CN109594139B - Quick-acting antibacterial functional master batch for polyolefin filamentous material, and preparation method and application thereof - Google Patents
Quick-acting antibacterial functional master batch for polyolefin filamentous material, and preparation method and application thereof Download PDFInfo
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- CN109594139B CN109594139B CN201811576636.5A CN201811576636A CN109594139B CN 109594139 B CN109594139 B CN 109594139B CN 201811576636 A CN201811576636 A CN 201811576636A CN 109594139 B CN109594139 B CN 109594139B
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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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
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
Abstract
The invention relates to a quick-acting antibacterial master batch for polyolefin filamentous materials, a preparation method and application thereof. The method comprises the steps of mixing nano-silver inorganic antibacterial master batches described in patent number ZL201310571129.3, guanidine salt polymer, polyolefin carrier resin, stabilizer and dispersing agent, and then carrying out melt extrusion granulation by double screws to obtain the master batches with the quick-acting antibacterial function. The master batch with the quick-acting antibacterial function prepared by the invention has good wire drawing or spinning performance in the processing process of polyolefin filamentous materials, and the period of replacing the screen and the period of replacing the spinning component are longer than that of other similar antibacterial master batches. The antibacterial polyolefin filamentous material prepared by the method contains the binary composite synergistic antibacterial component of nano-silver and guanidine salt polymer, so that the antibacterial polyolefin filamentous material has high quick-acting antibacterial performance, good washing durability and good whiteness, and is suitable for producing and processing antibacterial products such as disposable medical and sanitary product nonwovens, bath balls/bath towels, artificial lawn filaments, carpets and the like.
Description
Technical Field
The invention relates to the technical field of antibacterial materials. More specifically, the invention relates to a quick-acting antibacterial functional master batch for polyolefin filamentous materials, a preparation method of the quick-acting antibacterial functional master batch, and application of the quick-acting antibacterial functional master batch.
Background
The antibacterial material is used as a novel material with antibacterial and bactericidal functions, is applied to daily life of people, and can well establish a green barrier, improve the living environment and reduce diseases. Such as non-woven fabrics of disposable medical and sanitary articles, non-woven fabrics of disposable antifouling clothes, agricultural fabrics, fabrics for furniture, linings of shoe industry, bath balls/bath towels, artificial lawn filaments, carpets and other materials, and one or more specific antibacterial agents are added in the production and manufacturing process, so that the antibacterial product can be prepared. The antibacterial agent used in the market is mainly an inorganic antibacterial agent, the inorganic antibacterial agent is generally a carrier compound such as zeolite, phosphate, soluble glass, hydroxyapatite and the like loaded with metal ions such as silver, copper, zinc and the like, and metal ion antibacterial components have a slow release effect due to carrier mesoporous or interlayer effect and show excellent antibacterial long-acting property. However, the particle size of the supported silver antibacterial agent is controlled in the micron order, generally 1-10 μm, the process control difficulty of adding the supported silver antibacterial agent into the polyolefin filamentous material is high, the wire drawing is difficult, the antibacterial filamentous product obtained by preparation is generally carried out according to an antibacterial fiber product absorption method or a vibration method during testing, and the antibacterial component and the test strain cannot be fully contacted due to poor water absorption of the polyolefin filamentous product, particularly poor water absorption of a thicker filamentous product, the antibacterial effect of the material is difficult to effectively exert, and the antibacterial rate of the material cannot reach the standard. Particularly, in the actual use process of the disposable sanitary product, the contact time period (generally within 20 min), the antibacterial effect is required to be quick, and the above conventional inorganic silver-loaded antibacterial component needs to be contacted for more than 4h to exert the antibacterial effect. In order to achieve the purpose, researchers often achieve the purpose by adding organic antibacterial agents with high sterilization efficiency, but organic antibacterial agents such as quaternary ammonium salts, quaternary phosphine salts, imidazoles, pyridines, organic metals and the like have the defects of poor heat resistance, easy precipitation, low safety and the like, and are rarely applicable. In recent years, a guanidine salt polymer (polyguanidine) antibacterial agent becomes a plastic antibacterial additive with a good application prospect due to the advantages of high antibacterial efficiency, broad antibacterial spectrum, high safety, good stability, environmental protection, high heat resistance and the like. For example, the literature Synthesis and antimicrobial activity of polymeric guanidine and dbiguanidine salts, Polymer40(1999) 6189-6198 reports that polyhexamethylene (bis) guanidine hydrochloride and polyhexamethylene (bis) guanidine stearate still have good bactericidal effect on various bacteria and fungi at a temperature of 280 ℃, and thus can be used for antibacterial treatment of thermoplastic polymers such as polypropylene and nylon.
Patents CN1569923A, CN1445270A and US 7282538B2 describe a processing method of making guanidinium polymer into antibacterial masterbatch, and then using the antibacterial masterbatch to prepare antibacterial plastics, the single guanidinium polymer component is separated out quickly, and the product performance requirement of high antibacterial durability requirement of wading products cannot be met.
