CN111663221A - Preparation method of antibacterial yarn without remarkably reducing yarn breaking strength, antibacterial yarn and antibacterial fabric - Google Patents
Preparation method of antibacterial yarn without remarkably reducing yarn breaking strength, antibacterial yarn and antibacterial fabric Download PDFInfo
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- CN111663221A CN111663221A CN202010500493.0A CN202010500493A CN111663221A CN 111663221 A CN111663221 A CN 111663221A CN 202010500493 A CN202010500493 A CN 202010500493A CN 111663221 A CN111663221 A CN 111663221A
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/449—Yarns or threads with antibacterial properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
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- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a preparation method of antibacterial yarns without remarkably reducing the breaking strength of the yarns, and the antibacterial yarns and antibacterial fabrics thereof. The preparation method of the antibacterial yarn which does not remarkably reduce the breaking strength of the yarn comprises the following steps: 1) carrying out first mixing treatment on polymer matrix resin and a binder to obtain a mixture A of the polymer matrix resin with the binder spread on at least part of the surface; 2) adding an inorganic antibacterial agent into the mixture A, and carrying out second mixing treatment to obtain a mixture B of a polymer matrix resin, at least part of the surface of which is spread with a binder and adhered with the inorganic antibacterial agent; 3) spinning the mixture B according to a conventional yarn preparation process to prepare the antibacterial yarn with the surface and the interior uniformly dispersed with the inorganic antibacterial agent.
Description
Technical Field
The invention relates to an antibacterial yarn and an antibacterial fabric, in particular to a preparation method of the antibacterial yarn, the antibacterial yarn and the antibacterial fabric, wherein the preparation method of the antibacterial yarn does not remarkably reduce the breaking strength of the yarn.
Background
The antibacterial agent is combined with the textile yarn, so that the yarn has the capability of inhibiting the growth and reproduction of bacteria or killing the bacteria to make the yarn lose activity, and the yarn is the antibacterial yarn. And mixing the antibacterial yarns with the yarns without the antibacterial agent according to a certain proportion to obtain the antibacterial fabric. According to the national standard GB/T20944.2-2007 evaluation part 2 of the antibacterial performance of textiles: and (3) an absorption method is adopted to test the bacteriostasis rate of the antibacterial fabric to bacteria, wherein the bacteria mainly comprise escherichia coli and staphylococcus aureus … …. The preparation method of the antibacterial yarn can be divided into three main categories:
1. a melt spinning method: firstly, preparing proper antibacterial agent and matrix resin slices/particles into antibacterial master batch according to a certain process. The master batch is the concentrated carrier of the antibacterial agent. Secondly, in the production process of the yarn, the master batch and common antibacterial agent-free resin slices/particles are fully and uniformly mixed according to a certain mass ratio, and are subjected to melt spinning together to obtain the yarn containing the antibacterial agent. However, the method of preparing the master batch and then melt spinning has disadvantages that the antibacterial master batch and the common sliced particles are large, only macroscopic collision is caused and microcosmic contact is avoided in the mixing process, and the antibacterial agent is difficult to be uniformly dispersed in textile equipment due to short retention time and limited mixing degree. In addition, the method needs to add mixing and stirring equipment and power equipment before spinning, and the production cost is increased.
2. Post-finishing method: for the produced common yarn which does not contain the antibacterial agent, the antibacterial agent is combined on the surface of the yarn through the processes of a surface coating method, a resin finishing method and the like, the combination can be realized through simple physical adsorption or reaction connection of surface chemical groups, and is also called grafting, so that the surface of the common yarn has an antibacterial function. The post-finishing method usually uses an organic antibacterial agent, and has simple and flexible process and wide application range. The most important disadvantages are: firstly, in the process of combining the antibacterial agent and the yarn, the natural fibers and the synthetic fibers with different chemical compositions have great surface property differences, and the effective components of the antibacterial agent and the surface acting force thereof have strong or weak strength, so that the adhesive strength is difficult to control; secondly, in the using process of the yarn or fabric product, the antibacterial agent exists on the surface of the yarn or fabric, the adsorption strength is weak or the chemical bond connection is not firm, and after multiple times of abrasion or water washing, the antibacterial agent is easy to fall off from the surface of the yarn, so that the antibacterial capability of the antibacterial yarn is gradually reduced along with the falling of the antibacterial agent. Another disadvantage of afterfinishes is that the retention of the antimicrobial active is not stable, depending on the anisotropy of the yarn surface properties.
3. Fiber blending spinning method: and (3) adding an antibacterial agent and a dispersing agent into the spinning solution, and uniformly mixing to obtain the spinning solution. The method can realize one-step preparation of the antibacterial fiber. The main defects are as follows: firstly, the process is not flexible, the antibacterial agent and the dispersing agent must be added into the stock solution, and the addition amount must be strictly controlled at a very low proportion, because the added antibacterial agent and the dispersing agent have great influence on the physical properties of the spinning stock solution; and secondly, the inorganic antibacterial agent particles added simultaneously are easy to abrade the stirring device in the reactor along with the stirring in the reaction kettle, so that the equipment is abraded to a certain extent, and the inorganic antibacterial agent particles are another factor for strictly limiting the addition proportion of the antibacterial agent.
