WO2023103424A1 - 一种负离子防爆膜及其制备方法 - Google Patents

一种负离子防爆膜及其制备方法 Download PDF

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WO2023103424A1
WO2023103424A1 PCT/CN2022/110016 CN2022110016W WO2023103424A1 WO 2023103424 A1 WO2023103424 A1 WO 2023103424A1 CN 2022110016 W CN2022110016 W CN 2022110016W WO 2023103424 A1 WO2023103424 A1 WO 2023103424A1
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anion
negative ion
hardening coating
explosion
agent
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PCT/CN2022/110016
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English (en)
French (fr)
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张宁
姚俊
夏萍
张宏元
蔡彦
罗国旗
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湖北航天化学技术研究所
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Publication of WO2023103424A1 publication Critical patent/WO2023103424A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Definitions

  • the disclosure relates to the technical field of explosion-proof membranes, in particular to a negative ion explosion-proof membrane and a preparation method thereof.
  • Attaching the explosion-proof film to the glass can play the role of wear resistance and anti-scratch, and the most important thing is to prevent the fragments from hurting people when the glass bursts and breaks.
  • the current problem to be solved urgently by the explosion-proof membrane is that it can play the role of killing bacteria in the bathing environment and purifying the air.
  • the present disclosure provides an anion explosion-proof film, which includes a first anion hardening coating and a second anion hardening coating, a base film, an installation adhesive layer and a release film adjacent in sequence;
  • the content of the water-based anion of the first anion-hardening coating is less than the content of the water-based anion in the second anion-hardening coating
  • the particle size of the water-based negative ions in the first negative ion-hardening coating is smaller than the particle size of the water-based negative ions in the second negative-ion hardening coating.
  • the total thickness of the first anion hardening coating and the second anion hardening coating is 2 ⁇ m ⁇ 10 ⁇ m.
  • the layer thickness of the first negative ion hardening coating is 1 ⁇ m to 5 ⁇ m; the particle size of the negative ion agent in the first negative ion hardening coating is 20 nm to 60 nm; A mass percent content in the negative ion hardening coating is 0.01wt% to 0.1wt%. In some embodiments, the particle diameter of the anion agent in the first anion hardening coating is 20nm to 40nm.
  • the thickness of the second negative ion hardening coating is 1 ⁇ m to 5 ⁇ m; the particle size of the negative ion agent in the second negative ion hardening coating is 70 nm to 120 nm; The mass percent content in the negative ion hardening coating is 0.2wt%-0.5wt%. In some embodiments, the particle size of the anion agent in the second anion hardening coating is 80nm ⁇ 100nm.
  • the negative ion agent is made from the natural mineral tourmaline through ultrafine pulverization, coating modification, and ion exchange doping.
  • the material of the base film is PET, and the thickness of the base film is 20 ⁇ m ⁇ 200 ⁇ m. In some embodiments, the thickness of the base film is 50 ⁇ m ⁇ 100 ⁇ m. In some embodiments, the light transmittance of the base film is above 85%. In some embodiments, the light transmittance of the base film is above 90%.
  • the material of the installation adhesive layer is acrylic pressure-sensitive adhesive, and the thickness of the installation adhesive layer is 10 ⁇ m ⁇ 20 ⁇ m. In some embodiments, the thickness of the mounting adhesive layer is 12 ⁇ m ⁇ 15 ⁇ m. In some embodiments, the peeling force of the mounting adhesive layer is 5N-20N. In some embodiments, the peeling force of the mounting adhesive layer is 10N ⁇ 15N.
  • the release film is a PET film treated with fluorine or a silicon-coated release agent, and the thickness of the release film is 10 ⁇ m ⁇ 50 ⁇ m. In some embodiments, the thickness of the release film is 20 ⁇ m ⁇ 40 ⁇ m. In some embodiments, the release force of the release film is 0.05N-0.15N. In some embodiments, the release force of the release film is 0.08N-0.12N; the residual adhesion rate of the release film is greater than 85%. In some embodiments, the residual adhesion of the release film is greater than 90%.
  • the waterborne urethane acrylate oligomer is a waterborne aliphatic urethane acrylate resin
  • the mass percentage of the waterborne urethane acrylate oligomer in the negative ion hardening coating is 15 wt % to 80 wt %.
  • the mass percentage of the water-based polyurethane acrylate oligomer in the negative ion hardening coating is 30wt%-60wt%.
  • the photoinitiator is one of aqueous benzoin derivatives, aqueous benzophenone derivatives and alkylaryl ketone derivatives.
  • the photoinitiator is 2-hydroxy-2-methyl-phenylacetone; the mass percentage of the photoinitiator in the negative ion hardening coating is 1wt% ⁇ 10wt%. In some embodiments, the mass percent content of the photoinitiator in the negative ion hardening coating is 2wt% ⁇ 6wt%.
  • the present disclosure also provides a preparation method of negative ion explosion-proof film, said method comprising the steps of:
  • One side of the base film is coated with a layer of negative ion hardening paint by roller coating or scraping, after drying, it is cured by ultraviolet (UV), and then the surface is coated with a second layer of negative ion hardening paint in the same way. UV curing after drying to prepare a base film with negative ion hardening coating;
  • the other side of the base film is coated with mounting glue, and compounded with the release film to obtain an anion explosion-proof film.
  • the present disclosure provides a kind of preparation method of negative ion explosion-proof membrane, described method comprises the steps:
  • the content of the water-based anion of the first anion-hardening coating mixture is less than the content of the water-based anion in the second anion-hardening coating mixture;
  • the particle diameter of the water-based anion of the first anion-hardening coating mixture is smaller than the particle diameter of the water-based anion in the second anion-hardening coating mixture;
  • the first negative ion hardening coating mixture is coated on one side of the base film, and dried and cured to obtain the first negative ion hardening coating;
  • the second negative ion hardening coating mixture is coated on the first negative ion hardening coating, and dried and cured to obtain the second negative ion hardening coating;
  • the other side of the base film is coated with an installation adhesive, and compounded with a release film to obtain an anion explosion-proof film.
  • the layer thickness of the first negative ion hardening coating is 1 ⁇ m to 5 ⁇ m; the particle size of the negative ion agent in the first negative ion hardening coating is 20 nm to 60 nm; A mass percent content in the negative ion hardening coating is 0.01% to 0.1wt%. In some embodiments, the particle size of the anion agent in the first anion hardening coating is 20nm-40nm.
  • the thickness of the second negative ion hardening coating is 1 ⁇ m to 5 ⁇ m; the particle size of the negative ion agent in the second negative ion hardening coating is 70 nm to 120 nm; The mass percent content in the negative ion hardening coating is 0.2% to 0.5wt%. In some embodiments, the particle size of the anion agent in the second anion hardening coating is 80nm ⁇ 100nm.
  • Fig. 1 is the structural representation of negative ion explosion-proof membrane
  • Some embodiments of the present disclosure provide a negative ion explosion-proof membrane that releases negative ions efficiently and persistently.