Patent CN1282698C describes a method for preparing polyolefin functional masterbatch, which adds guanidine salt polymer component into polyolefin material by grafting process, and has great difficulty in process control and poor product stability.
Patent CN101724284B describes an antibacterial thermoplastic plastic composition and a preparation method thereof, wherein the composite antibacterial component comprises micro-nano inorganic or organic particles and guanidine salt polymer, the composite antibacterial agent has complex composition, and the system can meet the requirements of plastic processing technology but cannot meet the requirements of filament processing.
Patent CN102644162B introduces a method for preparing an antibacterial nonwoven fabric based on a nano silver simple substance antibacterial agent, the antibacterial master batch containing nano silver prepared by the method has good processing property, excellent antibacterial effect and extremely high hygienic safety in the nonwoven fabric, but in application practice, the control requirement of 80-100nm nano silver simple substance powder in the preparation process is found to be high, and the product performance stability is not good.
At present, the market always needs a preparation method of a quick-acting antibacterial functional master batch material for polyolefin filamentous materials, which has the advantages of simple production process, high production efficiency, energy conservation, environmental protection and stable performance, and the quick-acting antibacterial functional master batch is required to be smoothly drawn and not to block a net in the processing process of the polyolefin filamentous materials, and the prepared antibacterial polyolefin filamentous materials have the advantages of high antibacterial activity, excellent washing durability and high sanitary safety. For this reason, the present inventors have completed the present invention through a large number of experiments.
Disclosure of Invention
Technical problems to be solved
The invention aims to provide a preparation method of a quick-acting antibacterial master batch for polyolefin filamentous materials.
The invention also aims to provide a preparation method of the quick-acting antibacterial functional master batch.
The invention also aims to provide the application of the master batch with the quick-acting antibacterial function.
Technical solution ]
The invention is realized by the following technical scheme.
The invention relates to a quick-acting antibacterial functional master batch for polyolefin filamentary materials, which is characterized in that the content of nano-silver particles of the quick-acting antibacterial functional master batch is 400-1400ppm, and the particle size of the nano-silver particles is 5-100 nm; the content of guanidine salt polymer of the quick-acting antibacterial functional master batch is 1-10% by weight.
The invention also relates to a preparation method of the quick-acting antibacterial master batch for the polyolefin filamentous material. The method comprises the following steps:
(1) preparing nano silver inorganic antibacterial master batch
Taking nano-silver inorganic antibacterial master batch disclosed in patent number ZL 201310571129.3.
(2) Preparing quick-acting antibacterial functional master batch
Weighing the following components in parts by weight:
67.5-13 parts of polyolefin carrier resin
30-70 parts of nano-silver inorganic antibacterial master batch
1-10 parts of guanidine salt polymer
0.5-2 parts of stabilizer
1-5 parts of dispersant
The stabilizing agent is silicon dioxide ultrafine powder;
the dispersant is an ionomer;
firstly, adding the nano-silver inorganic antibacterial master batch, the polyolefin resin, the guanidine salt polymer, the stabilizer and the dispersing agent into a high-speed stirrer together, stirring at a low speed for 2-4min and at a high speed for 3-5min, then adding into a double-screw extruder, and performing melt extrusion granulation to prepare the polyolefin quick-acting antibacterial functional master batch.
According to a preferred embodiment of the invention, the polyolefin carrier resin is polyethylene, polyvinyl chloride or polypropylene.
According to another preferred embodiment of the present invention, the guanidine salt polymer is one of polyhexamethylene biguanide hydrochloride, polyhexamethylene biguanide phosphate or polyhexamethylene biguanide phosphate;
according to another preferred embodiment of the present invention, the silica micropowder is one of precipitated silica, fumed silica, or ultrafine silica gel.
According to another preferred embodiment of the invention, the ionomer is a polymer with Na+、Ca2+、Mg2+Or Zn2+An ethylene-acrylic acid copolymer of metal ions, said copolymer having a Brookfield viscosity of 4000-7000cps at 190 ℃.
According to another preferred embodiment of the present invention, the screw rotation speed of the twin-screw extruder is 200-350rpm, and the twin-screw extruder is equipped with an intensive devolatilization device.
The invention is based on the following principle: the nano silver and the guanidine salt polymer have very high bactericidal/bacteriostatic activity, and are compounded together through a plastic melt extrusion process to achieve the purposes of synergy and antibiosis; the porous structure of the stabilizing agent silicon dioxide ultrafine powder has strong adhesion to nano silver and guanidine salt polymers, so that the rapid precipitation of the stabilizing agent silicon dioxide ultrafine powder is delayed, and the sterilization/bacteriostasis aging is improved; in addition to the specific guanidino structure (NH) of guanidinium salt polymers2C (= NH) has a stabilizing effect on nano silver, so that the nano silver is not easy to discolor and yellow; the composite component of the nano-silver and the guanidine salt polymer is adopted, so that the antibacterial activity is high, the adding proportion in the polyolefin filamentous material is small, the dispersion is uniform, and the continuous filament breaking and the net blocking during the polyolefin wire drawing can be ensured; the method has the advantages of simple production process, high efficiency and low production cost, and is suitable for mass production of the polyolefin functional master batch with quick-acting antibacterial property, white color and high water-resistant durability.
