-rotating twin-screw extruder produced by Nanjing Keya Chemical Complete Equipment Co., Ltd. the

B. Preparation of antibacterial polyester fiber

Weigh 2-10 parts by weight of the antibacterial masterbatch prepared in step A) and 90-98 parts by weight of polyester resin, and spin by melt spinning to obtain the antibacterial polyester fiber. the

The melt spinning method is to heat and melt a polymer, then extrude it through the spinneret hole, cool and solidify in the air to form a fiber filament, and the polymer that can be used for melt spinning must be able to melt into a viscous fluid state A polymer that does not undergo significant decomposition. the

The antibacterial polyester fiber spinning process adopted in the present invention is consistent with the polyester fiber spinning process in the prior art, so it will not be repeated in the description of this application. the

The present invention also relates to the antibacterial polyester fiber produced by the method. the

The antibacterial polyester fiber produced by the method of the invention is a fiber whose core is polyester resin, and the outer surface of the polyester resin is coated with an antibacterial agent. The antibacterial polyester fiber of the invention has excellent antibacterial performance, and the antibacterial effect is long-lasting, and the performance will not be weakened due to washing or the like. In addition, the antibacterial fiber has a good appearance and no yellowing phenomenon. Most importantly, the ultrafine powder of the antibacterial agent of the present invention has been coated and surface-treated during use, has good compatibility with the matrix resin, and has good dispersion performance in the resin, so that the antibacterial material can be used in When spinning, it shows good spinnability, and the cycle of changing the screen and the cycle of replacing the spinning component is compared with other similar spinning-grade antibacterial masterbatches (such as the general zirconium phosphate silver-loaded antibacterial masterbatch on the market). Relatively long, thereby effectively reducing equipment loss. the

The antibacterial polyester fiber is produced by the method of the invention, and the spinning cycle is long. The pressure filter value (DF value) of the antibacterial masterbatch of the present invention is less than 2.0×105Pa·cm ² /g; the cycle of changing the screen is ≥1 piece/12 hours, and the cycle of changing the components is ≥15 days. However, the spinning cycle of antibacterial polyester fiber prepared by adopting the antibacterial masterbatch of zirconium phosphate loaded with silver on the market is ≥1 piece/8 hours, and the component replacement cycle is ≥6 days. It can be seen that the spinnability of the antibacterial masterbatch of the present invention is very good.

The present invention also relates to the application of the antibacterial polyester fiber in resisting Escherichia coli, Staphylococcus aureus and Candida albicans. the

1. Excellent antibacterial performance

According to the standard test of AATCC100-2004 "performance evaluation of antibacterial finishing of textile materials", after the antibacterial polyester fiber produced by the method of the present invention is woven into fabric, the antibacterial rate to Escherichia coli, Staphylococcus aureus and Candida albicans is more than 99%. The results are listed in Table 1. the

Table 1: Antibacterial test results of the antibacterial polyester fiber of the present invention

Two kinds of antibacterial agents zeolite silver-loaded zinc antibacterial agent and zirconium phosphate silver-loaded antibacterial agent that the present invention selects have synergistic effect,

The antibacterial effect of antibacterial agents is judged by the minimum inhibitory concentration method, and the minimum inhibitory concentration is determined according to 2.1.7.3 of the Ministry of Health Disinfection Technical Specifications (2002 Edition). the

First test the minimum inhibitory concentration (MIC) of the individual components. Each antibacterial agent was diluted with ethanol-water solution (1:1 by volume) as a solvent to a concentration of 10,000ppm, and then the minimum inhibitory concentration of a single component was tested. The test results are listed in Table 2. the

Table 2 The minimum inhibitory concentration (MIC) of a single component of antibacterial agents on bacteria

Then, mix the two antibacterial agents in a 1:1 ratio to obtain a mixed solution, and the concentration of each component in the mixed solution is also 10000ppm. The minimum inhibitory concentration method is also used to test the compound components. minimum inhibitory concentration. the