  • two layers of hardened coatings are coated on one side of the base film, and the two layers of hardened coatings respectively contain negative ion agents with different concentrations and different particle sizes.
  • the concentration of anion agent in a layer of anion hardening coating close to the base film is higher and the particle size is larger, while the concentration of anion agent in a layer of anion hardening coating far away from the base film is lower and the particle size is larger. smaller diameter.
  • this design utilizes the concentration gradient of the anion agent formed between the two layers of anion-hardening coatings to provide migration power for the anion agent particles, migrating from a high-concentration area to a low-concentration area, while , due to the large particle size of the anion agent in the anion hardening coating close to the basement membrane, the migration resistance is relatively large, which reduces the migration rate of the anion agent and prolongs the release of anion on the surface; while it is far away from the basement membrane
  • the particle size of the negative ion agent in one layer of negative ion hardening coating is small, which is conducive to its migration to the outermost layer, and plays the role of releasing negative ions.
  • a negative ion explosion-proof membrane includes a first negative ion hardening coating 11 and a second negative ion hardening coating 12 , a base film 2 , an installation glue layer 3 and a release film 4 adjacent in sequence.
  • the content of the water-based anion of the first anion-hardening coating 11 is less than the content of the water-based anion in the second anion-hardening coating 12;
  • the particle size of the water-based negative ions in the first negative-ion hardening coating 11 is smaller than the particle size of the water-based negative ions in the second negative-ion hardening coating 12 .
  • the material of the base film is PET.
  • the thickness of the base film may be between 20 ⁇ m and 200 ⁇ m.
  • the thickness of the base film may be, for example, 50 ⁇ m ⁇ 180 ⁇ m, 70 ⁇ m ⁇ 150 ⁇ m, or 90 ⁇ m ⁇ 120 ⁇ m, such as 20 ⁇ m, 40 ⁇ m, 60 ⁇ m, 80 ⁇ m, 100 ⁇ m, 120 ⁇ m, 140 ⁇ m, 160 ⁇ m, 180 ⁇ m, 200 ⁇ m.
  • the base film is a PET film with a thickness of 50 ⁇ m ⁇ 100 ⁇ m.
  • the light transmittance of the base film is above 85%.
  • the light transmittance of the base film can be, for example, 85% to 99%, 87% to 95%, or 89% to 92%, such as 85%, 87%, 90%, 92%, 94%, 96%. %, 98%, 99%.
  • the PET film has a light transmittance above 90%.
  • the material of the installation adhesive layer is acrylic pressure-sensitive adhesive.
  • the thickness of the mounting adhesive layer may be between 10 ⁇ m and 20 ⁇ m. In some embodiments, the thickness of the mounting adhesive layer may be 11 ⁇ m ⁇ 18 ⁇ m, 11.5 ⁇ m ⁇ 17 ⁇ m, 12 ⁇ m ⁇ 15 ⁇ m or 13 ⁇ m ⁇ 14 ⁇ m, such as 10 ⁇ m, 12 ⁇ m, 14 ⁇ m, 16 ⁇ m, 18 ⁇ m, 20 ⁇ m.
  • the peeling force of the mounting adhesive layer is 5N ⁇ 20N. In some embodiments, the peeling force may be 7N-18N, 10N-15N or 12N-14N acrylate pressure sensitive adhesive.
  • the release film is a PET film treated with fluorine-coated or silicon-coated release agent.
  • the thickness of the release film may range from 10 ⁇ m to 50 ⁇ m. In some embodiments, the thickness of the release film may be 15 ⁇ m ⁇ 45 ⁇ m, 20 ⁇ m ⁇ 40 ⁇ m, 25 ⁇ m ⁇ 35 ⁇ m, or 28 ⁇ m ⁇ 32 ⁇ m.
  • the release force of the release film is 0.05N-0.15N. In some embodiments, the release force of the release film may be 0.06N-0.13N, 0.08N-0.12N or 0.09N-0.11N. In some embodiments, the residual adhesion of the release film is greater than 85%. In some embodiments, the residual adhesion rate is greater than 90%.
  • the total thickness of the negative ion hardening coating is 2 ⁇ m ⁇ 10 ⁇ m.
  • the negative ion hardening coating 11 has a thickness of 1 ⁇ m to 5 ⁇ m, such as 1.5 ⁇ m to 4.5 ⁇ m, 2 ⁇ m to 4 ⁇ m or 2.5 ⁇ m to 3.5 ⁇ m, such as 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m.
  • the negative ion hardening coating 12 has a thickness of 1 ⁇ m to 5 ⁇ m, such as 1.5 ⁇ m to 4.5 ⁇ m, 2 ⁇ m to 4 ⁇ m or 2.5 ⁇ m to 3.5 ⁇ m, such as 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m.
  • the negative ion hardening coating comprises the following components: waterborne urethane acrylate oligomer, photoinitiator, negative ion agent, deionized water or distilled water.
  • the waterborne urethane acrylate oligomer used is a waterborne aliphatic urethane acrylate resin.
  • the water-based aliphatic polyurethane acrylic resin can be selected: 6166W, DR-W425, DR-W450, DR-W470, DR-W482, DR-W495, DR-W402S, DR-W413S, DR- One or both of the W485S.
  • the mass percentage of the waterborne polyurethane acrylate resin in the negative ion hardening coating is 15wt%-80wt%.
  • the percentage of waterborne urethane acrylate resin in the negative ion hardening coating is, for example, 20wt% to 75wt%, 25wt% to 70wt%, 30wt% to 60wt%, or 35wt% to 55wt%, such as 15wt% , 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%.
  • the photoinitiator is one of aqueous benzoin derivatives, aqueous benzophenone derivatives and alkylaryl ketone derivatives.
  • the photoinitiator is 2-hydroxy-2-methyl-phenylacetone (1173), a derivative of an alkyl aryl ketone.
  • the mass percent content of the photoinitiator in the negative ion hardening coating is 1 wt % ⁇ 10 wt %.
  • the mass percent content of the photoinitiator in the negative ion hardening coating is, for example, 1.5wt% to 8wt%, 2wt% to 7wt%, 2wt% to 6wt%, or 3wt% to 5wt%, such as 1wt% , 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%.
  • the negative ion agent is obtained from the natural mineral tourmaline through ultra-fine pulverization, coating modification, ion exchange doping and other methods.
  • the particle size range of the negative ion agent is between 20nm ⁇ 120nm, such as 30nm ⁇ 110nm, 40nm ⁇ 100nm or 50nm ⁇ 90nm, such as 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm , 110nm, 120nm.
  • the layer thickness of the first negative ion hardening coating is 1 ⁇ m to 5 ⁇ m, for example 1.5 ⁇ m to 4.5 ⁇ m, 2 ⁇ m to 4 ⁇ m or 2.5 ⁇ m to 3.5 ⁇ m, such as 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m. .
  • the particle size of the negative ion agent in the first negative ion hardening coating is 20nm ⁇ 60nm, for example, the particle size is 20nm ⁇ 50nm, 20nm ⁇ 40nm, 25nm ⁇ 35nm or 20nm ⁇ 25nm, such as 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm.