The application of the antibacterial yarn comprises the following steps: the antibacterial yarn has a high-efficiency antibacterial effect, and the fabric with the antibacterial function can be obtained according to the production process of the textile fabric. In addition, the antibacterial yarns and the common yarns which do not contain the antibacterial agent are prepared into the fabric according to a certain mass ratio, and the obtained mixed fabric has high-efficiency antibacterial capability.
Chinese patent CN110512297A discloses a method for manufacturing high-efficiency antibacterial fiber, which comprises three steps of preparation of antibacterial master batch, preparation of antibacterial fiber and preparation of antibacterial FDY fiber filaments. The efficient antibacterial fiber is prepared by utilizing the characteristics of small crystal size, large specific surface area, high silver-carrying capacity and the like of the nano silver-carrying molecular sieve.
Chinese patent CN110424087A discloses an antibacterial fiber fabric, the preparation method of which comprises: the antibacterial fiber fabric is prepared by preparing an antibacterial fiber solution from a natural antibacterial substance and a proper amount of auxiliary agent, preparing antibacterial composite fiber yarns through wet spinning, coagulating and washing, drafting and winding, twisting the antibacterial composite fiber yarns into yarns, and weaving.
Chinese patent CN110106575A discloses a method for preparing high-strength improved antibacterial fiber. The single carboxyl chitosan powder prepared by a specific method is reacted with raw and auxiliary materials such as polyester materials, and the high-strength improved antibacterial fiber is prepared by the processes of preparing a gel mixture, granulating, high-voltage electrostatic spinning, washing and the like.
Disclosure of Invention
The invention aims to provide a preparation method of antibacterial yarns without remarkably reducing the breaking strength of the yarns, the antibacterial yarns and an antibacterial fabric. The preparation method realizes the uniform dispersion of the inorganic antibacterial agent in the fiber polymer, can realize the stable and durable antibacterial performance of the yarn by adding a very small amount of the inorganic antibacterial agent, and can ensure that the breaking strength of the antibacterial yarn is not remarkably reduced by adding the inorganic antibacterial agent because inorganic antibacterial agent particles are uniformly dispersed due to the small addition amount.
In a first aspect, the present invention provides a method for preparing an antimicrobial yarn without significantly reducing the breaking strength of the yarn, comprising the steps of:
firstly, carrying out first mixing treatment on polymer matrix resin and a binder to obtain a mixture A of the polymer matrix resin with the binder spread on at least part of the surface;
secondly, adding an inorganic antibacterial agent into the mixture A, and carrying out second mixing treatment to obtain a mixture B of a polymer matrix resin, at least part of the surface of which is spread with a binder and the inorganic antibacterial agent is adhered;
and finally, spinning the mixture B according to a conventional yarn preparation process to prepare the antibacterial yarn with the inorganic antibacterial agent uniformly dispersed on the surface and in the yarn.
Preferably, the inorganic antibacterial agent has a dispersion size of 300nm or less in the antibacterial yarn. The method realizes the uniform dispersion of the inorganic antibacterial agent in the fiber polymer in the size form with the grain diameter of less than 300nm, so that the obtained antibacterial yarn has stable and lasting antibacterial effect. If the dispersion size of the inorganic antibacterial agent in the antibacterial yarn is larger than 300nm, two technical defects are mainly caused, firstly, the antibacterial agent is wasted due to the fact that the inorganic antibacterial agent particles are too large, and the antibacterial agent agglomerated inside the particles cannot play an antibacterial function; secondly, the mechanical properties of the yarn, including the breaking strength, are significantly reduced.
The preparation method of the invention enables the inorganic antibacterial agent to be in full contact with the polymer matrix resin on a microscopic scale, and combines the physical and chemical characteristics of the selected binder, so that the dispersion size of the inorganic antibacterial agent in the yarn can reach below 300 nm.
The dispersion size of the inorganic antibacterial agent in the antibacterial yarn is preferably 100-300 nm. The dispersion size can not obviously reduce the breaking strength of the antibacterial yarns, and meanwhile, the stability and the reliability of the antibacterial effect can be completely ensured through more sufficient dispersion. The key point for realizing the control of the dispersed particle size is that the core process step of the preparation method is combined with the physical and chemical characteristics and the dosage of the selected binder, so that the antibacterial agent is fully contacted with the matrix resin on a microscopic scale, and the aim of full dispersion is fulfilled. If the dispersion size is less than 100nm, this causes a significant increase in production cost.
Preferably, the preparation method does not comprise: before spinning, preparing the antibacterial master batch by using raw materials comprising polymer matrix resin, a binder and an inorganic antibacterial agent. The step of preparing the master batch not only causes the complicated preparation steps and the increase of the cost, but also has the defect that the antibacterial master batch and the common sliced particles are large, only macroscopic collision and microcosmic contact are caused in the mixing process, and even if the contact and mixing time in spinning equipment is limited, the uniform distribution of the antibacterial agent is difficult to ensure.
Preferably, the polymer matrix resin is in the shape of chips and/or particles.