The present invention will be described in more detail below.
The invention relates to a quick-acting antibacterial master batch for polyolefin filamentary materials, which is characterized in that the content of nano-silver particles of the antibacterial master batch is 400-1400ppm, the particle size of the nano-silver particles is 5-100nm, and the content of guanidine salt polymer of the antibacterial master batch is 1-10% by weight.
It is known that Nano Silver (Nano Silver) is a metallic Silver simple substance having a particle size of a nanometer order. Researches find that the nano-silver is a bactericide stronger than antibiotics, and can quickly and directly kill 650 bacteria to make the bacteria lose reproductive capacity; the nano silver has strong permeability, and can promote wound healing, cell growth and damaged cell repair; the antibacterial agent has lasting antibacterial effect, is safe and nontoxic, and has no any irritation reaction to skin; no drug resistance, etc.
The guanidine salt polymer is used as an environment-friendly high polymer, and the hydrophilic group part of the guanidine salt polymer has strong electropositivity, adsorbs various bacteria and viruses which are usually electronegative, enters a cell membrane, inhibits the synthesis of intramembrane liposome, causes the apoptosis of thalli and achieves the optimal bactericidal effect; has broad bactericidal spectrum; the effective concentration is low; the action speed is high; the property is stable; long-term bacteriostasis without side effect; no corrosion; colorless and odorless; is nontoxic; the material is non-combustible, non-explosive and safe to use; the price is moderate; the transportation is convenient.
According to a preferred embodiment of the invention, the polyolefin material is polyethylene, polyvinyl chloride or polypropylene
The invention also relates to a preparation method of the quick-acting antibacterial master batch for the polyolefin filamentous material. The method comprises the following steps:
(1) preparing nano silver inorganic antibacterial master batch
Taking nano-silver inorganic antibacterial master batch disclosed in patent number ZL 201310571129.3.
In the step, the content of silver particles of the nano-silver inorganic antibacterial master batch disclosed in the patent number ZL201310571129.3 is 600-2000ppm, and the particle size of the silver particles is 5-100 nm.
The above patent describes a preparation method of the nano-silver inorganic antibacterial master batch, which comprises the following steps:
a: adding 1-5 parts by weight of silver salt and 95-99 parts by weight of volatile solvent containing active hydroxyl or ketone into a reaction kettle with a reflux device, and stirring at 35-60 ℃ for 60-180min to completely dissolve the silver salt in the solvent to obtain a uniform and transparent solution;
b: adding 5-20 parts by weight of the uniform transparent solution obtained in the step A, 93-100 parts by weight of high-transparency polyolefin carrier resin, 1-5 parts by weight of polyvinylpyrrolidone or polyethylene glycol and 0.5-2 parts by weight of ground molecular weight ionomer into a high-speed stirrer with heating and solvent recovery equipment, carrying out high-speed mixing and stirring treatment for 30-60min at the temperature of 60-80 ℃, and simultaneously drying and recovering about 90% of redundant solvent;
c: and C, adding the fully mixed material obtained in the step B into a mixture with the length-diameter ratio of 40: 1 to 64: 1, in the double-screw extruder of the double-screw extruder, under the condition that the processing temperature is 150-240 ℃, the nano-silver inorganic antibacterial master batch with the silver particle content of 600-2000ppm and the nano-silver particle size of 5-100nm is obtained through melt extrusion granulation;
in the above patent, the silver salt is silver nitrate, silver acetate, silver citrate or silver tartrate.
In the above patent, the volatile solvent containing an active hydroxyl group or ketone group is methanol, ethanol or acetone.
In the above patent, the polyvinylpyrrolidone is 45000-130000 polyvinylpyrrolidone;
in the above patent, the polyethylene glycol is polyethylene glycol having a molecular weight of 200-4000.
In the above patents, the polyalkene carrier resin is polyethylene, polyvinyl chloride or polypropylene.
(2) Preparing quick-acting antibacterial functional master batch
Weighing the following components in parts by weight:
67.5-13 parts of polyolefin carrier resin
30-70 parts of nano-silver inorganic antibacterial master batch
1-10 parts of guanidine salt polymer
0.5-2 parts of stabilizer
1-5 parts of dispersant
The stabilizing agent is silicon dioxide ultrafine powder;
the dispersant is an ionomer.