In this test, the antibacterial synergistic effect of the two antibacterial compound components was evaluated by referring to the fractional inhibitory concentration index method (fractional inhibitory concentration, FIC) commonly used in combination with antibiotics. the

The formula for calculating the FIC index is:

The FIC index calculated by people according to the above formula can determine the interaction between the components of the compound of A and B. When FIC≤0.5, the two components A and B show synergistic effect; when 0.5<FIC≤1, the two components A and B show superimposed effect; when 1<FIC<2, the two components A and B show irrelevance. When FIC≥2, components A and B exhibit antagonistic effects. The MIC and FIC results of the two compound components of the zeolite silver-loaded zinc antibacterial agent and the zirconium phosphate silver-loaded antibacterial agent of the present invention are listed in Table 3. the

Table 3: Minimum Inhibitory Concentration (MIC) of the antibacterial agent compound components of the present invention to bacteria

And the graded inhibitory concentration index (FIC) between the compound components

Generally, a material whose minimum inhibitory concentration against bacteria is less than 800ppm can be considered as having antibacterial properties. For example, the minimum inhibitory concentration specified in the industry standard HG/T3794-2005 "Inorganic Antibacterial Agents - Performance and Evaluation" must be less than 800ppm. As can be seen from the results of the minimum inhibitory concentration (MIC) of the single antibacterial component of Table 2, the minimum inhibitory concentration of the selected antibacterial component of the present invention is all far less than 800ppm, so all have shown good bacteriostatic activity . The results in Table 3 show that, compared with the effect of a single antibacterial agent component, the minimum inhibitory concentrations of the components of the antibacterial agent system after compounding are all reduced more. Judging the interaction between the two antibacterial agent components according to the graded bacteriostatic concentration index method, for two kinds of bacteria, the FIC index of the selected two antibacterial agents is all less than 0.5, which shows that the selected composite components of the present invention all have Synergistic, and the synergistic effect is very good. the

2. Antibacterial persistence

The antibacterial polyester fiber fabric produced by the method of the invention has long-term antibacterial property and excellent washing resistance. Compared with the antibacterial polyester fiber prepared by the post-finishing method, the water resistance is obviously improved, and the antibacterial rate is still greater than 98% after 30 times of washing. Generally, the antibacterial polyester fiber or fabric produced by post-finishing method is difficult to keep the antibacterial rate above 90% after washing for 30 times. the

The test refers to the washing procedure of FZ/T 73023-2006 "Antibacterial Knitwear Appendix C Antibacterial Fabric Sample Washing Test Method", and the test results are listed in Table 4. the

Table 4: Antibacterial effect of polyester antibacterial fabrics prepared by different methods after washing 30 times

It can be seen from the results in Table 4 that the antibacterial polyester prepared by the present invention not only has excellent antibacterial effect, but also has very good washability. After 30 washes, the antibacterial performance can still be maintained above 99%. It is far superior to the fabric prepared by the conventional post-finishing method. As can be seen from the above table, the fabric prepared by the post-finishing method is washed 30 times. The antibacterial performance drops very seriously. the

3. Security

According to the test method stipulated in Ministry of Public Health Disinfection Technical Standard (2002 edition) 2.3.3, the antibacterial polyester fiber fabric produced by the inventive method is carried out skin irritation test:

The experimental animals are New Zealand white rabbits weighing 2.13-2.69 kg. the

The test results are listed in Table 5. the

Table 5: Skin irritation test results of antibacterial polyester fiber fabrics

The test result listed in table 5 shows that the antibacterial polyester fiber fabric produced by the inventive method is non-irritating to the skin. the

[beneficial effect]

The beneficial effects of the present invention are:

The antibacterial polyester fiber produced by the method of the invention has long spinning cycle and very good spinnability. The pressure filter value (DF value) of the antibacterial masterbatch of the present invention is less than 2.0×10 ⁵ Pa·cm ² /g; the cycle of changing the screen is ≥1 piece/12 hours, and the cycle of changing the components is ≥15 days. However, the antibacterial masterbatch system of the prior art is used to prepare antibacterial polyester fibers with a screen change cycle of ≥1 piece/8 hours and a component change cycle of ≥6 days.