Preferably, the polymer matrix resin is a polyester polymer and/or a polyamide polymer; the polyester polymer is at least one of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; the polyamide polymer is at least one of polyamide 6, polyamide 66, polyamide 610 and polyamide 1010.
Preferably, the inorganic antibacterial agent accounts for 0.2-1.0% of the oven-dry mass ratio of the high-efficiency antibacterial yarn.
Preferably, the particle size of the inorganic antibacterial agent itself is 25 to 350nm, preferably 30 to 100 nm. The size of the inorganic antimicrobial agent itself is different from the dispersion size of the inorganic antimicrobial agent in the yarn product (less than 300nm, preferably 200 nm).
In a first aspect, the invention further provides the antibacterial yarn obtained by the preparation method of the high-efficiency antibacterial yarn which does not significantly reduce the breaking strength of the yarn.
The macro-morphological structure of the antibacterial yarn comprises a skin-core structure and a circular, oval and spiral section morphological structure; preferably, the macro-morphological structure of the antibacterial yarn is a skin-core structure, and the cross section of the antibacterial yarn is circular; more preferably, in the antibacterial yarn of the skin-core structure, the inorganic antibacterial agent is distributed on the surface layer of the skin-core structure, and the core layer does not contain the inorganic antibacterial agent.
In a third aspect, the invention further provides an antibacterial fabric, wherein the yarn raw material of the antibacterial fabric comprises the antibacterial yarn, and the antibacterial yarn accounts for 20-100% of the yarn raw material by mass. According to the national standard GB/T20944.2-2007 evaluation part 2 of the antibacterial performance of textiles: by the absorption method, the antibacterial rate of the antibacterial fabric to escherichia coli and staphylococcus aureus is greater than 99%.
Drawings
FIG. 1 is a flow chart of the preparation of a high-efficiency antibacterial yarn according to an embodiment of the present invention; wherein, 1 is dried polymer matrix resin slice/particle, 2 is adhesive, 3 is inorganic antibacterial agent;
FIG. 2 is a cross-sectional SEM photograph of the antimicrobial yarn of example 1;
FIG. 3 is a cross-sectional SEM image of the antimicrobial yarn of example 2;
fig. 4 is a cross-sectional SEM image of the antimicrobial yarn of example 3.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive. Unless otherwise specified, each percentage is a mass percentage unless otherwise specified.
The following exemplifies a method for preparing a highly effective antibacterial yarn without decreasing the breaking strength of the yarn.
First, a raw material of the antibacterial yarn is selected. The antibacterial yarn at least comprises three raw materials which are respectively as follows: polymer matrix resin chips/particles, inorganic antimicrobial agents and binders.
The raw materials are preferably subjected to drying and water removal treatment in advance, and oven drying can be adopted. In some embodiments, the required parts of the raw materials are weighed based on 100 parts of all raw materials by mass. The invention discloses a high-efficiency antibacterial yarn without reducing the breaking strength of the yarn, which comprises the following raw materials in parts by weight, 97-99.76 parts of polymer matrix resin slices/particles and inorganic antibacterial agents: 0.2-1.0 part of binder: 0.04-1.0 part. In some embodiments, the inorganic antimicrobial agent is preferably 0.2 to 0.4 parts.
In addition, the addition amount of the inorganic antibacterial agent is related to the breaking strength of the antibacterial yarn. If the addition amount of the inorganic antibacterial agent is too large, the content of the inorganic antibacterial agent on the cross section of the yarn is easily higher, so that the breaking strength of the yarn is reduced; meanwhile, the inorganic antibacterial agent is easy to disperse poorly, the aggregate is large, and the breaking strength of the yarn is further reduced remarkably.
The polymer matrix resin chips/particles can be selected from common high molecular polymers which can form a flowing melt after the temperature reaches the melting temperature. The invention preferably comprises the following components: polyesters: polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and the like; polyamides: polyamide 6(PA6), polyamide 66(PA66), polyamide 610(PA610), polyamide 1010(PA 1010).
The inorganic antibacterial agent can be selectedUsing CuO, ZnO, TiO2、SiO2、、WO3And the like, and mixtures of one or more of them.
The inorganic antibacterial agent has an average particle size of 25nm to 350nm, preferably 30 to 100 nm.
The inorganic antibacterial agent can be prepared without any surface modifier, coupling agent, surfactant and the like; or surface-treated with a surface modifier, a coupling agent, a surfactant, or the like. Wherein the coupling agent is preferably selected from silane-based vinyltriethoxysilane (CAS number: 78-08-0, optionally Wacker chemical), gamma-aminopropyltriethoxysilane (KH550, optionally Japanese shin-Etsu chemical), gamma-methacryloxypropyltrimethoxysilane (KH570), N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane (KH792, CAS number: 1760-24-3), etc., and titanate coupling agent, can be selected from bis (dioctyloxypyrophosphate) ethylene titanate (CAS number: 65467-75-6), isopropyl tri (dioctylpyrophosphate) titanate (CAS number: 67691-13-8), and di (acetylacetone) (ethoxy) isopropyl titanate (CAS number: 445398-76-5). The amount of the silane coupling agent, titanate coupling agent, aluminate coupling agent or rare earth coupling agent added is 0.5 to 20%, preferably 0.5 to 3% with respect to the mass of the inorganic antibacterial agent.