  • the mass percentage of anion agent in the first anion hardening coating is 0.01wt% ⁇ 0.1wt%, such as mass percentage is 0.02wt% ⁇ 0.08wt%, 0.03wt% ⁇ 0.07wt % or 0.04wt% ⁇ 0.06wt%, such as 0.01wt%, 0.02wt%, 0.03wt%, 0.04wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, 1wt%.
  • the thickness of the second negative ion hardening coating is 1 ⁇ m to 5 ⁇ m, such as 1.5 ⁇ m to 4.5 ⁇ m, 2 ⁇ m to 4 ⁇ m or 2.5 ⁇ m to 3.5 ⁇ m, such as 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m.
  • the particle size of the negative ion agent in the second negative ion hardening coating is 70nm ⁇ 120nm, for example, the particle size can be 75nm ⁇ 110nm, 80nm ⁇ 100nm, 80nm ⁇ 90nm or 85nm ⁇ 90nm, such as 70nm, 80nm, 90nm, 100nm, 110nm.
  • the mass percentage of the anion agent in the second anion hardening coating is 0.2wt% to 0.5wt%, such as 0.24% to 0.48wt%, 0.26% to 0.42wt%, or 0.3% to 0.4wt%, such as 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%, 0.5wt%.
  • Some embodiments of the present disclosure provide a kind of preparation method of negative ion explosion-proof membrane, comprise the steps:
  • the content of the water-based anion of the first anion-hardening coating mixture is less than the content of the water-based anion in the second anion-hardening coating mixture;
  • the particle diameter of the water-based anion of the first anion-hardening coating mixture is smaller than the particle diameter of the water-based anion in the second anion-hardening coating mixture;
  • the other side of the base film is coated with mounting glue, and compounded with the release film to obtain an anion explosion-proof film.
  • the layer thickness of the first anion hardening coating is 1 ⁇ m ⁇ 5 ⁇ m;
  • the particle diameter of anion agent in the first anion hardening coating is 20nm ⁇ 60nm;
  • the mass of anion agent in the first anion hardening coating The percentage content is 0.01%-0.1wt%.
  • the particle size of the anion agent in the first anion hardening coating is 20nm ⁇ 40nm.
  • the thickness of the second anion hardening coating is 1 ⁇ m ⁇ 5 ⁇ m;
  • the particle diameter of the anion agent in the second anion hardening coating is 70nm ⁇ 120nm;
  • the mass percent of the anion agent in the second anion hardening coating The component content is 0.2% ⁇ 0.5wt%.
  • the particle diameter of the anion agent in the second anion hardening coating is 80nm ⁇ 100nm.
  • the negative ion explosion-proof film provided by the present disclosure can make the explosion-proof film attached to the bathroom glass have the ability to release negative ions, and can play the role of killing bacteria in the bathing environment and purifying the air.
  • the principle of the antibacterial effect is to grind anion mineral crystals into nano-scale anion agents, add them to the hardener, and coat them on the surface of optical grade PET to form a hardened coating with anion function. Water molecules adsorbed on the surface of the film by ionization Produce negative ions, negative ions combine with oxygen molecules in the air to produce negative oxygen ions, which can effectively remove harmful gases such as formaldehyde in the air and eliminate bacteria.
  • the negative ion explosion-proof membrane of the present disclosure has basic functions such as good wear resistance, high hardness, and preventing glass from bursting and hurting people. environment.
  • the total thickness of the anion hardening coating is 6 ⁇ m, wherein, the layer thickness of the second anion hardening coating 12 is 3 ⁇ m, the mass percentage of the anion agent is 0.4%, and the particle diameter of the anion agent is 80nm ⁇ 90nm;
  • the layer thickness of the anion hardening coating 11 is 3 ⁇ m, the mass percentage of the anion agent is 0.05%, and the particle diameter of the anion agent is 20nm ⁇ 25nm.
  • the component contents of the first negative ion hardening coating 11 and the second negative ion hardening coating 12 are shown in Table 1.
  • Preparation method weigh each component according to Table 1, and mix evenly with a high-speed stirrer to obtain anion hardening solution. Then it was coated on a PET base film with a thickness of 50 ⁇ m by a micro gravure roller, and the thickness of the second anion hardening coating 12 was 3 ⁇ m. After drying at 100°C, pass through a UV lamp at a speed of 15m/min with a radiation intensity of 400mJ/cm 2 , and after curing, an anion-cured film can be obtained. Then it is coated with the first anion hardening coating 11 with a thickness of 3 ⁇ m by the same process.
  • Raw material composition the total thickness of the anion hardening coating is 6 ⁇ m, wherein, the layer thickness of the second anion hardening coating 12 is 3 ⁇ m, the mass percentage of anion agent is 0.3%, and the particle diameter of anion agent is 90nm ⁇ 95nm;
  • the layer thickness of the anion hardening coating 11 is 3 ⁇ m, the mass percent content of the anion agent is 0.03%, and the particle diameter of the anion agent is 25nm ⁇ 30nm.
  • the component contents of the first negative ion hardening coating 11 and the second negative ion hardening coating 12 are shown in Table 2.
  • Preparation method Weigh each component according to Table 2, and prepare the explosion-proof film.
  • the preparation method is the same as in Example 1.
  • the total thickness of the anion hardening coating is 6 ⁇ m, wherein, the layer thickness of the second anion hardening coating 12 is 3 ⁇ m, the mass percentage of the anion agent is 0.5%, and the particle diameter of the anion agent is 95nm ⁇ 100nm;
  • the layer thickness of the anion hardening coating 11 is 3 ⁇ m, the mass percentage of the anion agent is 0.08%, and the particle diameter of the anion agent is 35nm ⁇ 40nm.
  • the component contents of the first negative ion hardening coating 11 and the second negative ion hardening coating 12 are shown in Table 3.
  • Preparation method Weigh each component according to Table 3, and prepare the explosion-proof film.
  • the preparation method is the same as in Example 1.
  • Table 4 has listed each component and the mass percentage of each component in the negative ion hardening coating of comparative example 1, and the negative ion hardening coating thickness is 6 ⁇ m in comparative example 1, and the addition of negative ion agent is 0.45%, The particle size of the negative ion agent is 20nm ⁇ 25nm;
  • the production process conditions and method of the negative ion explosion-proof film of comparative example 1 are the same as that of Example 1, the only difference is: only one layer of negative ion hardening coating is applied.
  • composition of each component and the mass percentage of each component of the negative ion hardening coating of comparative example 2 and comparative example 1 are the same, and the difference is that the particle diameter of the water-based negative ions in the negative ion hardening coating of comparative example 2 is 80nm ⁇ 90nm .
  • the negative ion hardening coating was only coated with one layer.