After the antibacterial polyester fiber produced by the method of the invention is woven into a fabric, the antibacterial rate against Escherichia coli, Staphylococcus aureus and Candida albicans is more than 99%. the

The antibacterial polyester fiber fabric produced by the method of the invention has long-term antibacterial properties, excellent washing resistance, and obviously improved water resistance, and the antibacterial rate is still greater than 98% after 30 times of washing. Generally, the antibacterial polyester fiber or fabric produced by post-finishing method is difficult to keep the antibacterial rate above 90% after washing for 30 times. the

The antibacterial polyester fiber fabric produced by the method of the invention has no irritation to the skin. the

【Detailed ways】

The present invention will be better understood by the following examples. the

Embodiment 1: produce antibacterial polyester fiber

The implementation steps are as follows:

A. Preparation of antibacterial masterbatch

The zirconium phosphate silver-loaded silver antimicrobial agent of 2.8% of the silver content that 10 parts by weight of Shanghai Runhe Company produces, the zeolite silver-loaded zinc antimicrobial agent of silver content 0.2% and zinc content 3.5% of 10 parts by weight of Beijing Sublime Nano Co., Ltd. In the SHR-10A type mixer produced by Zhangjiagang Chuangjia Machinery Co., Ltd., add 0.2 parts by weight of discoloration inhibitor natural hydrotalcite, and process it for 15min under the condition of mixer rotating speed 3000rpm; then add 2 parts by weight of coupling dispersant ethylene Base triethoxysilane, mix 5min under the condition of rotating speed 500rpm, obtain a kind of mixture that contains antibacterial agent; Mix for 4 minutes under the condition of 500rpm, mix the materials evenly, release the materials, add them to the TE-65 twin-screw extruder produced by Nanjing Keya, and perform granulation under the following conditions to obtain an antibacterial masterbatch: The temperature is 240°C, the temperature in the second and third zones is 250°C, the temperature in the fourth, fifth, and sixth zones is 260°C, the temperature in the seventh and eighth zones is 250°C, and the temperature of the machine head is 245°C , the feeding is 20Hz, and the host speed is 220rpm. the

B. Preparation of antibacterial polyester fiber

Add 4 parts by weight of the antibacterial masterbatch prepared in the above step A) to 96 parts by weight of PET resin sold by Sinopec Yizheng Chemical Fiber Co., Ltd., and spin by melt spinning to obtain a polyester fiber with antibacterial function. the

Embodiment 2: produce antibacterial polyester fiber

The implementation steps are as follows:

A. Preparation of antibacterial masterbatch

5 parts by weight of zirconium phosphate-loaded silver antimicrobial agent with silver content of 3.0% produced by Shanghai Runhe Company, 15 parts by weight of zeolite-loaded silver-zinc antimicrobial agent with silver content of 0.3% and zinc content of 2.0% produced by Haier Kehua Company were added to Zhangjiagang In the SHR-10A mixer produced by City Chuangjia Machinery Co., Ltd., add 0.015 parts by weight of the discoloration inhibitor alumina magnesium calcined product [Mg _0.7 Al _0.6 O _1.15 ], and process it for 10 minutes at the mixer speed of 2800 rpm; then add 0.3 parts by weight of coupling dispersant distearoyloxyisopropyl aluminate, mixed for 3min under the condition of rotating speed 500rpm, to obtain a mixture containing antibacterial agent; finally, the mixture was mixed with 90 parts by weight of PetroChina Liaoyang The PET polyester chips sold by the petrochemical company are mixed for 3 minutes at a speed of 600rpm, the materials are mixed evenly, and the materials are released, and then added to the TE-65 twin-screw extruder produced by Nanjing Keya for granulation under the following conditions , to obtain an antibacterial masterbatch: the temperature in the first zone is 240°C, the temperature in the second and third zones is 250°C, the temperature in the fourth, fifth, and sixth zones is 255°C, and the temperature in the seventh and eighth zones is 250°C. The temperature of the machine is 245°C, the temperature of the head is 240°C, the feeding is 20Hz, and the speed of the host is 210rpm.