Firstly, adding the nano-silver inorganic antibacterial master batch, polyolefin carrier resin, guanidine salt polymer, stabilizer and dispersant into a high-speed stirrer together, stirring at a low speed for 2-4min and at a high speed for 3-5min, then adding into a double-screw extruder, and performing melt extrusion granulation to prepare the polyolefin quick-acting antibacterial functional master batch.
According to a preferred embodiment of the present invention, the polyolefin carrier resin is polyethylene, polyvinyl chloride or polypropylene, all of which are commercially available materials.
According to another preferred embodiment of the present invention, the guanidine salt polymer is one of polyhexamethylene biguanide hydrochloride, polyhexamethylene biguanide phosphate or polyhexamethylene biguanide phosphate, all of which are commercially available materials.
According to another preferred embodiment of the present invention, the silica micropowder is one of precipitated silica, fumed silica, or ultrafine silica gel.
Silica, commonly known as white carbon, is a porous material, and its composition may be SiO2·nH2O represents, wherein nH2O is present in the form of surface hydroxyl groups. It is soluble in caustic alkali and hydrofluoric acid, and insoluble in water, solvent and acid (except hydrofluoric acid). High temperature resistance, non-combustion, tastelessness, odorless, good electrical insulation, water absorption and porosity; large internal surface area, good reinforcing and tackifying functions, good dispersion, suspension property and vibration liquid habit. The high-temperature vulcanized silicone rubber is used as an environment-friendly auxiliary with excellent performance and is mainly used in the fields of rubber products (including high-temperature vulcanized silicone rubber), textiles, papermaking, pesticides and food additives.
Wherein the silicon dioxide ultrafine powder is a conventional product sold in the market, the purity requirement of the silicon dioxide ultrafine powder is more than 98 percent, and the specific surface area requirement of the silicon dioxide ultrafine powder is 100-1000 m2(ii) in terms of/g. The silicon dioxide used by the invention is a product produced and sold by a Xinan chemical group or a Shouguangtai micro-nano chemical factory in Shandong province.
According to another preferred embodiment of the invention, the ionomer is a low molecular weight ionomer which is a polymer containing several ionic groups attached to polymer chains,the main chain monomer is olefin (ethylene, butadiene, etc.), the ionic groups are carboxyl (COO-) and sulfonic acid (S03-), it is prepared by neutralizing ethylene-acrylic acid copolymer with low relative molecular mass, and the metal ion is Na+、Ca2+、Mg2+Or Zn2 +. The low molecular weight ionomers used in the present invention are commercially available from Honeywell corporation, USA under the trade designation AClyn201A, 246A, 272A, 295A or 291A, and the Brookfield viscosity at 190 ℃ of the copolymer is 4000-7000 cps.
According to another preferred embodiment of the invention, said twin-screw extruder belongs to the high aspect ratio type and must be a normal co-rotating twin-screw extruder with powerful devolatilization means or a dedicated twin-screw extruder of the deashing type. The co-rotating twin-screw extruder used in the invention is a TE-65 type extruder produced by Nanjing Dalitun extrusion machinery Co., Ltd or a high-capacity devolatilization type twin-screw extruder produced by Nanjing Lixuan mechanical equipment Co., Ltd.
According to another preferred embodiment of the present invention, the screw speed is 200-350 rpm. Preferably, the selected screw speed is 250-300 rpm. The rotation speed of the screw is lower than 200rpm, so that the retention time of the materials in the screw can be ensured, but the production efficiency is influenced; and after the rotating speed of the screw is higher than 350rpm, the materials generate strong shearing on the screw, so that the structures of the nano silver particles and the guanidine salt polymer are damaged, and the antibacterial activity is influenced.
According to another preferred embodiment of the present invention, the processing temperature of the screw extruder is 150-240 ℃. When the temperature is lower than 150 ℃, the uniform dispersion of the guanidinium polymer is not facilitated; and when the temperature is higher than 240 ℃, decomposition of the guanidinium polymer is easily caused.
According to another preferred embodiment of the method, the double-screw extruder is provided with a strong devolatilization device, so that a small amount of toxic and harmful gas generated in the high-temperature heating and melting process is extracted out in time through the device and collected in a special waste gas recovery storage tank, and the obtained antibacterial master batch is safer to use.
The invention also relates to the application of the master batch with the quick-acting antibacterial function or the master batch with the quick-acting antibacterial function obtained by the method, which is mainly applied to polyolefin filamentous products such as non-woven fabrics of disposable medical and sanitary products, non-woven fabrics of disposable antifouling clothes, agricultural fabrics, fabrics for furniture, linings of shoe industry, bath balls/bath towels, artificial lawn filaments, carpets and the like through the melt extrusion drawing or spinning process of an extruder.
The invention also relates to the application of the quick-acting antibacterial functional master batch or the quick-acting antibacterial functional master batch obtained by the method in polyolefin filamentous materials, wherein the content of nano silver particles is 15-100ppm, the content of guanidine salt polymer is 0.04-0.5 percent by weight, and the composite antibacterial component of the nano silver particles and the guanidine salt polymer is contacted with escherichia coli, staphylococcus aureus and candida albicans for 1min, the antibacterial rate is up to more than 99 percent, and the obtained antibacterial polyolefin filamentous product has excellent antibacterial durability, and the effective antibacterial time is even longer than 10 years as shown by technical data.