  • Example 1 and Comparative Example 1 have an initial release of anion concentrations close to each other. But Example 1 has better durability. This is because the anion agent in the anion hardening coating needs to migrate to the surface of the film to release anion, and the anion agent in Example 1 has a certain concentration gradient, which prolongs the effective time of the anion agent. That is, the anion agent on the surface is sufficient to provide immediate anion release capability, while the inner layer contains a higher concentration of anion agent, which makes it more durable through continuous migration to the outer layer.
  • Example 4-6 In order to investigate the durability of the anion release effect when the first anion hardening coating 11 and the second anion hardening coating 12 contain anion agents with different particle sizes, the anion explosion-proof membranes in Examples 4-6 were produced. The difference from Example 1 is the particle size of the anion agent in Examples 4-6; the types and contents of the remaining components, the concentration gradient of the anion agent and the manufacturing process are all the same in the anion hardening coating.
  • the total thickness of the negative ion hardening coating is 6 ⁇ m, wherein, the thickness of the second negative ion hardening coating 12 is 3 ⁇ m, the content of anion agent is 0.4%, and the particle size is 20nm ⁇ 25nm; the thickness of the first negative ion hardening coating 11 is 3 ⁇ m, and the negative ion
  • the additive content is 0.05%, and the particle size is 20nm-25nm. Except that the content and particle size of the anion agent are different, the composition and content of other components of each layer of anion hardening coating are the same as those shown in Table 1 in Example 1.
  • the total thickness of the negative ion hardening coating is 6 ⁇ m, wherein, the thickness of the second negative ion hardening coating 12 is 3 ⁇ m, the content of anion agent is 0.4%, and the particle size is 80nm ⁇ 90nm; the thickness of the first negative ion hardening coating 11 is 3 ⁇ m, and the negative ion
  • the additive content is 0.05%, and the particle size is 80nm-90nm. Except that the content and particle size of the anion agent are different, the composition and content of other components of each layer of anion hardening coating are the same as those shown in Table 1 in Example 1.
  • the total thickness of the negative ion hardening coating is 6 ⁇ m, wherein, the thickness of the second negative ion hardening coating 12 is 3 ⁇ m, the content of anion agent is 0.4%, and the particle size is 20nm ⁇ 25nm; the thickness of the first negative ion hardening coating 11 is 3 ⁇ m, and the negative ion
  • the additive content is 0.05%, and the particle size is 80nm-90nm. Except that the content and particle size of the anion agent are different, the composition and content of other components of each layer of anion hardening coating are the same as those shown in Table 1 in Example 1.
  • Example 6 It can be seen from Table 6 that the migration rate of the negative ion agent particles is related to the size of the particles, the migration of the small particle size is fast, and the migration of the large particle size is slow.
  • Example 1 it can be seen that in Example 1, the large particle size anion agent is distributed on the layer (inner layer) close to the basement membrane, and the small particle size anion agent is distributed on the layer far away from the basement membrane.
