WO2021253720A1 - Organic electret masterbatch for melt-blown nonwoven fabric used in face masks and preparation method thereof, and melt-blown nonwoven fabric prepared therefrom - Google Patents

Organic electret masterbatch for melt-blown nonwoven fabric used in face masks and preparation method thereof, and melt-blown nonwoven fabric prepared therefrom Download PDF

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WO2021253720A1
WO2021253720A1 PCT/CN2020/129279 CN2020129279W WO2021253720A1 WO 2021253720 A1 WO2021253720 A1 WO 2021253720A1 CN 2020129279 W CN2020129279 W CN 2020129279W WO 2021253720 A1 WO2021253720 A1 WO 2021253720A1
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Prior art keywords
electret
melt
masterbatch
masks
fluorine
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PCT/CN2020/129279
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French (fr)
Chinese (zh)
Inventor
李力
王斌
王道娟
杨友强
杨曦
程文建
刘乐文
杨霄云
陈平绪
叶南飚
黄险波
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金发科技股份有限公司
广东金发科技有限公司
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Publication of WO2021253720A1 publication Critical patent/WO2021253720A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D04H1/544—Olefin series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/14—Homopolymers or copolymers of vinyl fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the invention relates to the field of melt-blown non-woven fabrics, in particular to organic electret masterbatch special for melt-blown non-woven fabrics for masks, a preparation method thereof, and a melt-blown non-woven fabric made.
  • Melt-blown non-woven fabric for masks is a material for preparing filter masks. Although the filtration efficiency can be improved by electret treatment, only the electret treatment of the non-woven fabric itself can improve the filtration efficiency to a limited extent. In order to achieve an ideal filtering effect, electret materials or electret masterbatches are generally added to the formula of meltblown non-woven fabrics for masks.
  • Electret masterbatch can be divided into inorganic electret masterbatch and organic electret masterbatch. The most common inorganic electret masterbatch is obtained by adding ultra-high melting index polypropylene as the matrix, and dispersing tourmaline powder with a smaller particle size in the matrix after adding a dispersant.
  • the patent CN1718910A provides a melt blown
  • the modified polypropylene masterbatch and the preparation method and application thereof are used to modify the surface of the tourmaline by a coupling agent, and then add a dispersant to uniformly distribute the tourmaline powder in the PP matrix to obtain the electret masterbatch.
  • agglomeration is easy to occur, and in the meltblown equipment used for meltblown non-woven fabrics, the spinneret has a small aperture.
  • these agglomerated tourmaline powders have a greater chance of staying On the spinneret, the risk of clogging of the spinneret is caused, and higher costs are required for shutdown and cleaning.
  • Patent CN109354767A discloses the preparation of an organic electret masterbatch, which uses electrets including natural wax, rosin, plexiglass, fatty acids with 6 to 20 carbon atoms or their salts, etc.
  • the organic electret masterbatch is combined with The high melting index polypropylene is added in a weight ratio of 1:20, and the filtration efficiency of the produced meltblown non-woven fabric can basically reach more than 95%.
  • these electrets still have the risk of precipitation and migration due to their small molecular weight.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a special organic electret masterbatch for meltblown non-woven fabrics for masks.
  • the electret effect is ideal and lasting, and There is no blockage in the production process of meltblown non-woven fabrics.
  • Another object of the present invention is to provide a preparation method of the special organic electret masterbatch for the meltblown non-woven fabric for masks.
  • Another object of the present invention is to provide a melt-blown non-woven fabric containing the organic electret masterbatch dedicated to the melt-blown non-woven fabric for masks.
  • a special organic electret masterbatch for meltblown non-woven fabrics for masks is made of the following components calculated by weight percentage:
  • the average particle size of the particles of the fluorine electret powder is 0.05-3um;
  • the compatibilizer is maleic anhydride grafted olefin copolymer/elastomer or glycidyl methacrylate grafted olefin copolymer/elastomer;
  • the polypropylene resin is homopolypropylene and/or copolymer polypropylene, and its melt index MFI is not less than 1000g/10min at 230°C/2.16kg;
  • the screw length-to-diameter ratio of the twin-screw extruder used for preparing the special organic electret masterbatch for the meltblown non-woven fabric for masks is greater than or equal to 40:1;
  • the fluorine electret powder is a fine powder of a high polymer or copolymer formed from a fluorine-containing vinyl monomer.
  • Fluorine electret powder is a type of fluorine-containing organic polymer particles. It has been reported to be used as an electret for the preparation of electrophoretic particles for porous filter membranes or large-screen displays, but it has not been used for the preparation of masks. A report of electret masterbatch for spraying non-woven fabrics. The reason is that although this kind of material has a higher molecular weight than ordinary organic electret powder, it is not easy to migrate, but it is more difficult to disperse uniformly than conventional organic electret powder, and it needs to be added in a larger amount in meltblown non-woven fabrics. The ideal electret effect can only be achieved under the following conditions.
  • the particle size of the fluorine electret powder is controlled within the above-mentioned range, with a suitable compatibilizer and a suitable screw length-to-diameter ratio, the fluorine electret powder can be more easily dispersed in the electret. In the masterbatch, the ideal electret effect can be achieved with a small amount of addition.
  • the fluorine electret powder is polytetrafluoroethylene micropowder, polyvinylidene fluoride micropowder, tetrafluoroethylene/hexafluoroethylene copolymer micropowder, and difluoroethylene/hexafluoroethylene copolymer micropowder.
  • the fluorine-based electret powder is most preferably ethylene fluoride/hexafluoroethylene copolymer fine powder.
  • the type of compatibilizer has a significant impact on the dispersion effect of fluorine electret powder.
  • Maleic anhydride grafted olefin copolymer/elastomer or glycidyl methacrylate grafted olefin copolymer/elastomer can make fluorine
  • the electret powder is well dispersed in the system, so that the effect of the electret masterbatch can be reflected.
  • the compatibilizer is maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, maleic anhydride grafted POE, glycidyl methacrylate grafted polypropylene, and glycidyl methacrylate grafted.
  • the compatibilizer is more preferably maleic anhydride grafted olefin copolymer/elastomer, specifically, the compatibilizer is more preferably maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene Or maleic anhydride grafted POE.
  • the compatibilizer is more preferably maleic anhydride grafted polypropylene or maleic anhydride grafted polyethylene.
  • processing aids are usually added to the masterbatch.
  • the processing aid is a lubricant, an antioxidant or an anti-aging agent.
  • antioxidants are, for example, antioxidant 1010 (tetra [ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester), antioxidant 168 (three (2,4- Di-tert-butylphenyl) phosphite) and the like.
  • Commonly used anti-aging agents are, for example, light stabilizer 944, UV-531, UV-770 and so on.