The binder used in the present invention has the following characteristics: the liquid is liquid with better fluidity at normal temperature, has higher boiling point, is non-volatile, does not decompose and carbonize at the melting temperature of the polymer, and has stable chemical property; while having an affinity for the selected matrix resin chips/particles and dispersant particles. When the base resin slices/particles and the dispersing agent are in a molten state, the adhesive has good compatibility and affinity with the melt; meanwhile, the adhesive has better affinity to the inorganic antibacterial agent and is easy to spread on the inorganic antibacterial agent.
In the present invention, the binder may be selected from: polyhydric alcohol or polyalcohol, such as glycerol (water content < 1%), polyethylene glycol (water content < 1%), optionally PEG-200, PEG-300, PEG-400, PEG-600, PEG-800, PEG-1000, and PEG-1500; polyvinyl alcohol (water content < 1%) can be selected from SevolTM 165SF,205S of Japan waterlogging chemistry; esters of polyols, polyester polyols, optionally: propylene glycol methyl ether acetate PMA (CAS number: 108-65-6), or hydrocarbon mixture with carbon number of 12-36, such as liquid paraffin (distillation temperature >300 deg.C, CAS number: 8042-47-5, optionally Macelin product), white wax (distillation temperature 150-.
The present invention preferably uses several types of adhesives as described above because: 1. the decomposition of matrix resin or the reduction of the yarn quality in the yarn production process caused by the overhigh water content in the binder is avoided, and 2, the poor dispersibility of the inorganic antibacterial agent in the yarn caused by the overlow boiling point of certain binder components is avoided; 3. the binder is prevented from having color or changing color in the granulation process; 4. from the perspective of ecological and physiological safety, the side effect of toxic and side effects of the binder on downstream products or ecological environment is avoided.
The invention can efficiently spread on the surfaces of polymer matrix resin slices/particles, dispersant particles and inorganic powder particles by reasonably selecting the anhydrous liquid binder, and simultaneously, the invention does not generate chemical reaction in the production process of yarns and has no side effect on final products.
The antibacterial masterbatch is a concentrate of the antibacterial agent, wherein the antibacterial agent content is high. In the production process of common antibacterial yarns, a certain proportion of antibacterial master batch needs to be added. That is, the antibacterial base particles contain a large amount of the antibacterial agent, and the ordinary base resin chips/particles do not contain the antibacterial agent. The inorganic antibacterial agent is uniformly adhered to the surface of each base resin slice/particle by the aid of the adhesive, so that the dispersion of the antibacterial agent in the final antibacterial yarn is facilitated. Meanwhile, the production steps of the antibacterial master batch are not carried out, and the process is simpler in general.
In some embodiments, the antibacterial yarn comprises the following raw materials in parts by weight, 97 to 99.76 parts by weight of polymer matrix resin slices/particles, and an inorganic antibacterial agent: 0.2-1.0 part of dispersant: 0-1.0 part of binder: 0.04-1.0 part. The dispersing agent can be polyethylene wax, and preferably has a molecular weight of 1500-5000, and CAS: 9002-88-4, at least one selected from domestic H1001 polyethylene wax, carboxylated polyethylene wax, oxidized polyethylene wax, polyacid, and polycarboxylic acid, preferably with molecular weight of 3000-15000, stearic acid, calcium stearate, zinc stearate, cadmium stearate, and N, N' -ethylene bisstearamide.
Secondly, mixing the required raw materials: polymer matrix resin chips/particles, inorganic antimicrobial agent, dispersant, and removing moisture in a drying apparatus, for example, by oven drying.
Subsequently, mixing of the polymer matrix resin chips/particles, the dispersant particles and the binder is performed. 97-99.76 parts of dried polymer matrix resin slices/particles and 0-1.0 part of dispersing agent are weighed, 0.04-1.0 part of binding agent is added, and the mixture is uniformly mixed in conventional mixing equipment (such as a low-speed mixer and a high-speed mixer). Rotating speed of mixing equipment: 30 to 3000 rpm, preferably 60 to 300 rpm. The purpose is as follows: the adhesive selected by the invention has good affinity with polymer matrix resin slices/particles and dispersant particles, and can be quickly and uniformly spread on the surfaces of the polymer matrix resin slices/particles and the dispersant particles, so that the combination of the polymer matrix resin slices/particles and the dispersant particles with the dried inorganic antibacterial agent is facilitated.
Then, 0.1 to 1.0 part of the dried inorganic antibacterial agent is added to the mixture obtained in the second step, and mixed uniformly in a conventional mixing apparatus (e.g., a low-speed mixer, a high-speed mixer). The mixing device speed is 30-3000 rpm, preferably 60-300 rpm. The purpose is as follows: after the second step, a layer of adhesive is uniformly spread on the surfaces of the polymer matrix resin slices/particles and the dispersing agent particles, and after the dried inorganic antibacterial agent is added, the adhesive can well adhere the inorganic antibacterial agent particles to the surfaces of the polymer matrix resin slices/particles and the dispersing agent particles. The function is as follows: on one hand, the dried inorganic antibacterial agent is adhered to the surfaces of polymer matrix resin slices/particles and dispersing agent particles by the adhesive, so that the problem of dust flying and waste caused by the inorganic antibacterial agent in the mixing process is reduced or solved. On the other hand, the inorganic antibacterial agent powder particles are uniformly adhered to the surfaces of each polymer matrix resin slice/particle and each dispersing agent particle, so that the antibacterial agent content in the finally obtained antibacterial yarn is uniformly distributed.