The performance test of the quick-acting antibacterial master batch prepared by the invention is explained in detail below.
The detection method and the detection result are as follows.
A. The invention discloses a wire drawing extrusion evaluation test (taking a polyolefin PE bath ball material as an example) applied by quick-acting antibacterial master batch:
the PE-based rapid-effect antibacterial master batch is uniformly mixed with polyolefin PE resin according to a certain proportion, and then is melted, extruded and drawn by a screw to prepare thicker wires, wherein the content of nano silver particles in the prepared PE wire material is 40ppm, the content of guanidine salt polymer is 0.3 percent by weight, and the diameter of the obtained antibacterial PE wire is 0.2 mm. A PE antibacterial master batch prepared from a conventional antibacterial component zirconium phosphate silver-loaded superfine powder antibacterial agent is selected to carry out a wire drawing comparison evaluation experiment, and meanwhile, an antibacterial PE filament which is not added with a nano-silver inorganic antibacterial component but is only added with a single antibacterial agent of 0.3% guanidinium polymer is also prepared and used as an additional control sample for later use.
Processing tests show that the PE wire drawing processing period of the PE wire added with the quick-acting antibacterial master batch obtained by the invention is long when the PE wire with the same specification (the wire diameter is 0.2 mm) is produced: the net changing period is more than or equal to 1 piece/48 hours; the component replacement period is more than or equal to 45 days; the wire drawing processing cycle of adding the zirconium phosphate silver-loaded antibacterial agent is as follows: the net changing period is more than or equal to 1 piece/12 hours; the component replacement period is more than or equal to 20 days.
B. The invention discloses an antibacterial performance evaluation test (taking a polyolefin PE bath ball material as an example) applied by quick-acting antibacterial functional master batch:
the antibacterial PE filament prepared in the step A is tested according to the standard GB15979-2002 'appendix C vibration method for Disposable sanitary products', and the result shows that the antibacterial PE filament has the contact effect with escherichia coli (ATCC 25922), staphylococcus aureus (ATCC6538) and candida albicans (ATCC10231) for 1min, and the antibacterial rate is over 99%.
C. The invention discloses an antibacterial durability evaluation test (taking a polyolefin PE bath ball material as an example) applied by quick-acting antibacterial functional master batch:
the antibacterial PE filaments prepared in the step A are tested according to the standard FZ/73023 and 2006 washing test method of antibacterial fabric appendix C antibacterial fabric sample, and the result shows that the antibacterial rate of the antibacterial PE filaments to escherichia coli (ATCC 25922), staphylococcus aureus (ATCC6538) and candida albicans (ATCC10231) is still more than 90% after the antibacterial PE filaments are washed for 100 times; meanwhile, a water washing test experiment for adding only a single guanidine salt polymeric component antibacterial PE filament in the A shows that the antibacterial rate of the antibacterial filament to escherichia coli (ATCC 25922), staphylococcus aureus (ATCC6538) and candida albicans (ATCC10231) is still more than 99% before water washing, and after the antibacterial filament is washed by the same method for 100 times, the antibacterial rates to escherichia coli (ATCC 25922), staphylococcus aureus (ATCC6538) and candida albicans (ATCC10231) are respectively 50%, 30% and 28%, and the antibacterial rates are greatly reduced, because the guanidine salt polymer is good in water solubility, the antibacterial filament prepared from the single component is fast in water precipitation, and the water washing durability is poor. The comparative experiment further shows that the antibacterial functional master batch prepared by the method has more excellent washing durability by matching the formula components.
D. The whiteness evaluation test of the antibacterial wire material obtained by applying the quick-acting antibacterial functional master batch of the invention (taking a polyolefin PE bath ball material as an example) is as follows:
the antibacterial PE filament prepared in the step A is tested according to the standard GB/T17644-2008 'test method for whiteness degree of textile fibers', and the result shows that the whiteness W of the antibacterial PE filament is 76.5760%, and the difference is very small compared with 77.4870% of the whiteness of a blank PE filament prepared without the antibacterial component.