  • the polypropylene resin is homopolypropylene and/or copolymer polypropylene. More preferably, the melt index MFI of the polypropylene resin is preferably 1000-1500 g/10min at 230°C/2.16kg. Depending on the melt index of the polypropylene resin, it will also affect the filtration efficiency of the final meltblown non-woven fabric. Therefore, when the melt index of polypropylene resin is greater than or equal to 1000g/10min, it can already meet the filtration capacity of ordinary medical masks (YY/T 0969-2013 "Disposable Medical Masks"). When the melt index MFI of the polypropylene resin is 1500g/10min, the filtering effect required by KN95 can be achieved.
  • the fluorine electret powder can be added directly or dispersed into an emulsion and then added to the organic electret masterbatch formulation. Disperse the fluorine electret powder in the emulsion and then add it, the dispersion effect will be more ideal, but the production process of the masterbatch needs to remove the solvent in the emulsion, which makes the process more complicated.
  • the advantage of direct addition is that the production process is simpler, but the dispersion effect is slightly worse than the former.
  • the emulsion is preferably an aqueous solution containing a surfactant.
  • the preparation method of the special organic electret masterbatch for the meltblown non-woven fabric for masks is obtained by melt blending and extruding the components with a twin-screw extruder and pelletizing, and the process temperature is 130-220°C. Larger screw length-to-diameter ratio is conducive to the uniform dispersion of the components in the masterbatch, so that the masterbatch can be mixed with the polypropylene resin for meltblown non-woven fabrics to achieve better results. More preferably, the screw length-to-diameter ratio of the twin-screw extruder is 40:1 to 48:1.
  • a melt-blown non-woven fabric for masks the special organic electret masterbatch for melt-blown non-woven fabrics for masks and polypropylene for melt-blown non-woven fabrics, and the special organic electret masterbatch for melt-blown non-woven fabrics for masks
  • the weight ratio to polypropylene for melt-blown non-woven fabrics is 1: (19-49).
  • the melt index MFI of the polypropylene for meltblown non-woven fabrics is usually at 230°C/2.16kg, which is greater than or equal to 1000g/10min.
  • the present invention has the following beneficial effects:
  • the invention prepares electret masterbatch by adding fluorine electret powder of specific size instead of traditional inorganic electret powder or organic electret powder, which overcomes the ease of the existing electret masterbatch in the production process of meltblown non-woven fabrics. Because of the blocking phenomenon caused by the precipitation of electret powder, at the same time, selecting suitable compatibilizers and adjusting the screw length-to-diameter ratio, so that the fluorine electret powder can be better dispersed uniformly, so as to achieve the ideal under a small amount of addition. Electret effect.
  • homopolymer polypropylene purchased from Jinfa Technology Company, with a melt index MFI of 1500g/10min at 230°C/2.16kg
  • homopolymer polypropylene purchased from Jinfa Technology Company, with a melt index MFI of 230°C/2.16kg , Is 1000g/10min
  • PTFE powder purchased from Nanjing Tianshi New Material Technology Co., Ltd., with an average particle size of 0.05um-3um
  • PTFE/hexafluoroethylene copolymer powder A purchased from 3M, with an average particle size of 0.05 um-3um
  • tetrafluoroethylene/hexafluoroethylene copolymer micropowder B purchased from 3M company, its average particle size is about 5um
  • difluoroethylene/hexafluoroethylene copolymer micropowder purchased from Japan Daikin company, its average
  • the particle size is 0.05um-3um
  • sodium triazine phenolate purchased from Lucky Chemicals, with an average particle size of about 7um
  • nano tourmaline powder purchased from Tianjin Hongyan Tianshan Stone Industry Nanotechnology Co., Ltd.
  • maleic anhydride grafted polypropylene Purchased from Aaron, USA, brand/model is BONDYRAM 1001CN
  • the materials of Examples 1 to 5 and 7 to 8 were mixed in a high-speed mixer, and melted, blended and extruded through a twin-screw extruder with a length-to-diameter ratio of 40:1.
  • the temperature of the melting section was 150-210. °C, the special organic electret masterbatch for the meltblown non-woven fabric for masks was obtained.
  • Example 9 Add the polytetrafluoroethylene micropowder in Example 9 to 500 mL of water containing surfactants, disperse to form an emulsion, and mix it in a high-speed mixer according to the formula in Table 1, and pass through a twin-screw extruder with a length-to-diameter ratio of 40:1 Melt blending and extrusion, combined with vacuum treatment to remove water during extrusion, the temperature of the melting section is 150-210°C, to obtain special organic electret masterbatch for meltblown non-woven fabrics for masks.
  • Example 6 the material of Example 6 was mixed in a high-speed mixer, and melted and extruded through a twin-screw extruder with a length-to-diameter ratio of 48:1. The temperature of the melting section was 150-210°C to obtain a melt for masks. Organic electret masterbatch for spray non-woven fabric.
  • Comparative Examples 1 to 5 were mixed in a high-speed mixer, and melted and extruded through a twin-screw extruder with a length-to-diameter ratio of 40:1.
  • the temperature of the melting section was 150-210°C to obtain a mask.
  • the material of Comparative Example 6 was mixed in a high-speed mixer, and melted and extruded through a twin-screw extruder with a length-to-diameter ratio of 36:1.
  • the temperature of the melting section was 150-210°C to obtain a melting point for masks.
  • Sample test example 1 Filtration efficiency and resistance, electret effect, blockage test
  • the special organic electret masterbatches for meltblown non-woven fabrics for masks prepared in the above Examples 1-9 and Comparative Examples 1-6 were mixed with homopolypropylene resin (melt index 1500g/10min), wherein the mask uses polypropylene
  • the weight ratio of electret masterbatch material to PP resin is 1:19.
  • Correspondences are recorded as sample test examples 1-9 and sample comparative examples 1-6.
  • the obtained mixture is melted by a single screw, and is metered by a metering pump and sprayed through a spinneret to form fibers.
  • the fibers are drawn by hot air at 230-270°C to form test samples.
  • the test sample is subjected to 300kV electret treatment and then rewinded to obtain a sample meltblown non-woven material.
  • the special organic electret masterbatch for meltblown non-woven fabrics for masks prepared with the formula of Example 9 is mixed with homopolypropylene resin (melt index 1500g/10min), wherein the special organic meltblown non-woven fabrics for masks
  • the weight ratio of electret masterbatch to PP resin is 1:49.
  • the obtained mixture is melted by a single screw, and is metered by a metering pump and sprayed through a spinneret to form fibers.
  • the fibers are drawn by hot air at 230-270°C to form test samples.
  • the test sample is subjected to 300kV voltage electret treatment and then rewinded to obtain the sample melt-blown non-woven fabric material.