And finally, producing the antibacterial yarn. The mixture obtained by the steps is as follows: a homogeneous mixture of polymer matrix resin chips/particles, dispersant particles, inorganic antimicrobial agent, binder. The surfaces of each polymer matrix resin chip/particle, dispersant particle are uniformly spread with adhesive and inorganic antibacterial agent is adhered.
Conventional yarns are produced using conventional polymer chips/particles, a conventional operation, and conventional techniques known to those skilled in the textile industry and to those skilled in the art of producing such yarns. According to the invention, the high-efficiency antibacterial yarn without reducing the breaking strength of the yarn can be obtained by the mixture obtained by the steps according to the conventional operation of yarn production.
The preparation process of the antibacterial yarn is simple, no special equipment is needed, and the process is flexible. The antibacterial yarn can be directly produced by using the inorganic antibacterial agent, the binder and the dispersing agent.
The inorganic antibacterial agent of the high-efficiency antibacterial yarn is uniformly distributed in the yarn. In some embodiments, the inorganic antimicrobial agent particles have a dispersed size of about 200 nm. Therefore, the breaking strength of the antibacterial yarn is not reduced in the range of 0.2 to 1.0 part of the inorganic antibacterial agent.
The invention has the following beneficial effects:
1. due to the fact that the size difference between the polymer matrix resin slices/particles and the powder is large, the polymer matrix resin slices/particles and the powder cannot be mixed uniformly and effectively by direct mixing, and therefore the content of the powder in the finally obtained yarn is not uniform. The invention uniformly adheres the powder on the surfaces of polymer matrix resin slices/particles and dispersant particles by means of a proper binder, thereby solving the problem of non-uniform dispersion of the polymer matrix resin slices/particles and the dispersant particles. Meanwhile, by means of a proper dispersing agent, the inorganic antibacterial agent in the finally obtained antibacterial yarn is uniformly dispersed.
2. According to the invention, by means of a proper binder and a proper adding sequence, inorganic antibacterial agent particles are adhered to the surfaces of the polymer matrix resin slices/particles and the dispersing agent particles, so that the problems of antibacterial agent waste and dust flying are effectively reduced.
3. The inorganic antibacterial agent has good dispersion effect in the antibacterial yarn: under the action of the binder, the antibacterial agent powder is uniformly adhered to the surfaces of the polymer matrix resin slices/particles and the dispersing agent particles, and the antibacterial agent powder in the finally obtained antibacterial yarn is uniformly dispersed.
4. Firstly, the binder is added to enable the binder to spread on the surfaces of the polymer matrix resin slices/particles and the dispersing agent particles, and then the dried inorganic antibacterial agent particles are added to effectively and uniformly adhere the inorganic antibacterial agent particles on the surfaces of the polymer matrix resin slices/particles and the dispersing agent particles.
The preparation method disclosed by the invention has the advantages that the inorganic antibacterial agent is uniformly adhered to the surface of each base resin slice/particle, in the production process of the yarn, after the heating temperature reaches the melting temperature of the base resin slices/particles, the base resin slices/particles are melted to form a melt with fluidity, and under the action of mechanical equipment such as screw conveying and filtering, the inorganic antibacterial agent is uniformly dispersed in the melt by virtue of the dispersion effect of the adhesive, so that the inorganic antibacterial agent is uniformly dispersed in the finally obtained yarn.
The macro-morphological structure of the antibacterial yarn can be round, oval, spiral, skin-core structure and the like. The antibacterial yarn can be further used for textile fabrics, and the preferable macro-morphological structure is a skin-core structure, and the cross section of the antibacterial yarn is circular. The effective antibacterial component of the antibacterial yarn of the skin-core layer structure is preferably distributed on the surface layer of the skin-core structure, and the core layer does not contain the inorganic antibacterial component.
The antibacterial yarn with the skin-core layer structure can be prepared by a co-extrusion wire-drawing mode of a high-speed spinning machine. It is understood that the skin and core polymeric materials, crystallinity, etc. may differ. The thickness of the skin layer of the yarn with the skin-core layer structure is preferably 0.2-2 μm, or 0.1-5 μm, or 0.5-10 μm, or 1-20 μm.
Ordinary yarns without the antibacterial agent can be prepared into fabrics of various styles according to the "textile materials science (fourth edition)" published by the Chinese textile Press, which is a conventional technology known by technical personnel and production personnel in the textile industry.
The high-efficiency antibacterial textile fabric can be obtained by spinning the antibacterial yarn. The mass percentage of the antibacterial yarn in the fabric raw material can be 20-100%. The oven-dry mass percentage of the inorganic antibacterial agent in the finally obtained antibacterial fabric can be 0.2-1.0%.