  • inner layer and outer layer are all small particle size negative ion agents, although initial negative ion release concentration is high, but persistence is low ;
  • the inner layer and the outer layer are large particle size anion agents, and the anion release persistence is higher, but the anion release concentration is lower;
  • the small particle size anion agent is distributed in the inner layer, and the large particle size The negative ion agent is distributed in the outer layer, the initial negative ion release concentration is low, and the negative ion persistence is medium. Therefore, the negative ion hardening coating is divided into two layers of coating.
  • the negative ion agent contained in the two layers has a concentration gradient, and the inner layer is a larger-sized particle anion agent, and the outer layer is distributed with a smaller-sized particle anion agent, so that the negative ion explosion-proof While the membrane provides high-efficiency negative ion release capability, it also makes it more durable.
  • the disclosure provides a negative ion explosion-proof membrane and a preparation method thereof.
  • the negative ion explosion-proof membrane has basic functions such as good wear resistance, high hardness, and preventing glass from bursting and hurting people, and at the same time has an efficient and durable negative ion release function, thereby providing People provide a durable safe, healthy and hygienic environment, so it has excellent industrial practical performance.

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Abstract

本公开提供了一种负离子防爆膜及其制备方法，该负离子防爆膜表面含有两层硬化涂层，硬化涂层中分别含有不同浓度、不同粒径的负离子剂颗粒，而且负离子剂浓度具有一定梯度。靠里一层的负离子剂浓度较高、颗粒粒径较大，外层负离子剂浓度较低、颗粒粒径较小，从而使防爆膜具备高效、持久的负离子释放能力。

Description

一种负离子防爆膜及其制备方法
相关申请的交叉引用
本公开要求于2021年12月06日提交中国专利局的申请号为CN202111481609.1、名称为“一种负离子防爆膜及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及防爆膜技术领域，特别涉及一种负离子防爆膜及其制备方法。
背景技术
将防爆膜贴附在玻璃上可以起到耐磨、防划伤的作用，最重要的是防止玻璃爆裂破碎时产生碎片伤人。
卫浴玻璃由于长期处于相对潮湿的环境，且通常浴室采光较差，较容易滋生细菌。因此，目前防爆膜亟待解决的问题是其自身可以起到杀灭沐浴环境中的细菌、净化空气的作用。
发明内容
本公开提供一种负离子防爆膜，所述负离子防爆膜包括依次相邻的第一负离子硬化涂层和第二负离子硬化涂层、基膜、安装胶层和离型膜；
其中，所述第一负离子硬化涂层和所述第二负离子硬化涂层中皆含有水性聚氨酯丙烯酸酯低聚物、光引发剂、负离子剂和水；
所述第一负离子硬化涂层的水性负离子的含量小于所述第二负离子硬化涂层中的水性负离子的含量；
所述第一负离子硬化涂层的水性负离子的粒径小于所述第二负离子硬化涂层中的水性负离子的粒径。
在一些实施方式中，所述第一负离子硬化涂层和第二负离子硬化涂层的总厚度为2μm～10μm。
在一些实施方式中，所述第一负离子硬化涂层的层厚度为1μm～5μm；在所述第一负离子硬化涂层中所述负离子剂的粒径为20nm～60nm；所述负离子剂在第一负离子硬化涂层中的质量百分含量为0.01wt％～0.1wt％。在一些实施方式中，在所述第一负离子硬化涂层中所述负 离子剂的粒径为20nm～40nm。
在一些实施方式中，所述第二负离子硬化涂层的厚度为1μm～5μm；在第二负离子硬化涂层中所述负离子剂的粒径为70nm～120nm；所述负离子剂在所述第二负离子硬化涂层中的质量百分含量为0.2wt％～0.5wt％。在一些实施方式中，在第二负离子硬化涂层中所述负离子剂的粒径为80nm～100nm。
在一些实施方式中，所述负离子剂由天然矿物电气石经过超细化粉碎、包覆改性、离子交换掺杂制得。
在一些实施方式中，所述基膜材质为PET，所述基膜的厚度为20μm～200μm。在一些实施方式中，所述基膜厚度为50μm～100μm。在一些实施方式中，所述基膜的透光率在85％以上。在一些实施方式中，所述基膜透光率在90％以上。
在一些实施方式中，所述安装胶层的材质为丙烯酸酯类压敏胶，所述安装胶层的厚度为10μm～20μm。在一些实施方式中，所述安装胶层厚度为12μm～15μm。在一些实施方式中，所述安装胶层的剥离力为5N～20N。在一些实施方式中，所述安装胶层的剥离力为10N～15N。
在一些实施方式中，所述离型膜为用氟或涂硅离型剂处理的PET薄膜，所述离型膜的厚度为10μm～50μm。在一些实施方式中，所述离型膜厚度为20μm～40μm。在一些实施方式中，所述离型膜的离型力为0.05N～0.15N。在一些实施方式中，所述离型膜的离型力为0.08N～0.12N；所述离型膜的残余粘着率大于85％。在一些实施方式中，所述离型膜的残余粘着力大于90％以上。
在一些实施方式中，所述水性聚氨酯丙烯酸酯低聚物为水性脂肪族聚氨酯丙烯酸树脂，所述水性聚氨酯丙烯酸酯低聚物在负离子硬化涂层中的质量百分含量为15wt％～80wt％。在一些实施方式中，所述水性聚氨酯丙烯酸酯低聚物在负离子硬化涂层中的质量百分含量为30wt％～60wt％。
在一些实施方式中，所述光引发剂为水性安息香衍生物、水性二苯乙二酮衍生物和烷基芳酮衍生物中的一种。在一些实施方式中，所述光引发剂为2-羟基-2-甲基-苯基丙酮；所述光引发剂在所述负离子硬化涂层中的质量百分含量为1wt％～10wt％。在一些实施方式中，所述光引发剂在所述负离子硬化涂层中的质量百分含量为2wt％～6wt％。
本公开还提供一种负离子防爆膜的制备方法，所述方法包括如下步骤：
称量好原材料后，加入一定比例的去离子水或蒸馏水，用高速搅拌器搅拌均匀；