  • the meltblown non-woven fabric material is tested with the TSI8130 automatic filter material tester, using the GB19083-2010 "Technical Requirements for Medical Protective Masks" standard.
  • the medium uses NaCl particles with a median particle size of 0.075 ⁇ 0.02 ⁇ m, and the test flow rate is 85L/min. Carry out filtration efficiency and suction resistance tests.
  • we use the accelerated decay method which uses the accelerated charge decay under high temperature and high humidity conditions.
  • the blockage is evaluated by using a 500-mesh filter on the melt blown cloth machine for continuous production, and the time before the pressure is increased by 0.5 MPa before the machine produces the filter.
  • sample test examples 1-9 all the masterbatches under the formula of the present invention make the production of meltblown non-woven fabrics smoother. It can be seen from the sample test examples 1 to 3 that the filtration efficiency of the fluorine-based electret is the most preferred ethylene fluoride/hexafluoroethylene copolymer micropowder. It can be seen from the sample test example 6 that the longer the aspect ratio of the extruder, the more even the dispersion of the materials in the masterbatch, which makes the filtration effect and electret retention rate of the masterbatch better when it is applied to the meltblown non-woven fabric. good.

Abstract

Disclosed is an organic electret masterbatch for a melt-blown nonwoven fabric used in face masks and preparation method thereof, and the melt-blown nonwoven fabric prepared therefrom. Said organic electret masterbatch is prepared from the following constituents by weight percentage: 80-90% of polypropylene resin, 2-10% of fluorine electret powder, 1-10% of compatibilizer, and 0.05-0.5% of processing aid; the average particle diameter of said fluorine electret powder being 0.05-3 μm; said compatibilizer being a maleic anhydride grafted-olefin copolymer/elastomer or a glycidyl methacrylate grafted-olefin copolymer/elastomer; the melt flow index of said polypropylene resin being not less than 1000g/10min, and the length-to-diameter ratio of a screw for preparing the organic electret masterbatch for the melt-blown nonwoven fabric being greater than or equal to 40:1. The present organic electret masterbatch overcomes the blockage problem of current electret masterbatches caused by electret powder separation during the production process of the melt-blown nonwoven fabric, and, as the fluorine electret powder is more evenly dispersed, the addition of a small amount thereof can yield a good electret effect.

Description

口罩用熔喷无纺布专用有机驻极母粒及其制备方法、制成的熔喷无纺布Special organic electret masterbatch for melt-blown non-woven fabric for masks, preparation method thereof, and prepared melt-blown non-woven fabric 技术领域Technical field
本发明涉及熔喷无纺布领域，特别涉及口罩用熔喷无纺布专用有机驻极母粒及其制备方法、制成的熔喷无纺布。The invention relates to the field of melt-blown non-woven fabrics, in particular to organic electret masterbatch special for melt-blown non-woven fabrics for masks, a preparation method thereof, and a melt-blown non-woven fabric made.
背景技术Background technique
口罩用熔喷无纺布是一种制备过滤口罩的材料，尽管可以通过驻极处理提高其过滤效率，但是仅仅对无纺布自身进行驻极处理过滤效率的提升程度有限。为了达到理想的过滤效果，一般在口罩用熔喷无纺布的配方中，加入驻极材料或驻极母粒。驻极母粒又可以分为无机驻极母粒及有机驻极母粒两类。最常见的无机驻极母粒是以超高熔指的聚丙烯作为基体，经过添加分散剂等将粒径较小的电气石粉在基体实现分散后得到的，如专利CN1718910A提供了一种熔喷用改性聚丙烯母粒及其制备方法和用途，其通过偶联剂对电气石表面进行改性，然后添入分散剂将电气石粉均匀地分布在PP基体中而得到的驻极母粒。但是由于电气石粉粒径较小，很容易发生团聚，而且熔喷非纺织布使用的熔喷设备中，其喷丝板的孔径较小，长期使用过程中，这些团聚电气石粉有较大几率停留在喷丝板上，造成喷丝板堵塞的风险，停机清理需要较高的成本。Melt-blown non-woven fabric for masks is a material for preparing filter masks. Although the filtration efficiency can be improved by electret treatment, only the electret treatment of the non-woven fabric itself can improve the filtration efficiency to a limited extent. In order to achieve an ideal filtering effect, electret materials or electret masterbatches are generally added to the formula of meltblown non-woven fabrics for masks. Electret masterbatch can be divided into inorganic electret masterbatch and organic electret masterbatch. The most common inorganic electret masterbatch is obtained by adding ultra-high melting index polypropylene as the matrix, and dispersing tourmaline powder with a smaller particle size in the matrix after adding a dispersant. For example, the patent CN1718910A provides a melt blown The modified polypropylene masterbatch and the preparation method and application thereof are used to modify the surface of the tourmaline by a coupling agent, and then add a dispersant to uniformly distribute the tourmaline powder in the PP matrix to obtain the electret masterbatch. However, due to the small particle size of tourmaline powder, agglomeration is easy to occur, and in the meltblown equipment used for meltblown non-woven fabrics, the spinneret has a small aperture. During long-term use, these agglomerated tourmaline powders have a greater chance of staying On the spinneret, the risk of clogging of the spinneret is caused, and higher costs are required for shutdown and cleaning.
有机驻极母粒相对于无机驻极母粒的优势是其不具有团聚的风险。专利CN109354767A公开了一种有机驻极母粒的制备，其使用的驻极剂包括天然蜡、松香、有机玻璃、碳原子数为6～20的脂肪酸或其盐等，该有机驻极母粒与高熔指聚丙烯以1:20重量比添入，生产出来的熔喷布无纺布过滤效率基本可以达到95％以上。但是，这些驻极剂因为分子量较小，依然有析出迁移的风险。The advantage of organic electret masterbatch over inorganic electret masterbatch is that it does not have the risk of agglomeration. Patent CN109354767A discloses the preparation of an organic electret masterbatch, which uses electrets including natural wax, rosin, plexiglass, fatty acids with 6 to 20 carbon atoms or their salts, etc. The organic electret masterbatch is combined with The high melting index polypropylene is added in a weight ratio of 1:20, and the filtration efficiency of the produced meltblown non-woven fabric can basically reach more than 95%. However, these electrets still have the risk of precipitation and migration due to their small molecular weight.
发明内容Summary of the invention
本发明的目的在于克服现有技术的不足，提供一种口罩用熔喷无纺布专用有机驻极母粒，该母粒用于熔喷无纺布生产时，驻极效果理想且持久，并且熔喷无纺布生产过程无堵塞现象。The purpose of the present invention is to overcome the shortcomings of the prior art and provide a special organic electret masterbatch for meltblown non-woven fabrics for masks. When the masterbatch is used in the production of meltblown non-woven fabrics, the electret effect is ideal and lasting, and There is no blockage in the production process of meltblown non-woven fabrics.