B. Preparation of antibacterial polyester fiber

Add 10 parts by weight of the antibacterial masterbatch prepared in the above step A) to 90 parts by weight of PET resin sold by Liaoyang Petrochemical Company of PetroChina, and spin by melt spinning to obtain a polyester fiber with antibacterial function. the

Embodiment 3: produce antibacterial polyester fiber

The implementation steps are as follows:

A. Preparation of antibacterial masterbatch

Zirconium phosphate silver-loaded antimicrobial agent with 3.0% silver content of 15 parts by weight of the trade name zeomic produced by Toya Synthesis in Japan, 5 parts by weight of zeolite silver-loaded zinc with silver content of 0.3% and zinc content of 2.0% produced by Beijing Sublime Nano Co., Ltd. Add the antibacterial agent to the SHR-10A mixer produced by Zhangjiagang Chuangjia Machinery Co., Ltd., and then add 0.6 parts by weight of discoloration inhibitor, 1 part by weight of aluminum silicate and 1 part by weight of natural hydrotalcite. Treat for 30 minutes; then add 0.6 parts by weight of aluminum-titanium composite coupling dispersant and mix for 4 minutes at a speed of 600 rpm to obtain a mixture containing an antibacterial agent; finally, sell the mixture with 75 parts by weight of Sinopec Yizheng Chemical Fiber Co. PET polyester chips were mixed for 5 minutes under the condition of rotating speed 600rpm, the materials were mixed evenly, and the materials were discharged, added to the TE-65 twin-screw extruder produced by Nanjing Keya, and granulated under the following conditions to obtain a Antibacterial masterbatch: the temperature in the first zone is 240°C, the temperature in the second and third zones is 250°C, the temperature in the fourth, fifth, and sixth zones is 265°C, and the temperature in the seventh and eighth zones is 255°C ℃, head temperature is 245 ℃, feeding is 20Hz, host speed is 230rpm. the

B. Preparation of antibacterial polyester fiber

Add 2 parts by weight of the antibacterial masterbatch prepared in the above step A to 98 parts by weight of PET resin sold by Sinopec Yizheng Chemical Fiber Co., Ltd., and spin by melt spinning to obtain a polyester fiber with antibacterial function. the

The antibacterial polyester fibers prepared in Examples 1-3 were subjected to the following antibacterial tests. the

1. Antibacterial properties:

According to the standard test of AATCC100-2004 "Performance Evaluation of Antibacterial Finishing of Textile Materials", the results are listed in Table 4:

Table 4: Antibacterial test results of antibacterial polyester fiber

2. Antibacterial persistence:

Refer to the washing procedure of FZ/T 73023-2006 "Antibacterial Knitwear Appendix C Antibacterial Fabric Sample Washing Test Method", after washing the antibacterial fiber 30 times, the antibacterial results are listed in Table 5. the

Table 5 Antibacterial effect of antibacterial polyester fiber after washing 30 times

3. Security:

According to the skin irritation test method stipulated in 2.3.3 of the Ministry of Health Disinfection Technical Specifications (2002 Edition). the

The experimental animals are New Zealand white rabbits weighing 2.13-2.69 kg. the

These tests have fully proved that the antibacterial polyester fibers produced in Examples 1, 2, and 3 are nonirritating to the skin. the

Embodiment 4: produce antibacterial polyester fiber

The implementation steps are as follows:

A. Preparation of antibacterial masterbatch

The production brand of 1 weight part lofty Nano Co., Ltd. is the zirconium phosphate silver-loaded antimicrobial agent of silver content 2.8% of AMR, and 20 weight parts of Beijing lofty nano company production brand is the zeolite silver-loaded silver content of 0.2% and zinc content 3.5% of AM. Add the zinc antibacterial agent to the SHR-10A mixer produced by Zhangjiagang Chuangjia Machinery Co., Ltd., and then add 2 parts by weight of the discoloration inhibitor benzotriazole (CAS 95-14-7). Under the condition of the mixer speed of 3000rpm Treat 15min; Then add 0.8 parts by weight coupling dispersant gamma-aminopropyltriethoxysilane, mix 5min under the condition of rotating speed 500rpm, obtain a kind of mixture that contains antibacterial agent; Finally, described mixture and 85 The PET polyester chips sold by Sinopec Yizheng Chemical Fiber Co., Ltd. are mixed for 4 minutes at a rotating speed of 500rpm. The materials are mixed evenly, and the materials are released, and added to the TE-65 twin-screw extruder produced by Nanjing Keya under the following conditions Granulate under the following conditions to obtain an antibacterial masterbatch: the temperature in the first zone is 240°C, the temperature in the second and third zones is 250°C, the temperature in the fourth, fifth, and sixth zones is 260°C, and the temperature in the seventh zone The temperature of zone 8 and zone 8 is 250°C, the temperature of the machine head is 245°C, the feeding is 20Hz, and the speed of the host machine is 220rpm. the

B. Preparation of antibacterial polyester fiber

Add 6 parts by weight of the antibacterial masterbatch prepared in the above step A) to 94 parts by weight of PET resin sold by Sinopec Yizheng Chemical Fiber Co., Ltd., and spin by melt spinning to obtain a polyester fiber with antibacterial function. the

Embodiment 5: produce antibacterial polyester fiber

The implementation steps are as follows:

A. Preparation of antibacterial masterbatch

Add 20 parts by weight of zirconium phosphate-loaded silver-loaded silver antibacterial agent with silver content of 3.0% produced by Shanghai Runhe Company, and 1 weight part of zeolite-loaded silver-loaded zinc antibacterial agent with silver content of 0.3% and zinc content of 2.0% produced by Haier Kehua Company to Zhangjiagang In the SHR-10A mixer produced by City Chuangjia Machinery Co., Ltd., add 1 weight part of discoloration inhibitor tolyltriazole potassium, and process it for 10 minutes at the mixer speed of 2800rpm; then add 0.5 weight part of coupling dispersion Agent DL-411, mix 3min under the condition of rotating speed 500rpm, obtain a kind of mixture that contains antibacterial agent; Finally, the PET polyester chip that described mixture is sold with 82 parts by weight of PetroChina Liaoyang Petrochemical Company, at rotating speed is 600rpm Mix under the following conditions for 3 minutes, mix the materials evenly, release the materials, add them to the TE-65 twin-screw extruder produced by Nanjing Keya, and perform granulation under the following conditions to obtain an antibacterial masterbatch: the temperature in the first zone is 240°C, the temperature in the second and third zones is 250°C, the temperature in the fourth, fifth, and sixth zones is 255°C, the temperature in the seventh and eighth zones is 245°C, and the temperature of the machine head is 240°C. The material is 20Hz, and the host speed is 210rpm. the

B. Preparation of antibacterial polyester fiber

8 parts by weight of the antibacterial masterbatch prepared by the above steps A are added to 92 parts by weight of the PET resin sold by PetroChina Liaoyang Petrochemical Company, and the melt spinning method is used to spin to obtain a polyester fiber with antibacterial function. the

Embodiment 6: produce antibacterial polyester fiber

The implementation steps are as follows:

A. Preparation of antibacterial masterbatch

The zirconium phosphate silver-loaded silver-loaded antibacterial agent of the silver content 3.0% that 15 parts by weight of Japanese SR trading companies are produced, 5 parts by weight of the zeolite silver-loaded zinc antimicrobial agent that the silver content 0.3% and the zinc content 2.0% of the silver content of AM of AM company production are added To the SHR-10A mixer produced by Zhangjiagang Chuangjia Machinery Co., Ltd., add 0.6 parts by weight of the discoloration inhibitor methyl benzotriazole (CAS 21412-99), and process it for 30 minutes at the mixer speed of 3000rpm; then Add 0.6 parts by weight of isopropyl tristearate titanate, mix 4min under the condition of rotating speed 600rpm, obtain a kind of mixture that contains antibacterial agent; PET polyester chips, mixed for 5 minutes under the condition of rotating speed 600rpm, the materials were mixed evenly, and the materials were discharged, added to the TE-65 twin-screw extruder produced by Nanjing Keya, and granulated under the following conditions to obtain an antibacterial Masterbatch: The temperature in the first zone is 240°C, the temperature in the second and third zones is 250°C, the temperature in the fourth, fifth, and sixth zones is 265°C, and the temperature in the seventh and eighth zones is 255°C , the head temperature is 245°C, the feeding is 20Hz, and the host speed is 230rpm. the