在基膜的一面采用辊涂或刮涂的方式涂布一层负离子硬化涂料，经烘干后，采用紫外(UV)固化，然后将其表面采用同种方式涂布第二层负离子硬化涂料，烘干后UV固化，从 而制得带有负离子硬化涂层的基膜；
在基膜的另一面涂布安装胶，并与离型膜进行复合，从而制得负离子防爆膜。
本公开提供一种负离子防爆膜的制备方法，所述方法包括如下步骤：
将水性聚氨酯丙烯酸酯低聚物、光引发剂、负离子剂和水混合、搅拌，得到第一负离子硬化涂层混合料和第二负离子硬化涂层混合料；
所述第一负离子硬化涂层混合料的水性负离子的含量小于所述第二负离子硬化涂层混合料中的水性负离子的含量；
所述第一负离子硬化涂层混合料的水性负离子的粒径小于所述第二负离子硬化涂层混合料中的水性负离子的粒径；
将所述第一负离子硬化涂层混合料涂布于基膜的一面，经烘干、固化，得到第一负离子硬化涂层；
将所述第二负离子硬化涂层混合料涂布于所述第一负离子硬化涂层上，经烘干、固化，得到第二负离子硬化涂层；
在所述基膜的另一面涂布安装胶，并与离型膜进行复合，从而制得负离子防爆膜。
在一些实施方式中，所述第一负离子硬化涂层的层厚度为1μm～5μm；在所述第一负离子硬化涂层中所述负离子剂的粒径为20nm～60nm；所述负离子剂在第一负离子硬化涂层中的质量百分含量为0.01％～0.1wt％。在一些实施方式中，在所述第一负离子硬化涂层中所述负离子剂的粒径为20nm～40nm。
在一些实施方式中，所述第二负离子硬化涂层的厚度为1μm～5μm；在第二负离子硬化涂层中所述负离子剂的粒径为70nm～120nm；所述负离子剂在所述第二负离子硬化涂层中的质量百分含量为0.2％～0.5wt％。在一些实施方式中，在第二负离子硬化涂层中所述负离子剂的粒径为80nm～100nm。
附图说明
为了更清楚地说明本公开的实施，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本公开的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为负离子防爆膜的结构示意图；
附图标记：11-第一负离子硬化涂层，12-第二负离子硬化涂层，2-基膜，3-安装胶层，4-离型膜。
具体实施方式
下面对本公开的实施方式作详细描述。显然，所描述的实施方式和实施例仅是本公开的一部分实施方式和实施例，而不是所有实施方式和实施例的穷举。需要说明的是，在不冲突的情况下，本公开中的实施方式以及实施方式中的特征可以相互组合，实施例及实施例中的特征可以相互组合。
说明书和权利要求书中的术语“第一”、“第二”等(如果存在)是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换，以便这里描述的实施例能够以除了在这里图示或描述的内容以外的顺序实施。此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设备，不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
应当理解，本文中使用的术语“和/或”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。另外，本文中字符“/”，一般表示前后关联对象是一种“或”的关系。
除非另外指明，以下各实施例中所使用的材料、试剂等均可通过常规商购途径获得。
本公开的一些实施方式提供了一种高效、持久释放负离子的负离子防爆膜。
在一些实施方式中，在基膜的一侧表面上涂布两层硬化涂层，这两层硬化涂层中分别含有不同浓度、不同粒径的负离子剂。在一些实施方式中，靠近基膜的一层负离子硬化涂层中的负离子剂浓度较高、颗粒粒径较大，而远离基膜的一层负离子硬化涂层中负离子剂浓度较低、颗粒粒径较小。据信，不受理论的约束，这种设计方案利用了负离子剂在两层负离子硬化涂层之间形成的浓度梯度，为负离子剂颗粒提供迁移动力，由高浓度区域迁移至低浓度区域，同时，由于靠近基膜的一层负离子硬化涂层中负离子剂的颗粒粒径较大，因此迁移阻力也相对较大，降低了负离子剂迁移速率，起到延长表层负离子释放的功效；而远离基膜的一层负离子硬化涂层中的负离子剂颗粒粒径较小，有利于其迁移至最外层，起到释放负离子的作用。通过设置含有不同粒径大小及不同浓度的负离子剂的两层负离子硬化涂层，使防爆膜具备高效、持久的负离子释放能力。
如图1所示，一种负离子防爆膜，包括依次相邻的第一负离子硬化涂层11和第二负离子硬化涂层12、基膜2、安装胶层3和离型膜4。
第一负离子硬化涂层11和第二负离子硬化涂层12中皆含有水性聚氨酯丙烯酸酯低聚物、光引发剂、负离子剂和水；
第一负离子硬化涂层11的水性负离子的含量小于第二负离子硬化涂层12中的水性负离子的含量；
第一负离子硬化涂层11的水性负离子的粒径小于第二负离子硬化涂层12中的水性负离子的粒径。
在一些实施方式中，基膜材质为PET。在一些实施方式中，基膜的厚度可在20μm～200μm之间。在一些实施方式中，基膜的厚度可以为例如50μm～180μm、70μm～150μm或90μm～120μm，诸如20μm、40μm、60μm、80μm、100μm、120μm、140μm、160μm、180μm、200μm。在一些实施方式中，基膜为厚度为50μm～100μm的PET膜。在一些实施方式中，基膜的透光率在85％以上。在一些实施方式中，基膜的透光率可以为例如85％～99％、87％～95％或89％～92％，诸如85％、87％、90％、92％、94％、96％、98％、99％。在一些实施方式中，透光率在90％以上的PET膜。
在一些实施方式中，安装胶层材质为丙烯酸酯类压敏胶。在一些实施方式中，安装胶层的厚度可在10μm～20μm之间。在一些实施方式中，安装胶层的厚度可以为11μm～18μm、11.5μm～17μm、12μm～15μm或13μm～14μm，诸如10μm、12μm、14μm、16μm、18μm、20μm。在一些实施方式中，安装胶层的剥离力为5N～20N。在一些实施方式中，剥离力可以为7N～18N、10N～15N或12N～14N的丙烯酸酯压敏胶。
在一些实施方式中，离型膜为涂氟或涂硅离型剂处理的PET薄膜,。在一些实施方式中，离型膜的厚度可在10μm～50μm。在一些实施方式中，离型膜的厚度可以为15μm～45μm、20μm～40μm、25μm～35μm或28μm～32μm。在一些实施方式中，离型膜的离型力为0.05N～0.15N。在一些实施方式中，离型膜的离型力可以为0.06N～0.13N、0.08N～0.12N或0.09N～0.11N。在一些实施方式中，离型膜的残余粘着率大于85％。在一些实施方式中，残余粘着率大于90％以上。
在一些实施方式中，负离子硬化涂层总厚度为2μm～10μm。在一些实施方式中，负离子硬化涂层11厚度为1μm～5μm，例如1.5μm～4.5μm、2μm～4μm或2.5μm～3.5μm，诸如1μm、1.5μm、2μm、2.5μm、3μm、3.5μm、4μm、4.5μm、5μm。在一些实施方式中，负离子硬化涂层12厚度为1μm～5μm，例如1.5μm～4.5μm、2μm～4μm或2.5μm～3.5μm，诸如1μm、1.5μm、2μm、2.5μm、3μm、3.5μm、4μm、4.5μm、5μm。
在一些实施方式中，负离子硬化涂层包含如下组分：水性聚氨酯丙烯酸酯低聚物、光引发剂、负离子剂、去离子水或蒸馏水。
在一些实施方式中，所使用的水性聚氨酯丙烯酸酯低聚物为水性脂肪族聚氨酯丙烯酸树 脂。在一些实施方式中，水性脂肪族聚氨酯丙烯酸树脂可选用：长兴公司的6166W、DR-W425、DR-W450、DR-W470、DR-W482、DR-W495、DR-W402S、DR-W413S、DR-W485S中的一种或两种。在一些实施方式中，水性聚氨酯丙烯酸酯树脂在负离子硬化涂层中的质量百分含量为15wt％～80wt％。在一些实施方式中，水性聚氨酯丙烯酸酯树脂在负离子硬化涂层中的百分含量为例如20wt％～75wt％、25wt％～70wt％、30wt％～60wt％或35wt％～55wt％，诸如15wt％、20wt％、25wt％、30wt％、35wt％、40wt％、45wt％、50wt％、55wt％、60wt％、65wt％、70wt％、75wt％、80wt％。