本发明的另一目的在于提供所述口罩用熔喷无纺布专用有机驻极母粒的制备方法。Another object of the present invention is to provide a preparation method of the special organic electret masterbatch for the meltblown non-woven fabric for masks.
本发明的另一目的在于提供一种含有所述口罩用熔喷无纺布专用有机驻极 母粒的熔喷无纺布。Another object of the present invention is to provide a melt-blown non-woven fabric containing the organic electret masterbatch dedicated to the melt-blown non-woven fabric for masks.
本发明的上述目的通过如下技术方案予以实现：The above objectives of the present invention are achieved through the following technical solutions:
一种口罩用熔喷无纺布专用有机驻极母粒，所述有机驻极母粒由以下重量百分比计算的组分制成：A special organic electret masterbatch for meltblown non-woven fabrics for masks, the organic electret masterbatch is made of the following components calculated by weight percentage:
Figure PCTCN2020129279-appb-000001
Figure PCTCN2020129279-appb-000001
所述氟类驻极粉的颗粒平均粒径为0.05～3um；The average particle size of the particles of the fluorine electret powder is 0.05-3um;
所述相容剂为马来酸酐接枝烯烃共聚物/弹性体或甲基丙烯酸缩水甘油酯接枝的烯烃共聚物/弹性体；The compatibilizer is maleic anhydride grafted olefin copolymer/elastomer or glycidyl methacrylate grafted olefin copolymer/elastomer;
所述聚丙烯树脂为均聚聚丙烯和/或共聚聚丙烯，其熔融指数MFI在230℃/2.16kg下，不低于1000g/10min；The polypropylene resin is homopolypropylene and/or copolymer polypropylene, and its melt index MFI is not less than 1000g/10min at 230°C/2.16kg;
制备所述口罩用熔喷无纺布专用有机驻极母粒采用的双螺杆挤出机的螺杆长径比大于等于40:1；The screw length-to-diameter ratio of the twin-screw extruder used for preparing the special organic electret masterbatch for the meltblown non-woven fabric for masks is greater than or equal to 40:1;
所述氟类驻极粉为含氟乙烯基单体形成的高聚物或共聚物的微粉。The fluorine electret powder is a fine powder of a high polymer or copolymer formed from a fluorine-containing vinyl monomer.
氟类驻极粉是一类含氟有机聚合物的颗粒，已有报道将其作为驻极剂用于制备多孔过滤膜或大画面显示器的电泳颗粒，但未有将其用于制备口罩用熔喷无纺布的驻极母粒的报道。其原因是，这类物质虽然分子量较普通的有机驻极粉分子量大，不容易发生迁移，但其较常规有机驻极粉更难分散均匀，在熔喷无纺布中需要在较大添加量下才能达到理想的驻极效果，然而其在较大添加量时，在生产过程中容易造成断丝，并且因为分散不均容易导致驻极效果不持久。发明人意外发现，当把氟类驻极粉的粒径控制在上述范围时，配合适合的相容剂，以及合适的螺杆长径比，能使氟类驻极粉更容易地分散在驻极母粒中，并且使得在较少的添加量下，就能达到理想的驻极效果。Fluorine electret powder is a type of fluorine-containing organic polymer particles. It has been reported to be used as an electret for the preparation of electrophoretic particles for porous filter membranes or large-screen displays, but it has not been used for the preparation of masks. A report of electret masterbatch for spraying non-woven fabrics. The reason is that although this kind of material has a higher molecular weight than ordinary organic electret powder, it is not easy to migrate, but it is more difficult to disperse uniformly than conventional organic electret powder, and it needs to be added in a larger amount in meltblown non-woven fabrics. The ideal electret effect can only be achieved under the following conditions. However, when it is added in a large amount, it is easy to cause wire breakage during the production process, and the electret effect is not lasting due to uneven dispersion. The inventor unexpectedly discovered that when the particle size of the fluorine electret powder is controlled within the above-mentioned range, with a suitable compatibilizer and a suitable screw length-to-diameter ratio, the fluorine electret powder can be more easily dispersed in the electret. In the masterbatch, the ideal electret effect can be achieved with a small amount of addition.
更优选地，所述氟类驻极粉为聚四氟乙烯微粉、聚偏氟乙烯微粉、四氟乙烯/六氟乙烯共聚物微粉，二氟乙烯/六氟乙烯共聚物微粉。最优选地，所述氟类驻极粉最优选为二氟乙烯/六氟乙烯共聚物微粉。More preferably, the fluorine electret powder is polytetrafluoroethylene micropowder, polyvinylidene fluoride micropowder, tetrafluoroethylene/hexafluoroethylene copolymer micropowder, and difluoroethylene/hexafluoroethylene copolymer micropowder. Most preferably, the fluorine-based electret powder is most preferably ethylene fluoride/hexafluoroethylene copolymer fine powder.
相容剂的种类对氟类驻极粉的分散效果有较明显的影响，马来酸酐接枝烯烃 共聚物/弹性体或甲基丙烯酸缩水甘油酯接枝的烯烃共聚物/弹性体能使氟类驻极粉在体系中很好地分散，使得驻极母粒的效果得以体现。The type of compatibilizer has a significant impact on the dispersion effect of fluorine electret powder. Maleic anhydride grafted olefin copolymer/elastomer or glycidyl methacrylate grafted olefin copolymer/elastomer can make fluorine The electret powder is well dispersed in the system, so that the effect of the electret masterbatch can be reflected.
优选地，所述相容剂为马来酸酐接枝聚丙烯，马来酸酐接枝聚乙烯、马来酸酐接枝POE、甲基丙烯酸缩水甘油酯接枝聚丙烯、甲基丙烯酸缩水甘油酯接枝POE、甲基丙烯酸缩水甘油酯接枝EPDM中的一种或几种。Preferably, the compatibilizer is maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, maleic anhydride grafted POE, glycidyl methacrylate grafted polypropylene, and glycidyl methacrylate grafted. One or more of POE and glycidyl methacrylate grafted EPDM.
更优选地，所述相容剂更优选为马来酸酐接枝烯烃共聚物/弹性体，具体地，所述相容剂更优选为马来酸酐接枝聚丙烯，马来酸酐接枝聚乙烯或马来酸酐接枝POE。所述相容剂更优选为马来酸酐接枝聚丙烯或马来酸酐接枝聚乙烯。More preferably, the compatibilizer is more preferably maleic anhydride grafted olefin copolymer/elastomer, specifically, the compatibilizer is more preferably maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene Or maleic anhydride grafted POE. The compatibilizer is more preferably maleic anhydride grafted polypropylene or maleic anhydride grafted polyethylene.