The high-efficiency antibacterial property of the fabric depends on the dispersibility of the inorganic antibacterial agent. The better the dispersibility is, the better the antibacterial effect of the fabric is. The antibacterial fabric is obtained according to the invention, and according to the evaluation part 2 of antibacterial performance of textiles in the national standard GB/T20944.2-2007: and (3) an absorption method is adopted to test the antibacterial rate of the fabric to escherichia coli and staphylococcus aureus. The antibacterial agents for escherichia coli and staphylococcus aureus are both more than 99 percent, and the fabric is efficient antibacterial fabric.
The invention adopts the following method to characterize the distribution of the inorganic antibacterial agent in the antibacterial yarn. The invention uses ImageJ software, version number 1.8.0, developed by the national institute of health. Measurements were made for the radial surface of the fiber. Scanning electron fiber pictures SEM, which can be obtained using a netherlands feminoscope. The inorganic antibacterial agent material is counted under the multiple of 5000-10000, and the diameter of the inorganic antibacterial agent material is measured. The calculation method is to determine the gray threshold value according to the difference of the gray values of the inorganic antibacterial agent and the high molecular material under the electron microscope photograph, for example, 125-255 is the inorganic antibacterial agent, and 125 below is the polymer matrix resin (i.e. the high molecular material). In some cases, the inorganic antibacterial agent is not distinguished from the polymer material significantly due to measurement noise or other influences, and it is necessary to enlarge the characteristics of the inorganic antibacterial agent material in the electron microscope photograph by a matrix thinning operation. The ratio of the pixels occupied by the inorganic antibacterial agent to the pixels in the sampling area is calculated, and the size of the inorganic antibacterial agent can also be inversely calculated through the number of the pixels. The ratio of the pixel area is expressed as a surface distribution ratio, and the number average diameter of the pixel size obtained by the inverse calculation is the diameter of the inorganic antibacterial agent in the yarn (i.e., the dispersion size).
The inorganic antibacterial agent of the antibacterial yarn is distributed on the radial surface in a preferable proportion of 100-200 ppmp (relative to million pixels, pixels per millilon pixels), or 150-3000 ppmp, or 2000-9000 ppmp, or 5000-20000 ppmp. The number average diameter (i.e. dispersion size) of the inorganic antibacterial agent in the antibacterial yarn is preferably 150-300 nm, or 170-350 nm, or 220-440 nm. The pixel calculation is to select an electron microscope analysis image, the image has L pixel points in length and W pixel points in width, and the pixel of the image is the product of the L pixel points and the W pixel points. The antibacterial agent is calculated as one pixel in the analysis image by taking the area of 1 pixel multiplied by 1 pixel as the minimum unit. The number of pixels it occupies divided by the number of pixels of the entire image can be expressed as ppmp.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
The technical scheme of the invention is further explained by combining the embodiment.
Example 1: terylene (PET) antibacterial yarn and preparation of corresponding antibacterial fabric
The first step is as follows: mixing the following raw materials: 99.76 parts of base resin particle PET, 0.2 part of inorganic antimicrobial agent nano zinc oxide ZnO and 0 part of dispersant (no dispersant), and water was removed in a drying apparatus. Wherein the melting temperature of the base resin particle PET was 261.4 ℃, and the average particle diameter of the inorganic antimicrobial agent nano zinc oxide ZnO was 100nm (surface modification was not performed).
The second step is that: mixing of the base resin particle PET with the binder anhydrous glycerin: weighing 99.76 parts of dried matrix resin particle PET, adding 0.04 part of binder anhydrous glycerin, and uniformly mixing in a mixing device to obtain a mixture. Rotating speed of mixing equipment: 150 rpm, mixing time 20 minutes.
The third step: 0.2 part of dried inorganic antibacterial agent nano zinc oxide ZnO is added into the mixture obtained in the second step for mixing. The mixing device speed was 150 rpm and the mixing time was 20 minutes. The purpose is as follows: after the second step, a layer of adhesive anhydrous glycerin is uniformly spread on the surface of the base resin particle PET, and after the dried inorganic antibacterial agent nano zinc oxide ZnO is added, the adhesive anhydrous glycerin can well adhere the inorganic antibacterial agent nano zinc oxide ZnO particles to the surface of the base resin particle PET.
The fourth step: the mixture obtained from the third step above was used to produce an antimicrobial yarn on conventional yarn production equipment, yarn type POY300D 288F. According to the test method of the tensile property of the short fiber of the chemical fiber of the national standard GB/T14337-. The sectional SEM image is shown in FIG. 2.
The fifth step: preparing the antibacterial POY300D288F yarn obtained in the fourth step into the yarn with the gram weight of 155g/m according to the conventional fabric production process2The oven dry mass ratio of the antibacterial POY300D288F yarn to the common POY300D288F yarn is 100:0, namely the antibacterial POY300D288F yarn is used for 100% of the fabric. According to the national standard GB/T20944.2-2007 evaluation part 2 of the antibacterial performance of textiles: and (3) an absorption method is adopted to test the antibacterial rate of the fabric to escherichia coli and staphylococcus aureus.