在一些实施方式中，光引发剂为水性安息香衍生物、水性二苯乙二酮衍生物和烷基芳酮衍生物中的一种。在一些实施方式中，光引发剂为烷基芳酮衍生物的2-羟基-2-甲基-苯基丙酮(1173)。在一些实施方式中，光引发剂在负离子硬化涂层中的质量百分含量为1wt％～10wt％。在一些实施方式中，光引发剂在负离子硬化涂层中的质量百分含量为例如1.5wt％～8wt％、2wt％～7wt％、2wt％～6wt％或3wt％～5wt％，诸如1wt％、2wt％、3wt％、4wt％、5wt％、6wt％、7wt％、8wt％、9wt％、10wt％。
在一些实施方式中，负离子剂为天然矿物电气石经过超细化粉碎、包覆改性、离子交换掺杂等途径制得。在一些实施方式中，负离子剂的粒径范围在20nm～120nm之间，例如30nm～110nm、40nm～100nm或50nm～90nm，诸如20nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm、100nm、110nm、120nm。
在一些实施方式中，第一负离子硬化涂层的层厚度为1μm～5μm，例如1.5μm～4.5μm、2μm～4μm或2.5μm～3.5μm，诸如1μm、1.5μm、2μm、2.5μm、3μm、3.5μm、4μm、4.5μm、5μm。。在一些实施方式中，在第一负离子硬化涂层中负离子剂的粒径为20nm～60nm，例如，粒径为20nm～50nm、20nm～40nm、25nm～35nm或20nm～25nm，诸如20nm、25nm、30nm、35nm、40nm、45nm、50nm、55nm、60nm。在一些实施方式中，负离子剂在第一负离子硬化涂层中的质量百分含量为0.01wt％～0.1wt％，例如质量百分含量为0.02wt％～0.08wt％、0.03wt％～0.07wt％或0.04wt％～0.06wt％，诸如0.01wt％、0.02wt％、0.03wt％、0.04wt％、0.05wt％、0.06wt％、0.07wt％、0.08wt％、0.09wt％、1wt％。在一些实施方式中，第二负离子硬化涂层的厚度为1μm～5μm，例如1.5μm～4.5μm、2μm～4μm或2.5μm～3.5μm，诸如1μm、1.5μm、2μm、2.5μm、3μm、3.5μm、4μm、4.5μm、5μm。在一些实施方式中，在第二负离子硬化涂层中负离子剂的粒径为70nm～120nm，例如粒径可以为75nm～110nm、80nm～100nm、80nm～90nm或85nm～90nm，诸如70nm、80nm、90nm、100nm、110nm。在一些实施方式中，负离子剂在第二负离子硬化涂层中的质量百分含量为0.2wt％～0.5wt％，例如可以为 0.24％～0.48wt％、0.26％～0.42wt％或0.3％～0.4wt％，诸如0.2wt％、0.25wt％、0.3wt％、0.35wt％、0.4wt％、0.45wt％、0.5wt％。
本公开一些实施方式提供负离子防爆膜的制备方法包括如下步骤：
称量好原材料后，加入一定比例的去离子水或蒸馏水，用高速搅拌器搅拌均匀；在基膜的一面采用辊涂或刮涂的方式涂布一层负离子硬化涂料，经烘干后，采用紫外(UV)固化，然后将其表面采用同种方式涂布第二层负离子硬化涂料，烘干后UV固化，从而制得带有负离子硬化涂层的基膜；在基膜的另一面涂布安装胶，并与离型膜进行复合，从而制得负离子防爆膜。
本公开的一些实施方式提供一种负离子防爆膜的制备方法，包括如下步骤：
将水性聚氨酯丙烯酸酯低聚物、光引发剂、负离子剂和水混合、搅拌，得到第一负离子硬化涂层混合料和第二负离子硬化涂层混合料；
第一负离子硬化涂层混合料的水性负离子的含量小于第二负离子硬化涂层混合料中的水性负离子的含量；
第一负离子硬化涂层混合料的水性负离子的粒径小于第二负离子硬化涂层混合料中的水性负离子的粒径；
将第一负离子硬化涂层混合料涂布于基膜的一面，经烘干、固化，得到第一负离子硬化涂层；
将第二负离子硬化涂层混合料涂布于第一负离子硬化涂层上，经烘干、固化，得到第二负离子硬化涂层；
在基膜的另一面涂布安装胶，并与离型膜进行复合，从而制得负离子防爆膜。
在一些实施方式中，第一负离子硬化涂层的层厚度为1μm～5μm；在第一负离子硬化涂层中负离子剂的粒径为20nm～60nm；负离子剂在第一负离子硬化涂层中的质量百分含量为0.01％～0.1wt％。在一些实施方式中，在第一负离子硬化涂层中负离子剂的粒径为20nm～40nm。
在一些实施方式中，第二负离子硬化涂层的厚度为1μm～5μm；在第二负离子硬化涂层中负离子剂的粒径为70nm～120nm；负离子剂在第二负离子硬化涂层中的质量百分含量为0.2％～0.5wt％。在一些实施方式中，在第二负离子硬化涂层中负离子剂的粒径为80nm～100nm。
本公开提供的负离子防爆膜，能使卫浴玻璃上贴附的防爆膜具有释放负离子的能力，可以起到杀灭沐浴环境中的细菌、净化空气的作用。该抑菌作用的原理是将负离子矿物晶体研 磨成纳米级负离子剂，加入到硬化剂中，涂布于光学级PET表面，形成具有负离子功能的硬化涂层，通过电离吸附在膜表面的水分子产生负离子，负离子跟空气中的氧分子结合产生负氧离子，从而能有效去除空气的甲醛等有害气体，并能消灭细菌。
同时本公开的负离子防爆膜具有耐磨性好、硬度高以及防止玻璃爆裂伤人等基本功能的同时，还具备高效、持久的负离子释放功能，从而为人们提供一种持久的安全、健康、卫生环境。
实施例
下面通过具体的实施例对本公开进行说明。
为了将涂布一层负离子硬化涂层和涂布两层负离子硬化涂层的防爆膜的负离子释放浓度和释放持久性进行对比，在单位面积膜样品负离子硬化涂层内的负离子剂含量相当的前提下，制作了实施例1和对比例1～2中的负离子防爆膜。
实施例1
原料组成：负离子硬化涂层总厚度为6μm，其中，第二负离子硬化涂层12的层厚度为3μm，负离子剂的质量百分含量为0.4％，负离子剂的粒径为80nm～90nm；第一负离子硬化涂层11的层厚度为3μm，负离子剂的质量百分含量为0.05％，负离子剂的粒径为20nm～25nm。本实施例中，第一负离子硬化涂层11和第二负离子硬化涂层12的组分含量如表1所示。
表1
Figure PCTCN2022110016-appb-000001
制备方法：按表1称量各组分，并用高速搅拌器混合均匀，即得负离子硬化液。然后将其用微凹辊涂布在50μm厚度的PET基膜上，第二负离子硬化涂层12的厚度为3μm。在100℃条件下烘干后，以15m/min的速度过UV灯，辐照强度为400mJ/cm 2，固化后即得负离子硬化膜。再将其以同样的工艺涂布一层厚度为3μm的第一负离子硬化涂层11。将PET膜另一面用微凹辊涂布安装胶，安装胶层厚度为15μm，在110℃条件下烘干后，与25μm厚的离型膜复合，即得负离子防爆膜。
实施例2
原料组成：负离子硬化涂层总厚度为6μm，其中，第二负离子硬化涂层12的层厚度为3μm，负离子剂的质量百分含量为0.3％，负离子剂的粒径为90nm～95nm；第一负离子硬化涂层11的层厚度为3μm，负离子剂的质量百分含量为0.03％，负离子剂的粒径为25nm～30nm。本实施例中，第一负离子硬化涂层11和第二负离子硬化涂层12的组分含量如表2所示。
表2
Figure PCTCN2022110016-appb-000002
制备方法：按表2称量各组分，进行防爆膜的制备，制备方法同实施例1。
实施例3
原料组成：负离子硬化涂层总厚度为6μm，其中，第二负离子硬化涂层12的层厚度为3μm，负离子剂的质量百分含量为0.5％，负离子剂的粒径为95nm～100nm；第一负离子硬化涂层11的层厚度为3μm，负离子剂的质量百分含量为0.08％，负离子剂的粒径为35nm～40nm。本实施例中，第一负离子硬化涂层11和第二负离子硬化涂层12的组分含量如表3所示。
表3
Figure PCTCN2022110016-appb-000003
制备方法：按表3称量各组分，进行防爆膜的制备，制备方法同实施例1。
对比例1