为了便于加工方便，还通常在母粒中还会加入加工助剂。优选地，所述加工助剂为润滑剂、抗氧剂或抗老化剂。常用的抗氧剂例如是抗氧剂1010(四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯)、抗氧剂168(三(2,4-二叔丁基苯基)亚磷酸酯)等。常用的抗老化剂例如是光稳定剂944，UV-531，UV-770等。In order to facilitate processing, processing aids are usually added to the masterbatch. Preferably, the processing aid is a lubricant, an antioxidant or an anti-aging agent. Commonly used antioxidants are, for example, antioxidant 1010 (tetra [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester), antioxidant 168 (three (2,4- Di-tert-butylphenyl) phosphite) and the like. Commonly used anti-aging agents are, for example, light stabilizer 944, UV-531, UV-770 and so on.
本发明中，所述聚丙烯树脂为均聚聚丙烯和/或共聚聚丙烯，更优选地，所述聚丙烯树脂的熔融指数MFI优选在230℃/2.16kg下，为1000～1500g/10min。根据聚丙烯树脂的熔融指数不同，也会影响最终熔喷无纺布的过滤效率。因此，当聚丙烯树脂的熔融指数大于等于1000g/10min时，已经能满足普通医护口罩(YY/T 0969-2013《一次性使用医用口罩》)的过滤能力。而当所述聚丙烯树脂的熔融指数MFI在1500g/10min时，能够达到KN95要求的过滤效果。In the present invention, the polypropylene resin is homopolypropylene and/or copolymer polypropylene. More preferably, the melt index MFI of the polypropylene resin is preferably 1000-1500 g/10min at 230°C/2.16kg. Depending on the melt index of the polypropylene resin, it will also affect the filtration efficiency of the final meltblown non-woven fabric. Therefore, when the melt index of polypropylene resin is greater than or equal to 1000g/10min, it can already meet the filtration capacity of ordinary medical masks (YY/T 0969-2013 "Disposable Medical Masks"). When the melt index MFI of the polypropylene resin is 1500g/10min, the filtering effect required by KN95 can be achieved.
氟类驻极粉可以直接添加或采用分散成乳液再添加至所述有机驻极母粒配方中。将氟类驻极粉分散在乳液中再添加，分散效果会更理想，但是母粒生产过程需要对乳液中的溶剂进行去除，导致工艺更复杂。直接添加的优点是生产过程较简单，但分散效果比前者稍差。所述乳液优选为含有表面活性剂的水溶液。The fluorine electret powder can be added directly or dispersed into an emulsion and then added to the organic electret masterbatch formulation. Disperse the fluorine electret powder in the emulsion and then add it, the dispersion effect will be more ideal, but the production process of the masterbatch needs to remove the solvent in the emulsion, which makes the process more complicated. The advantage of direct addition is that the production process is simpler, but the dispersion effect is slightly worse than the former. The emulsion is preferably an aqueous solution containing a surfactant.
所述口罩用熔喷无纺布专用有机驻极母粒的制备方法，将所述组分用双螺杆挤出机进行熔融共混挤出并造粒得到，工艺温度在130～220℃。更大的螺杆长径比有利于组分在母粒中均匀分散，使母粒与熔喷无纺布用聚丙烯树脂混合后能达到更好的效果。更优选地，所述双螺杆挤出机的螺杆长径比为40:1～48:1。The preparation method of the special organic electret masterbatch for the meltblown non-woven fabric for masks is obtained by melt blending and extruding the components with a twin-screw extruder and pelletizing, and the process temperature is 130-220°C. Larger screw length-to-diameter ratio is conducive to the uniform dispersion of the components in the masterbatch, so that the masterbatch can be mixed with the polypropylene resin for meltblown non-woven fabrics to achieve better results. More preferably, the screw length-to-diameter ratio of the twin-screw extruder is 40:1 to 48:1.
一种口罩用熔喷无纺布，所述口罩用熔喷无纺布专用有机驻极母粒及熔喷无纺布用聚丙烯，所述口罩用熔喷无纺布专用有机驻极母粒与熔喷无纺布用聚丙烯的重量比为1：(19～49)。A melt-blown non-woven fabric for masks, the special organic electret masterbatch for melt-blown non-woven fabrics for masks and polypropylene for melt-blown non-woven fabrics, and the special organic electret masterbatch for melt-blown non-woven fabrics for masks The weight ratio to polypropylene for melt-blown non-woven fabrics is 1: (19-49).
所述熔喷无纺布用聚丙烯的熔融指数MFI通常在230℃/2.16kg下，大于等于1000g/10min。The melt index MFI of the polypropylene for meltblown non-woven fabrics is usually at 230°C/2.16kg, which is greater than or equal to 1000g/10min.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明通过加入采用特定尺寸的氟类驻极粉代替传统的无机驻极粉或有机驻极粉制备成驻极母粒，克服了现有的驻极母粒在熔喷无纺布生产过程容易因为驻极粉析出而导致的堵塞现象，同时选用合适的相容剂和调整螺杆长径比，使氟类驻极粉能更好地实现分散均匀，从而在较小的添加量下达到理想的驻极效果。The invention prepares electret masterbatch by adding fluorine electret powder of specific size instead of traditional inorganic electret powder or organic electret powder, which overcomes the ease of the existing electret masterbatch in the production process of meltblown non-woven fabrics. Because of the blocking phenomenon caused by the precipitation of electret powder, at the same time, selecting suitable compatibilizers and adjusting the screw length-to-diameter ratio, so that the fluorine electret powder can be better dispersed uniformly, so as to achieve the ideal under a small amount of addition. Electret effect.
具体实施方式detailed description
如无特殊说明，本发明所用原料、试剂及溶剂，均为商业购买未经任何处理。下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式并不受下述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。另外，关于本说明书中“份”、“％”，除非特别说明，分别表示“质量份”、“质量％”。Unless otherwise specified, the raw materials, reagents and solvents used in the present invention are all purchased commercially without any treatment. The present invention will be further described in detail below in conjunction with examples, but the implementation of the present invention is not limited by the following examples, and any other changes, modifications, substitutions, and combinations made without departing from the spirit and principle of the present invention , Simplified, should be equivalent replacement methods, and are all included in the protection scope of the present invention. In addition, "parts" and "%" in this specification mean "parts by mass" and "% by mass", unless otherwise specified.