Example 2: terylene (PET) antibacterial yarn and preparation of corresponding antibacterial fabric
The first step is as follows: mixing the following raw materials: 99.0 parts of base resin particle PET, 0.6 part of inorganic antimicrobial agent nano zinc oxide ZnO and 0 part of dispersant (no dispersant), and water was removed in a drying apparatus. Wherein the melting temperature of the base resin particle PET was 261.4 ℃ and the average particle diameter of the inorganic antimicrobial agent nano zinc oxide ZnO was 50nm (surface modification was not performed).
The second step is that: mixing of base resin particles PET with binder liquid paraffin (distillate temperature >300 ℃): weighing 99.0 parts of dried matrix resin particle PET, adding 0.4 part of binder liquid paraffin, and uniformly mixing in a mixing device to obtain a mixture. Rotating speed of mixing equipment: 150 rpm, mixing time 20 minutes.
The third step: 0.6 part of dried inorganic antibacterial agent nano zinc oxide ZnO is added into the mixture obtained in the second step for mixing. The mixing device speed was 150 rpm and the mixing time was 20 minutes. The purpose is as follows: after the second step, a layer of adhesive liquid paraffin is uniformly spread on the surface of the base resin particle PET, and after the dried inorganic antibacterial agent nano zinc oxide ZnO is added, the adhesive liquid paraffin can well adhere the inorganic antibacterial agent nano zinc oxide ZnO particles to the surface of the base resin particle PET.
The fourth step: the mixture obtained from the third step above was used to produce an antimicrobial yarn on conventional yarn production equipment, yarn type POY300D 288F. According to the test method of the tensile property of the short fiber of the chemical fiber of the national standard GB/T14337-. The sectional SEM image is shown in FIG. 3.
The fifth step: the fourth step is to obtain the antibacterial POY300D288F yarn, and the gram weight is 155g/m according to the conventional fabric production process2The oven dry mass ratio of the antibacterial POY300D288F yarn to the common POY300D288F yarn is 40:60, namely the antibacterial POY300D288F yarn is used for 40% of the fabric. According to the national standard GB/T20944.2-2007 evaluation part 2 of the antibacterial performance of textiles: and (3) an absorption method is adopted to test the antibacterial rate of the fabric to escherichia coli and staphylococcus aureus.
Example 3: nylon (PA6) antibacterial yarn and preparation of corresponding antibacterial fabric
The first step is as follows: mixing the following raw materials: 97.0 parts of matrix resin particles PA6, 1.0 part of inorganic antibacterial agent nano zinc oxide ZnO and 1.0 part of dispersant polyethylene wax, and removing water in a drying device. Wherein the melting temperature of the matrix resin particles PA6 is 220 ℃, the melting point of the dispersant polyethylene wax is 110 ℃, and the average particle size of the inorganic antibacterial agent nano zinc oxide ZnO is 30 nm. Wherein the inorganic antibacterial agent is subjected to surface modification by a silane coupling agent KH570 with the mass fraction of 3%.
The second step is that: mixing of base resin particles PA6, dispersant polyethylene wax and binder liquid paraffin (distillation temperature >300 ℃): 97.0 parts of the dried matrix resin particles PA6 and 1.0 part of the dispersant polyethylene wax are weighed, 1.0 part of the binder liquid paraffin is added, and the mixture is uniformly mixed in a mixing device to obtain a mixture. Rotating speed of mixing equipment: 150 rpm, mixing time 20 minutes.
The third step: adding 1.0 part of dried inorganic antibacterial agent nano zinc oxide ZnO into the mixture obtained in the second step for mixing. The mixing device speed was 150 rpm and the mixing time was 20 minutes. The purpose is as follows: after the second step, a layer of adhesive liquid paraffin is uniformly spread on the surfaces of the matrix resin particles PA6 and the dispersant polyethylene wax, and after the dried inorganic antibacterial agent nano zinc oxide ZnO is added, the adhesive liquid paraffin can well adhere the inorganic antibacterial agent nano zinc oxide ZnO particles to the surfaces of the matrix resin particles PA6 and the dispersant polyethylene wax.
The fourth step: the production of the antimicrobial yarn, yarn type FDY140D136F, was carried out on conventional yarn production equipment from the mixture obtained in the third step above. According to the test method of the tensile property of the chemical fiber short fiber of the national standard GB/T14337-. The sectional SEM image is shown in FIG. 4.
The fifth step: the fourth step is to obtain the antibacterial FDY140D136F yarn, and the gram weight is 155g/m according to the conventional fabric production process2The oven dry mass ratio of the antibacterial FDY140D136F yarn to the common FDY140D136F yarn is 25:75, namely the fabric uses 25% of antibacterial FDY140D136F yarn. According to the national standard GB/T20944.2-2007 evaluation part 2 of the antibacterial performance of textiles: and (3) an absorption method is adopted to test the antibacterial rate of the fabric to escherichia coli and staphylococcus aureus.
As can be seen from fig. 2, 3 and 4, the inorganic antimicrobial agent is uniformly distributed on the surface and inside of the yarn, and the dispersion size of the inorganic antimicrobial agent particles is about 200 nm.