The nano silver component is taken from patent ZL201310571129.3, and the patent states that the particle size of the nano silver particles is 5-100nm, the distribution is uniform, the safety is high, the antibacterial performance is good, and the stability is excellent; meanwhile, in the preparation process of the antibacterial master batch, the environment-friendly and efficient guanidine salt polymer bactericide component is added, so that the antibacterial activity of the material is further improved, and the aim of quick acting is fulfilled. Through the test evaluation and test, the test result also clearly shows that the antibacterial activity of the quick-acting antibacterial functional master batch prepared by the invention is very high, under the condition that the composite antibacterial component is that the content of nano silver particles is 15-100ppm and the content of guanidine salt polymer is 0.1-0.5% by weight, the prepared antibacterial polyolefin filamentous material is contacted with escherichia coli (ATCC 25922), staphylococcus aureus (ATCC6538) and candida albicans (ATCC10231) for 1min, the antibacterial rate is more than 99%, and after 100 times of washing, the antibacterial rate still reaches more than 90%. Meanwhile, the quick-acting antibacterial master batch obtained by the invention has strong applicability and long processing period in the processing process of polyolefin drawing or spinning. In addition, the antibacterial polyolefin filamentous material prepared from the quick-acting antibacterial master batch has good whiteness, and meets the technical requirements of high-quality antibacterial products.
[ PROBLEMS ] the present invention
The invention has the following beneficial effects:
the method has the advantages of less used equipment, simple process, environmental friendliness and convenience for large-scale industrial production; the quick-acting antibacterial functional master batch prepared by the invention has high use safety, high antibacterial efficiency and quick acting, is particularly suitable for thicker filamentous polyolefin material products with poor water absorption, such as polyolefin PE bath ball filaments added with the antibacterial master batch of the invention, and contact action of escherichia coli, staphylococcus aureus and candida albicans for 1min, and has the antibacterial rate of over 99 percent and excellent washing durability; the quick-acting antibacterial master batch has low production cost and strong market competitiveness.
[ detailed description ] embodiments
The invention will be better understood from the following examples.
Example 1
(1) Preparing nano silver inorganic antibacterial master batch
The patent number ZL201310571129.3 in the specification of example 2 shows that the inorganic antibacterial master batch containing silver particles and containing 1200ppm LDPE-based nano silver is prepared.
(2) Preparing quick-acting antibacterial functional master batch
Weighing the following components in parts by weight:
59.5 parts of LDPE carrier resin
33.5 parts of nano-silver inorganic antibacterial master batch
Polyhexamethylene guanidine hydrochloride 3 parts
1 part of silica by vapor phase method
201A ionomer 3 parts
Firstly, adding the nano-silver inorganic antibacterial master batch, LDPE carrier resin, polyhexamethylene guanidine hydrochloride, gas phase method silicon dioxide and 201A ionomer into a high-speed stirrer to stir at a low speed for 2min and 4min at a high speed, then adding the mixture into a double-screw extruder to perform melt extrusion granulation at a processing temperature of 150 plus materials and 170 ℃ and a rotating speed of 250rpm, and preparing the quick-acting PE antibacterial functional master batch with the silver particle content of 400ppm and the polyhexamethylene guanidine hydrochloride content of 3 percent by weight.
Example 2
(1) Preparing nano silver inorganic antibacterial master batch
The patent number ZL201310571129.3 in the specification of example 2 shows that the inorganic antibacterial master batch containing silver particles and containing 1200ppm LDPE-based nano silver is prepared.
(2) Preparing quick-acting antibacterial functional master batch
Weighing the following components in parts by weight:
LLDPE polyethylene carrier resin 22 parts
67 parts of nano-silver inorganic antibacterial master batch
5 parts of polyhexamethylene biguanide hydrochloride
2 portions of silicon dioxide by precipitation method
291A ionomer 4 parts
Firstly, adding the nano-silver inorganic antibacterial master batch, LLDPE carrier resin, polyhexamethylene biguanide hydrochloride, precipitation method silicon dioxide and 291A ionomer into a high-speed stirrer to stir at a low speed for 4min and at a high speed for 5min, then adding the mixture into a double-screw extruder to perform melt extrusion granulation at a processing temperature of 150 plus 170 ℃ and a rotating speed of 250rpm, and preparing the LLDPE quick-acting antibacterial functional master batch with the silver particle content of 800ppm and the polyhexamethylene biguanide hydrochloride content of 5 percent by weight.
Example 3
(1) Preparing nano silver inorganic antibacterial master batch
The patent number ZL201310571129.3 in the specification of example 3 shows that the inorganic antibacterial master batch containing 1800ppm PP-based nano silver with silver particle content is prepared.
(2) Preparing quick-acting antibacterial functional master batch
Weighing the following components in parts by weight:
52.5 parts of PP polypropylene carrier resin
40 parts of nano-silver inorganic antibacterial master batch
5 parts of polyhexamethylene biguanide phosphate
0.5 part of superfine silica gel
2 parts of 201A ionomer
Firstly, adding the nano-silver inorganic antibacterial master batch, PP polypropylene carrier resin, polyhexamethylene biguanide phosphate, superfine silica gel and 201A ionomer into a high-speed stirrer together, stirring at a low speed for 2min and at a high speed for 4min, then adding the mixture into a double-screw extruder, and performing melt extrusion granulation at the processing temperature of 190 plus materials and 220 ℃ and the rotating speed of 300rpm to prepare the PP quick-acting antibacterial functional master batch with the silver particle content of 720ppm and the polyhexamethylene biguanide phosphate content of 5 percent by weight.