均聚聚丙烯，购自金发科技公司，其熔融指数MFI在230℃/2.16kg下，为1500g/10min，均聚聚丙烯，购自金发科技公司，其熔融指数MFI在230℃/2.16kg下，为1000g/10min，Homopolymer polypropylene, purchased from Jinfa Technology Company, with a melt index MFI of 1500g/10min at 230°C/2.16kg, homopolymer polypropylene, purchased from Jinfa Technology Company, with a melt index MFI of 230°C/2.16kg , Is 1000g/10min,
聚四氟乙烯微粉，购自南京天诗新材料科技有限公司，其平均粒径为0.05um-3um；四氟乙烯/六氟乙烯共聚物微粉A，购自3M公司，其平均粒径为0.05um-3um；四氟乙烯/六氟乙烯共聚物微粉B，购自3M公司，其平均粒径为约为5um；二氟乙烯/六氟乙烯共聚物微粉，购自日本大金公司，其平均粒径为0.05um-3um；三嗪苯酚钠，购自乐凯化学，其平均粒径约为7um；纳米电气石粉，购自天津鸿雁天山石业纳米技术有限公司；马来酸酐接枝聚丙烯购自美国Aaron，牌号/型号为BONDYRAM 1001CN；甲基丙烯酸缩水甘油酯接枝聚丙烯购自利安德巴塞尔，牌号/型号为PX6006；甲基丙烯酸缩水甘油酯接枝EPDM购自科通塑胶科技，牌号/型号为KT-7；马来酸酐接枝POE购自美国杜邦，牌号为N493；乙烯丙烯酸共聚物购自陶氏化学，牌号/型号为EA101；恶唑啉接枝聚苯乙烯购自浩正塑胶科技，牌号/型号为ST-8；抗氧剂1010及抗氧剂168均购自BASF。PTFE powder, purchased from Nanjing Tianshi New Material Technology Co., Ltd., with an average particle size of 0.05um-3um; PTFE/hexafluoroethylene copolymer powder A, purchased from 3M, with an average particle size of 0.05 um-3um; tetrafluoroethylene/hexafluoroethylene copolymer micropowder B, purchased from 3M company, its average particle size is about 5um; difluoroethylene/hexafluoroethylene copolymer micropowder, purchased from Japan Daikin company, its average The particle size is 0.05um-3um; sodium triazine phenolate, purchased from Lucky Chemicals, with an average particle size of about 7um; nano tourmaline powder, purchased from Tianjin Hongyan Tianshan Stone Industry Nanotechnology Co., Ltd.; maleic anhydride grafted polypropylene Purchased from Aaron, USA, brand/model is BONDYRAM 1001CN; glycidyl methacrylate grafted polypropylene is purchased from Lyondell Basel, brand/model is PX6006; glycidyl methacrylate grafted EPDM is purchased from Ketong Plastic Technology , Grade/model is KT-7; maleic anhydride grafted POE is purchased from DuPont, the grade is N493; ethylene acrylic acid copolymer is purchased from Dow Chemical, grade/model is EA101; oxazoline grafted polystyrene is purchased from Haozheng Plastic Technology, the brand/model is ST-8; Antioxidant 1010 and Antioxidant 168 are both purchased from BASF.
实施例1～9Examples 1-9
按照表1配方将实施例1～5、7～8的材料投到高速混合机混合，并通过长径比为40:1的双螺杆挤出机熔融共混挤出，熔融段温度150～210℃，得到口罩用熔喷无纺布专用有机驻极母粒。According to the formula in Table 1, the materials of Examples 1 to 5 and 7 to 8 were mixed in a high-speed mixer, and melted, blended and extruded through a twin-screw extruder with a length-to-diameter ratio of 40:1. The temperature of the melting section was 150-210. ℃, the special organic electret masterbatch for the meltblown non-woven fabric for masks was obtained.
将实施例9中的聚四氟乙烯微粉加入500mL含有表面活性剂的水，分散形成乳液，按照表1配方投到高速混合机混合，并通过长径比为40:1的双螺杆挤出机熔融共混挤出，挤出时结合真空处理除去水，熔融段温度150～210℃，得到口罩用熔喷无纺布专用有机驻极母粒。Add the polytetrafluoroethylene micropowder in Example 9 to 500 mL of water containing surfactants, disperse to form an emulsion, and mix it in a high-speed mixer according to the formula in Table 1, and pass through a twin-screw extruder with a length-to-diameter ratio of 40:1 Melt blending and extrusion, combined with vacuum treatment to remove water during extrusion, the temperature of the melting section is 150-210°C, to obtain special organic electret masterbatch for meltblown non-woven fabrics for masks.
按照表1配方将实施例6的材料投到高速混合机混合，并通过长径比为48:1的双螺杆挤出机熔融共混挤出，熔融段温度150～210℃，得到口罩用熔喷无纺布专用有机驻极母粒。According to the formula in Table 1, the material of Example 6 was mixed in a high-speed mixer, and melted and extruded through a twin-screw extruder with a length-to-diameter ratio of 48:1. The temperature of the melting section was 150-210°C to obtain a melt for masks. Organic electret masterbatch for spray non-woven fabric.
表1Table 1
Figure PCTCN2020129279-appb-000002
Figure PCTCN2020129279-appb-000002
对比例1～6Comparative example 1～6
按照表2配方将对比例1～5的材料投到高速混合机混合，并通过长径比为40:1的双螺杆挤出机熔融共混挤出，熔融段温度150～210℃，得到口罩用熔喷无纺布专用有机驻极母粒。According to the formula in Table 2, the materials of Comparative Examples 1 to 5 were mixed in a high-speed mixer, and melted and extruded through a twin-screw extruder with a length-to-diameter ratio of 40:1. The temperature of the melting section was 150-210°C to obtain a mask. Use organic electret masterbatch for meltblown non-woven fabric.
按照表2配方将对比例6的材料投到高速混合机混合，并通过长径比为36:1的双螺杆挤出机熔融共混挤出，熔融段温度150～210℃，得到口罩用熔喷无纺布专用有机驻极母粒。According to the formula in Table 2, the material of Comparative Example 6 was mixed in a high-speed mixer, and melted and extruded through a twin-screw extruder with a length-to-diameter ratio of 36:1. The temperature of the melting section was 150-210°C to obtain a melting point for masks. Organic electret masterbatch for spray non-woven fabric.