B. Preparation of antibacterial polyester fiber

Add 2 parts by weight of the antibacterial masterbatch prepared in the above step A to 98 parts by weight of PET resin sold by Sinopec Yizheng Chemical Fiber Co., Ltd., and spin by melt spinning to obtain a polyester fiber with antibacterial function. the

Claims (10)

1. a production method of antibacterial polyester fiber, characterized in that the steps of the production method are as follows: A. Preparation of antibacterial masterbatch In the mixer, use 0.015-2 parts by weight of anti-tarnish treatment agent to carry out surface anti-tarnish treatment to 1-20 parts by weight of zeolite silver-loaded zinc antibacterial agent and 1-20 parts by weight of zirconium phosphate-loaded silver antibacterial agent, and then add 0.3-1 Continue to process the coupling dispersant in parts by weight to obtain a mixture containing an antibacterial agent; then, mix the mixture with 75-90 parts by weight of polyester resin, and then use a twin-screw extruder at a heating temperature of 240-265°C 1. Under the conditions of host speed 200-230 rpm and feeding 18-24Hz, melt extrusion is carried out to obtain an antibacterial masterbatch; B, preparation of antibacterial polyester fiber Weigh 2-10 parts by weight of the antibacterial masterbatch prepared in step A and 90-98 parts by weight of polyester resin, and spin by melt spinning to obtain the antibacterial polyester fiber; The coupling dispersant is one or more coupling dispersants selected from silane series, aluminate series, titanate series or bimetallic composite coupling dispersants; The anti-tarnish treatment agent is one or more selected from benzotriazole, tolyltriazole, potassium tolyltriazole, natural hydrotalcite, synthetic hydrotalcite, calcined alumina magnesium or silicon Anti-tarnish treatment agent for acid aluminum. 2. The production method according to claim 1, characterized in that the silane series coupling dispersant is a compound of the following formula: R _n SiX _(4-n) In the formula: n=1~3; R is a methyl, vinyl, amino, epoxy, mercapto or acryloxypropyl functional group; X is an alkoxy, aryloxy, acyl or chloro group. 3. The production method according to claim 1, characterized in that the aluminate series is selected from distearoyloxyisopropyl aluminate, trimethyl aluminate, triisopropyl aluminate or aluminate Tribenzyl ester. 4. The production method according to claim 1, characterized in that the titanate series are compounds of the following formula: ROO _(4-n) Ti(OX-R'Y) _n In the formula: n=2 or 3; RO is a hydrolyzable short-chain alkoxy functional group; OX is a carboxyl, alkoxy, sulfonic or phosphoryl group. 5. The production method according to claim 1, characterized in that the bimetallic composite coupling agent is an aluminum-titanium composite coupling agent or an aluminum-zirconium composite coupling agent. 6. The production method according to claim 1, characterized in that the surface anti-tarnish treatment is carried out for 10-30 minutes at the mixer speed of 2800-3000rpm. 7. The production method according to claim 1, characterized in that the treatment of the coupling dispersant is at the mixer speed of 500-600rpm for 3-5 minutes. 8. The production method according to claim 1, characterized in that the polyester resin is mixed for 3-5 minutes at a mixer speed of 500-600 rpm. 9. The antibacterial polyester fiber produced according to the method described in any one of claims 1-8. 10. according to the purposes of the described antibacterial polyester fiber of claim 9 in anti-escherichia coli, Staphylococcus aureus and Candida albicans.