Example 4
(1) Preparing nano silver inorganic antibacterial master batch
The patent number ZL201310571129.3 in the specification of example 3 shows that the inorganic antibacterial master batch containing 1800ppm PP-based nano silver with silver particle content is prepared.
(2) Preparing quick-acting antibacterial functional master batch
Weighing the following components in parts by weight:
16 parts of PP polypropylene carrier resin
70 parts of nano-silver inorganic antibacterial master batch
Polyhexamethylene monoguanidine phosphate 8 parts
2 parts of fumed silica
201A ionomer 4 parts
Firstly, the nano-silver inorganic antibacterial master batch, PP polypropylene carrier resin, polyhexamethylene monoguanidine phosphate, fumed silica and 201A ionomer are added into a high-speed stirrer together and stirred at a low speed for 4min and 5min at a high speed, then the mixture is added into a double-screw extruder and melted and extruded for granulation at the processing temperature of 190 plus materials and 220 ℃ and the rotating speed of 300rpm to prepare the PP quick-acting antibacterial functional master batch with the silver particle content of 1260ppm and the polyhexamethylene monoguanidine phosphate content of 8 percent by weight
Example 5
(1) Preparing nano silver inorganic antibacterial master batch
The inorganic antibacterial master batch containing 1500ppm PVC-based nano-silver with silver particle content is prepared according to the description of example 4 in the specification of patent number ZL 201310571129.3.
(2) Preparing quick-acting antibacterial functional master batch
Weighing the following components in parts by weight:
42 parts of PVC polyvinyl chloride carrier resin
50 parts of nano-silver inorganic antibacterial master batch
4 parts of polyhexamethylene biguanide hydrochloride
1 part of silica by vapor phase method
246A ionomer 3 parts
Firstly, adding the nano-silver inorganic antibacterial master batch, PVC polyvinyl chloride carrier resin, polyhexamethylene biguanide salt, fumed silica and 246A ionomer into a high-speed stirrer together, stirring at a low speed for 2min and 4min at a high speed, then adding the mixture into a double-screw extruder, and performing melt extrusion granulation at the processing temperature of 190 ℃ and the rotating speed of 250rpm to prepare the PVC quick-acting antibacterial functional master batch with the silver particle content of 750ppm and the polyhexamethylene biguanide hydrochloride content of 4 percent by weight.
The performance of the masterbatch with quick-acting antibacterial function for polyolefin filamentous material prepared in examples 1 to 5 was tested by the test method described in this specification, and the test results are shown in table 1.
Claims (12)
1. A preparation method of quick-acting antibacterial master batch for polyolefin filamentous material is characterized by comprising the following steps:
(1) the preparation method of the nano-silver inorganic antibacterial master batch comprises the following steps:
a: adding 1-5 parts by weight of silver salt and 95-99 parts by weight of volatile solvent containing active hydroxyl or ketone into a reaction kettle with a reflux device, and stirring at 35-60 ℃ for 60-180min to completely dissolve the silver salt in the solvent to obtain a uniform and transparent solution; the silver salt is silver nitrate, silver acetate, silver citrate or silver tartrate, and the volatile solvent containing active hydroxyl or ketone groups is methanol, ethanol or acetone;
b: adding 5-20 parts by weight of the uniform transparent solution obtained in the step A, 93-100 parts by weight of high-transparency polyolefin carrier resin, 1-5 parts by weight of polyvinylpyrrolidone or polyethylene glycol and 0.5-2 parts by weight of low-molecular-weight ionomer into a high-speed stirrer with heating and solvent recovery equipment, carrying out high-speed mixing and stirring treatment for 30-60min at the temperature of 60-80 ℃, and simultaneously drying and recovering about 90% of redundant solvent; the polyvinylpyrrolidone is 45000-130000 polyvinylpyrrolidone, and the polyethylene glycol is polyethylene glycol with molecular weight of 200-4000;
c: and C, adding the fully mixed material obtained in the step B into a mixture with the length-diameter ratio of 40: 1 to 64: 1, in a double-screw extruder, under the condition that the processing temperature is 150-240 ℃, the nano silver inorganic antibacterial master batch with the silver particle content of 600-2000ppm and the nano silver particle diameter of 5-100nm is obtained through melt extrusion granulation;
(2) the quick-acting antibacterial master batch is prepared by weighing the following components in parts by weight:
67.5-13 parts of polyolefin carrier resin
30-70 parts of nano-silver inorganic antibacterial master batch
1-10 parts of guanidine salt polymer
0.5-2 parts of stabilizer
1-5 parts of dispersant
The stabilizing agent is silicon dioxide ultrafine powder;
the dispersant is an ionomer;
firstly, adding the nano-silver inorganic antibacterial master batch, the polyolefin carrier resin, the guanidine salt polymer, the stabilizer and the dispersing agent into a high-speed stirrer together, stirring at a low speed for 2-4min and at a high speed for 3-5min, then adding into a double-screw extruder, and performing melt extrusion granulation at the processing temperature of 150-240 ℃ to prepare the quick-acting antibacterial functional master batch for the polyolefin filament material;
the silicon dioxide ultrafine powder is one of precipitated silicon dioxide, gas-phase silicon dioxide or ultrafine silicon dioxide gel; the purity of the silicon dioxide is more than 98%, and the specific surface area of the silicon dioxide is 100-500 m2(ii)/g; the ionomer is a polymer with Na+、Ca2+、Mg2+Or Zn2+An ethylene-acrylic acid copolymer of metal ions, said copolymer having a Brookfield viscosity of 4000-7000cps at 190 ℃.