表2Table 2
Figure PCTCN2020129279-appb-000003
Figure PCTCN2020129279-appb-000003
样品测试例1：过滤效率及阻力、驻极效果、堵塞情况测试Sample test example 1: Filtration efficiency and resistance, electret effect, blockage test
过滤效率及阻力测试Filter efficiency and resistance test
将上述实施例1～9、对比例1～6制备的口罩用熔喷无纺布专用有机驻极母粒与均聚聚丙烯树脂(熔指1500g/10min)混合，其中所述口罩用聚丙烯驻极母粒材料与PP树脂的重量比为1:19。对应记为样品测试例1～9和样品对比例1～6。将所得的混合物经过单螺杆熔融，经计量泵计量后通过喷丝板喷出形成纤维。所述纤维经过230～270℃的热风牵引，形成测试样品。测试样品再经过300kV电压 驻极处理后再收卷，得到样品熔喷无纺布材料。The special organic electret masterbatches for meltblown non-woven fabrics for masks prepared in the above Examples 1-9 and Comparative Examples 1-6 were mixed with homopolypropylene resin (melt index 1500g/10min), wherein the mask uses polypropylene The weight ratio of electret masterbatch material to PP resin is 1:19. Correspondences are recorded as sample test examples 1-9 and sample comparative examples 1-6. The obtained mixture is melted by a single screw, and is metered by a metering pump and sprayed through a spinneret to form fibers. The fibers are drawn by hot air at 230-270°C to form test samples. The test sample is subjected to 300kV electret treatment and then rewinded to obtain a sample meltblown non-woven material.
另外，以实施例9的配方制备的口罩用熔喷无纺布专用有机驻极母粒与均聚聚丙烯树脂(熔指1500g/10min)混合，其中所述口罩用熔喷无纺布专用有机驻极母粒与PP树脂的重量比为1:49。对应记为样品测试例10。将所得的混合物经过单螺杆熔融，经计量泵计量后通过喷丝板喷出形成纤维。所述纤维经过230～270℃的热风牵引，形成测试样品。测试样品再经过300kV电压驻极处理后再收卷，得到样品熔喷无纺布材料。In addition, the special organic electret masterbatch for meltblown non-woven fabrics for masks prepared with the formula of Example 9 is mixed with homopolypropylene resin (melt index 1500g/10min), wherein the special organic meltblown non-woven fabrics for masks The weight ratio of electret masterbatch to PP resin is 1:49. Corresponding to the sample test example 10. The obtained mixture is melted by a single screw, and is metered by a metering pump and sprayed through a spinneret to form fibers. The fibers are drawn by hot air at 230-270°C to form test samples. The test sample is subjected to 300kV voltage electret treatment and then rewinded to obtain the sample melt-blown non-woven fabric material.
该熔喷无纺布材料使用TSI8130自动滤料测试仪测试，使用GB19083-2010《医用防护口罩技术要求》标准，介质采用数量中值粒径0.075±0.02μm的NaCl颗粒，测试流量85L/min，进行过滤效率及吸气阻力测试。对于驻极效果的长期性来看，我们使用了加速衰减的方法，利用在高温高湿情况下加速电荷的衰减，具体实施温度为85℃，湿度85％，放置24h后取出，平衡4h后，通过前面的方法测试其过滤效率及阻力，计算出比对其放进去前的过滤效率及吸气阻力，通过公式Q F＝-ln(过滤效率)/吸气阻力，分别计算出老化前后的品质因子Q F，驻极保持率％＝Q 1(加速老化后)/Q 0×100％。堵塞情况以熔喷布机器上使用500目滤网，连续生产，以机器生产滤网前压力提高0.5MPa的时间来评价。 The meltblown non-woven fabric material is tested with the TSI8130 automatic filter material tester, using the GB19083-2010 "Technical Requirements for Medical Protective Masks" standard. The medium uses NaCl particles with a median particle size of 0.075±0.02μm, and the test flow rate is 85L/min. Carry out filtration efficiency and suction resistance tests. For the long-term perspective of the electret effect, we use the accelerated decay method, which uses the accelerated charge decay under high temperature and high humidity conditions. The specific implementation temperature is 85°C, humidity 85%, placed for 24h, and then taken out, after balancing for 4h, Test the filtration efficiency and resistance through the previous method, calculate the filtration efficiency and suction resistance before putting it in, and calculate the quality before and after aging through the formula Q F =-ln (filtration efficiency)/inspiration resistance Factor Q F , electret retention %=Q 1 (after accelerated aging)/Q 0 ×100%. The blockage is evaluated by using a 500-mesh filter on the melt blown cloth machine for continuous production, and the time before the pressure is increased by 0.5 MPa before the machine produces the filter.
结果如表3所示。从样品对比例1、样品对比例2可以看出，当相容剂选择不合适时，产品较容易团聚，导致其过滤效果下降。从样品对比例3可以看出，当氟类驻极粉的粒径过大，导致产品容易断丝，布面不够紧密，从而使过滤效率降低。从样品对比例4、样品对比例5可以看出，常规使用的有机驻极粉或无机驻极粉，均在生产过程中会出现堵塞。从样品对比例6可以看出，当驻极母粒制备过程中挤出机的螺杆长度不够，也会影响含氟驻极粉的分散，从而影响驻极效果。The results are shown in Table 3. It can be seen from the sample comparative example 1 and the sample comparative example 2 that when the compatibilizer is not properly selected, the product is easier to agglomerate, resulting in a decrease in its filtering effect. It can be seen from the sample comparative example 3 that when the particle size of the fluorine electret powder is too large, the product is easy to break and the cloth surface is not tight enough, thereby reducing the filtration efficiency. It can be seen from the sample comparative example 4 and the sample comparative example 5 that the conventionally used organic electret powder or inorganic electret powder will be clogged during the production process. It can be seen from the sample comparative example 6 that when the length of the screw of the extruder is not enough during the preparation of the electret masterbatch, it will also affect the dispersion of the fluorine-containing electret powder, thereby affecting the electret effect.
表3table 3
Figure PCTCN2020129279-appb-000004
Figure PCTCN2020129279-appb-000004
Figure PCTCN2020129279-appb-000005
Figure PCTCN2020129279-appb-000005
从样品测试例1～9可以看出，本发明配方下的母粒均使熔喷无纺布生产更顺畅。从样品测试例1～3可以看出，以二氟乙烯/六氟乙烯共聚物微粉为最优选的氟类驻极剂的过滤效率。从样品测试例6可以看出，挤出机的长径比越长，能使母粒中各物料分散更均匀，使得母粒应用于熔喷无纺布时，过滤效果和驻极保持率更好。从样品测试例1、样品测试例7和8可以看出，马来酸酐接枝烯烃共聚物作为相容剂效果更好。从样品测试例9可以看出氟类驻极剂以乳液的形式加入母粒中，过滤效果有更好的提升，但工艺方面变得更为复杂。从样品测试例10可以看出，本发明的母粒，在添加量较小的情况下，依然具有良好的驻极效果。It can be seen from the sample test examples 1-9 that all the masterbatches under the formula of the present invention make the production of meltblown non-woven fabrics smoother. It can be seen from the sample test examples 1 to 3 that the filtration efficiency of the fluorine-based electret is the most preferred ethylene fluoride/hexafluoroethylene copolymer micropowder. It can be seen from the sample test example 6 that the longer the aspect ratio of the extruder, the more even the dispersion of the materials in the masterbatch, which makes the filtration effect and electret retention rate of the masterbatch better when it is applied to the meltblown non-woven fabric. good. It can be seen from Sample Test Example 1 and Sample Test Examples 7 and 8 that the maleic anhydride grafted olefin copolymer is more effective as a compatibilizer. It can be seen from Sample Test Example 9 that the fluorine electret is added to the masterbatch in the form of an emulsion, and the filtration effect is better improved, but the process becomes more complicated. It can be seen from the sample test example 10 that the masterbatch of the present invention still has a good electret effect when the addition amount is small.