The breaking strength of the antimicrobial yarns obtained in examples 1, 2 and 3, and the common control antimicrobial-free polyester yarn (size POY300D288F) and nylon yarn (size FDY140D136F) are shown in the following table. 5 replicates of each yarn were measured.
TABLE 1 yarn breaking Strength test Table
As can be seen from table 1, the analysis of the 5 parallel sample data and the average value of each yarn did not significantly decrease the breaking strength of the antimicrobial yarns of examples 1 and 2 compared to the conventional control antimicrobial-free polyester yarn (standard POY300D 288F). The antimicrobial yarn of example 3 did not have a significant decrease in breaking strength compared to the plain control antimicrobial-free nylon yarn (gauge FDY140D 136F).
Table 2 antibacterial table of antibacterial fabric of examples 1, 2 and 3
As can be seen from table 2, the antibacterial fabrics obtained in examples 1, 2, and 3 have antibacterial agents against escherichia coli and staphylococcus aureus of more than 99%, and are highly effective antibacterial fabrics.
The nylon antibacterial yarn obtained in example 3 (may also be referred to as antibacterial FDY140D136F yarn) was prepared into two antibacterial fabrics in which the antibacterial yarn amounts were 20 wt% and 33 wt%, respectively, and the fabrics were washed 30 times in accordance with japanese standard JIS L1902: 2015 biological bacteria liquid absorption method, testing the antibacterial activity value of the fabric on staphylococcus aureus and pneumonia bacillus before and after washing. The results are as follows:
table 3 example 3 antibacterial fabric antibacterial table after washing many times
And (4) judging the standard: when the antibacterial activity value is more than or equal to 2.2, the antibacterial fabric has excellent antibacterial performance. As can be seen from the table above, after washing for 30 times, the antibacterial activity values of the two antibacterial fabrics to staphylococcus aureus and pneumonia bacillus are still higher than the standard value of 2.2.
Comparative example 1
In the process of preparing the antibacterial yarn, the inorganic antibacterial agent is added firstly, and then the binder is added. However, the experimental process found that, after the addition of the inorganic antibacterial agent, a large amount of dust was generated during the mixing in the mixing device, thus terminating the experiment.
Claims (10)
1. A method for preparing an antibacterial yarn without significantly reducing the breaking strength of the yarn, comprising:
1) carrying out first mixing treatment on polymer matrix resin and a binder to obtain a mixture A of the polymer matrix resin with the binder spread on at least part of the surface;
2) adding an inorganic antibacterial agent into the mixture A, and carrying out second mixing treatment to obtain a mixture B of a polymer matrix resin, at least part of the surface of which is spread with a binder and adhered with the inorganic antibacterial agent;
3) spinning the mixture B according to a conventional yarn preparation process to prepare the antibacterial yarn with the surface and the interior uniformly dispersed with the inorganic antibacterial agent.
2. The production method according to claim 1, wherein the dispersion size of the inorganic antibacterial agent in the antibacterial yarn is 300nm or less, preferably 100-300 nm.
3. The method of manufacturing according to claim 1 or 2, characterized in that the method of manufacturing does not comprise: before spinning, preparing the antibacterial master batch by using raw materials comprising polymer matrix resin, a binder and an inorganic antibacterial agent.
4. The production method according to any one of claims 1 to 3, wherein the polymer matrix resin is in the shape of chips and/or particles.
5. The production method according to any one of claims 1 to 4, characterized in that the polymer matrix resin is a polyester polymer and/or a polyamide polymer; the polyester polymer is at least one of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; the polyamide polymer is at least one of polyamide 6, polyamide 66, polyamide 610 and polyamide 1010.
6. The production method according to any one of claims 1 to 5, wherein the inorganic antibacterial agent accounts for 0.2 to 1.0% of the antibacterial yarn in an oven-dry mass ratio.
7. The production method according to any one of claims 1 to 6, wherein the particle size of the inorganic antibacterial agent itself is 25 to 350nm, preferably 30 to 100 nm.
8. The antibacterial yarn obtained by the preparation method of the antibacterial yarn which does not significantly reduce the breaking strength of the yarn according to any one of claims 1 to 7, wherein the macro-morphological structure of the antibacterial yarn comprises a sheath-core structure and comprises a circular, oval and spiral cross-sectional morphological structure; preferably, the macro-morphological structure of the antibacterial yarn is a skin-core structure, and the cross section of the antibacterial yarn is circular; more preferably, in the antibacterial yarn of the skin-core structure, the inorganic antibacterial agent is distributed on the surface layer of the skin-core structure, and the core layer does not contain the inorganic antibacterial agent.
9. The antibacterial fabric is characterized in that the yarn raw material of the antibacterial fabric comprises the antibacterial yarn of claim 8, and the mass ratio of the antibacterial yarn to the yarn raw material is 20-100%.
10. The antibacterial fabric according to claim 9, wherein the antibacterial performance of the textile is evaluated according to the national standard GB/T20944.2-2007 part 2: by the absorption method, the antibacterial rate of the antibacterial fabric to escherichia coli and staphylococcus aureus is greater than 99%.
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