2. The method of claim 1, wherein the polyolefin carrier resin is polyethylene, polyvinyl chloride, or polypropylene.
3. The method of claim 1, wherein the guanidine salt polymer is one of polyhexamethylene biguanide hydrochloride, polyhexamethylene biguanide phosphate, or polyhexamethylene biguanide phosphate.
4. The method according to claim 1, wherein the screw speed of the twin-screw extruder is 200-350rpm, and the twin-screw extruder is equipped with a powerful devolatilization device.
5. A master batch with quick-acting antibacterial function for polyolefin filamentous materials prepared by the preparation method according to any one of claims 1-4.
6. The masterbatch with quick-acting antibacterial function for polyolefin filament material as claimed in claim 5, wherein the content of nano silver particles in the masterbatch with quick-acting antibacterial function is 400-1400ppm, and the particle size of the nano silver particles is 5-100 nm.
7. The masterbatch of claim 5, wherein the guanidine salt polymer of the masterbatch has a content of 1-10 wt%.
8. A polyolefin filamentous material comprising the master batch having a rapid-acting antibacterial function according to any one of claims 5 to 7.
9. The polyolefin filamentary material of claim 8 wherein the amount of nanosilver particles is 15 to 100ppm and the guanidinium polymer is 0.04 to 0.5 weight percent.
10. The polyolefin filamentary material of claim 8 or 9 wherein the polyolefin matrix resin is polyethylene, polyvinyl chloride or polypropylene.
11. The polyolefin filamentary material according to claim 8 or 9 wherein the composite antibacterial component of nano-silver particles and guanidinium polymer is contacted with escherichia coli, staphylococcus aureus and candida albicans for 1min, with an antibacterial rate of 99% or more.
12. The polyolefin filamentary material of claim 11 wherein the antibacterial composition of nanosilver particles and guanidinium polymer is contacted with e.coli, s.aureus and c.albicans for 1min at an antibacterial rate of 99% or more.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2112200A1 (en) * | 2007-02-05 | 2009-10-28 | Adeka Corporation | Resin additive master batch |
| CN101720785A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Compound antimicrobial and preparation method thereof |
| CN101724284A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Anti-bacterial thermoplastic composite and preparation method thereof |
| CN102453273A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Antibacterial master batch based on guanidinium polymer and preparation method thereof |
| CN102898727A (en) * | 2012-11-06 | 2013-01-30 | 北京崇高纳米科技有限公司 | Polypropylene master batch with functions of anti-bacteria, and mildew and algae prevention and preparation method of polypropylene master batch |
| CN103601959A (en) * | 2013-11-15 | 2014-02-26 | 李泽国 | High-transparency nano silver inorganic antimicrobial master batch for polyolefin plastics, and preparation method and application thereof |
| CN104372432A (en) * | 2014-11-03 | 2015-02-25 | 四川大学 | Preparation method of silver-bearing antibacterial polypropylene fiber |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101701498B1 (en) * | 2014-09-05 | 2017-02-03 | (주)비앤케이 | manufacturing method of 3D printer filament having antibacterial effects and 3D printer filament with antibacterial effects. |
-
2018
- 2018-12-23 CN CN201811576636.5A patent/CN109594139B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2112200A1 (en) * | 2007-02-05 | 2009-10-28 | Adeka Corporation | Resin additive master batch |
| CN101720785A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Compound antimicrobial and preparation method thereof |
| CN101724284A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Anti-bacterial thermoplastic composite and preparation method thereof |
| CN102453273A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Antibacterial master batch based on guanidinium polymer and preparation method thereof |
| CN102898727A (en) * | 2012-11-06 | 2013-01-30 | 北京崇高纳米科技有限公司 | Polypropylene master batch with functions of anti-bacteria, and mildew and algae prevention and preparation method of polypropylene master batch |
| CN103601959A (en) * | 2013-11-15 | 2014-02-26 | 李泽国 | High-transparency nano silver inorganic antimicrobial master batch for polyolefin plastics, and preparation method and application thereof |
| CN104372432A (en) * | 2014-11-03 | 2015-02-25 | 四川大学 | Preparation method of silver-bearing antibacterial polypropylene fiber |
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