Claims (10)

  1. 一种口罩用熔喷无纺布专用有机驻极母粒，其特征在于，所述有机驻极母粒由以下重量百分比计算的组分制成：A special organic electret masterbatch for meltblown non-woven fabrics for masks is characterized in that the organic electret masterbatch is made of the following components calculated by weight percentage:
    Figure PCTCN2020129279-appb-100001
    Figure PCTCN2020129279-appb-100001
    所述氟类驻极粉的颗粒平均粒径为0.05～3um；The average particle size of the particles of the fluorine electret powder is 0.05-3um;
    所述相容剂为马来酸酐接枝烯烃共聚物/弹性体或甲基丙烯酸缩水甘油酯接枝的烯烃共聚物/弹性体；The compatibilizer is maleic anhydride grafted olefin copolymer/elastomer or glycidyl methacrylate grafted olefin copolymer/elastomer;
    所述聚丙烯树脂为均聚聚丙烯和/或共聚聚丙烯，其熔融指数MFI在230℃/2.16kg下，不低于1000g/10min；The polypropylene resin is homopolypropylene and/or copolymer polypropylene, and its melt index MFI is not less than 1000g/10min at 230°C/2.16kg;
    制备所述口罩用熔喷无纺布专用有机驻极母粒采用的双螺杆挤出机的螺杆长径比大于等于40:1；The screw length-to-diameter ratio of the twin-screw extruder used for preparing the special organic electret masterbatch for the meltblown non-woven fabric for masks is greater than or equal to 40:1;
    所述氟类驻极粉为含氟乙烯基单体形成的高聚物或共聚物。The fluorine electret powder is a high polymer or copolymer formed from a fluorine-containing vinyl monomer.
  2. 根据权利要求1所述口罩用熔喷无纺布专用有机驻极母粒，其特征在于，所述氟类驻极粉为聚四氟乙烯、聚偏氟乙烯、四氟乙烯/六氟乙烯共聚物，二氟乙烯/六氟乙烯共聚物。The special organic electret masterbatch for meltblown non-woven fabric for masks according to claim 1, wherein the fluorine electret powder is polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene/hexafluoroethylene copolymer Material, difluoroethylene/hexafluoroethylene copolymer.
  3. 根据权利要求1所述口罩用熔喷无纺布专用有机驻极母粒，其特征在于，所述相容剂为马来酸酐接枝聚丙烯、马来酸酐接枝聚乙烯、马来酸酐接枝POE、甲基丙烯酸缩水甘油酯接枝聚丙烯、甲基丙烯酸缩水甘油酯接枝POE、甲基丙烯酸缩水甘油酯接枝EPDM中的一种或几种。The special organic electret masterbatch for meltblown non-woven fabrics for masks according to claim 1, wherein the compatibilizer is maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, maleic anhydride grafted One or more of grafted POE, glycidyl methacrylate grafted polypropylene, glycidyl methacrylate grafted POE, and glycidyl methacrylate grafted EPDM.
  4. 根据权利要求1或3所述口罩用熔喷无纺布专用有机驻极母粒，其特征在于，所述相容剂为马来酸酐接枝聚丙烯、马来酸酐接枝聚乙烯或马来酸酐接枝POE。The special organic electret masterbatch for meltblown non-woven fabric for masks according to claim 1 or 3, wherein the compatibilizer is maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene or maleic anhydride. POE grafted with acid anhydride.
  5. 根据权利要求1所述口罩用熔喷无纺布专用有机驻极母粒，其特征在于，所述加工助剂为润滑剂、抗氧剂或抗老化剂。The special organic electret masterbatch for meltblown non-woven fabric for masks according to claim 1, wherein the processing aid is a lubricant, an antioxidant or an anti-aging agent.
  6. 根据权利要求1所述口罩用熔喷无纺布专用有机驻极母粒，其特征在于，所述聚丙烯树脂为均聚聚丙烯和/或共聚聚丙烯，其熔融指数MFI在230℃/2.16kg下，为1000～1500g/10min。The special organic electret masterbatch for meltblown non-woven fabric for masks according to claim 1, wherein the polypropylene resin is homopolypropylene and/or copolymer polypropylene, and its melt index MFI is 230°C/2.16 Under kg, it is 1000～1500g/10min.
  7. 根据权利要求1所述口罩用熔喷无纺布专用有机驻极母粒，其特征在于，氟 类驻极粉直接添加或采用分散在乳液中的形式添加至所述有机驻极母粒中。The special organic electret masterbatch for meltblown non-woven fabric for masks according to claim 1, wherein the fluorine electret powder is added directly or dispersed in an emulsion to the organic electret masterbatch.
  8. 权利要求1至7任一项所述口罩用熔喷无纺布专用有机驻极母粒的制备方法，其特征在于，将所述组分用双螺杆挤出机进行熔融共混挤出并造粒得到，工艺温度在130～220℃。The method for preparing special organic electret masterbatch for meltblown non-woven fabric for masks according to any one of claims 1 to 7, characterized in that the components are melt-blended and extruded by a twin-screw extruder. Granules are obtained, and the process temperature is 130-220°C.
  9. 根据权利要求8所述制备方法，其特征在于，所述双螺杆挤出机的螺杆长径比为40:1～48:1。The preparation method according to claim 8, wherein the screw length-to-diameter ratio of the twin-screw extruder is 40:1 to 48:1.
  10. 一种口罩用熔喷无纺布，其特征在于，包含权利要求1至7任一项所述口罩用熔喷无纺布专用有机驻极母粒及熔喷无纺布用聚丙烯，所述口罩用熔喷无纺布专用有机驻极母粒与熔喷无纺布用聚丙烯的重量比为1：(19～49)。A melt-blown non-woven fabric for masks, characterized in that it comprises the special organic electret masterbatch for melt-blown non-woven fabrics for masks according to any one of claims 1 to 7 and polypropylene for melt-blown non-woven fabrics. The weight ratio of organic electret masterbatch for melt-blown non-woven fabrics for masks to polypropylene for melt-blown non-woven fabrics is 1: (19～49).
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