表4中列出了对比例1的负离子硬化涂层中的各组分及各组分的质量百分含量，对比例1中负离子硬化涂层厚度为6μm，负离子剂的添加量为0.45％，负离子剂的粒径为20nm～25nm；对比例1的负离子防爆膜的制作工艺条件及方法与实施例1相同，唯一区别为：仅涂布一层负离子硬化涂层。
表4
Figure PCTCN2022110016-appb-000004
对比例2
对比例2与对比例1的负离子硬化涂层的各组分组成及各组分的质量百分含量相同，不同的是对比例2的负离子硬化涂层中的水性负离子的粒径为80nm～90nm。对比例2中负离子硬化涂层只涂布一层。
将制备实施例1-3，对比例1和对比例2制备的负离子防爆膜按照JC/T2040-2010中规定的方法，测试其释放负离子浓度及其随放置时间的变化。测试结果如表5所示。
表5
Figure PCTCN2022110016-appb-000005
通过将实施例1与对比例1，对比例2进行对比，在单位面积膜样品负离子硬化涂层内的负离子剂含量相当的情况下，实施例1与对比例1具有接近的初始释放负离子浓度，但实 施例1具有更优的持久性。这是因为负离子硬化涂层中的负离子剂需要迁移至膜表面才能起到释放负离子的作用，而实施例1中的负离子剂具有一定的浓度梯度，延长了负离子剂的有效作用时间。即表层的负离子剂足够提供即时负离子释放能力，而内层含有浓度更高的负离子剂，通过不断的向外层迁移，使其具有更佳持久性。
实施例4～6
为了考察第一负离子硬化涂层11和第二负离子硬化涂层12中含有不同粒径的负离子剂时，负离子释放效果持久性，制作了实施例4～6中的负离子防爆膜。与实施例1不同的是实施例4～6中的负离子剂的颗粒尺寸；负离子硬化涂层中其余组分的种类及含量、负离子剂浓度梯度及制作工艺均相同。
实施例4
负离子硬化涂层总厚度为6μm，其中，第二负离子硬化涂层12的厚度为3μm，负离子剂含量为0.4％，粒径为20nm～25nm；第一负离子硬化涂层11的厚度为3μm，负离子剂含量为0.05％，粒径为20nm～25nm。除了负离子剂的含量及粒径不同外，每一层负离子硬化涂层的其他组分组成及含量与实施例1中的表1所示组分相同。
实施例5
负离子硬化涂层总厚度为6μm，其中，第二负离子硬化涂层12的厚度为3μm，负离子剂含量为0.4％，粒径为80nm～90nm；第一负离子硬化涂层11的厚度为3μm，负离子剂含量为0.05％，粒径为80nm～90nm。除了负离子剂的含量及粒径不同外，每一层负离子硬化涂层的其他组分组成及含量与实施例1中的表1所示组分相同。
实施例6
负离子硬化涂层总厚度为6μm，其中，第二负离子硬化涂层12的厚度为3μm，负离子剂含量为0.4％，粒径为20nm～25nm；第一负离子硬化涂层11的厚度为3μm，负离子剂含量为0.05％，粒径为80nm～90nm。除了负离子剂的含量及粒径不同外，每一层负离子硬化涂层的其他组分组成及含量与实施例1中的表1所示组分相同。
将制备的负离子防爆膜按照JC/T2040-2010中规定的方法，测试其释放负离子浓度及其随放置时间的变化。测试结果如表6所示。
表6
Figure PCTCN2022110016-appb-000006
Figure PCTCN2022110016-appb-000007
从表6可知，负离子剂颗粒的迁移速率与颗粒的大小有关，粒径小的迁移快，粒径大的迁移慢。通过将实施例1与实施例4～6进行对比可以看出：实施例1中，大粒径负离子剂分布在靠近基膜的一层(里层)，小粒径负离子剂分布在远离基膜的一层(外层)，其初始负离子浓度释放高，持久性也更佳；实施例4中，里层和外层均为小粒径负离子剂，虽然初始负离子释放浓度高，但持久性低；实施例5中，里层和外层均为大粒径负离子剂，负离子释放持久性较高，但负离子释放浓度较低；实施例6中，小粒径负离子剂分布在里层，大粒径负离子剂分布在外层，初始负离子释放浓度低，负离子持久性中等。因此，负离子硬化涂层分为两层涂布，两层内含有的负离子剂具有浓度梯度，且里层为较大尺寸颗粒负离子剂，外层中分布较小尺寸颗粒负离子剂，从而为负离子防爆膜提供高效负离子释放能力的同时，也使其具备更佳的持久性。
显然，本公开的上述实施例仅仅是为清楚地说明本公开所作的举例，而并非是对本公开的实施方式的限定，对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动，这里无法对所有的实施方式予以穷举，凡是属于本公开的技术方案所引伸出的显而易见的变化或变动仍处于本公开的保护范围之列。
工业实用性
本公开提供了一种负离子防爆膜及其制备方法，该负离子防爆膜具有耐磨性好、硬度高以及防止玻璃爆裂伤人等基本功能的同时，还具备高效、持久的负离子释放功能，从而为人们提供一种持久的安全、健康、卫生环境，因此具备优异的工业实用性能。

Claims (14)

  1. 一种负离子防爆膜，其特征在于，所述负离子防爆膜包括依次相邻的第一负离子硬化涂层和第二负离子硬化涂层、基膜、安装胶层和离型膜；
    其中，所述第一负离子硬化涂层和所述第二负离子硬化涂层中皆含有水性聚氨酯丙烯酸酯低聚物、光引发剂、负离子剂和水；
    所述第一负离子硬化涂层的水性负离子的含量小于所述第二负离子硬化涂层中的水性负离子的含量；
    所述第一负离子硬化涂层的水性负离子的粒径小于所述第二负离子硬化涂层中的水性负离子的粒径。
  2. 根据权利要求1所述的负离子防爆膜，其特征在于，所述第一负离子硬化涂层和第二负离子硬化涂层的总厚度为2μm～10μm。
  3. 根据权利要求1所述的负离子防爆膜，其特征在于，所述第一负离子硬化涂层的层厚度为1μm～5μm；在所述第一负离子硬化涂层中所述负离子剂的粒径为20nm～60nm，优选粒径为20nm～40nm；所述负离子剂在第一负离子硬化涂层中的质量百分含量为0.01％～0.1wt％。
  4. 根据权利要求1-3中任一项所述的负离子防爆膜，其特征在于，所述第二负离子硬化涂层的厚度为1μm～5μm；在第二负离子硬化涂层中所述负离子剂的粒径为70nm～120nm，优选粒径为80nm～100nm；所述负离子剂在所述第二负离子硬化涂层中的质量百分含量为0.2％～0.5wt％。
  5. 如权利要求1～4中任一项所述的负离子防爆膜，其特征在于，所述负离子剂由天然矿物电气石经过超细化粉碎、包覆改性、离子交换掺杂制得。
  6. 根据权利要求1～5中任一项所述的负离子防爆膜，其特征在于，所述基膜材质为PET，所述基膜的厚度为20μm～200μm；优选基膜厚度为50μm～100μm；所述基膜的透光率在85％以上，优选所述基膜透光率在90％以上。
  7. 根据权利要求1～6中任一项所述的负离子防爆膜，其特征在于，所述安装胶层的材质为丙烯酸酯类压敏胶，所述安装胶层的厚度为10μm～20μm；优选所述安装胶层厚度为12μm～15μm；所述安装胶层的剥离力为5N～20N，优选所述安装胶层的剥离力为10N～15N。
  8. 根据权利要求1～7中任一项所述的负离子防爆膜，其特征在于，所述离型膜为用氟或涂硅离型剂处理的PET薄膜，所述离型膜的厚度为10μm～50μm，优选所述离型膜厚度为20μm～40μm；所述离型膜的离型力为0.05N～0.15N，优选所述离型膜的离型力为0.08N～0.12N； 所述离型膜的残余粘着率大于85％，优选所述离型膜的残余粘着力大于90％以上。
  9. 根据权利要求1～8中任一项所述的负离子防爆膜，其特征在于，所述水性聚氨酯丙烯酸酯低聚物为水性脂肪族聚氨酯丙烯酸树脂，所述水性聚氨酯丙烯酸酯低聚物在负离子硬化涂层中的质量百分含量为15％～80wt％，优选质量含量为30％～60wt％。
  10. 如权利要求1～9中任一项所述的负离子防爆膜，其特征在于，所述光引发剂为水性安息香衍生物、水性二苯乙二酮衍生物和烷基芳酮衍生物中的一种，优选所述光引发剂为2-羟基-2-甲基-苯基丙酮；所述光引发剂在所述负离子硬化涂层中的质量百分含量为1％～10wt％，优选质量百分含量为2％～6wt％。
  11. 一种负离子防爆膜的制备方法，其特征在于，所述方法包括如下步骤：
    称量好原材料后，加入一定比例的去离子水或蒸馏水，用高速搅拌器搅拌均匀；
    在基膜的一面采用辊涂或刮涂的方式涂布一层负离子硬化涂料，经烘干后，采用紫外(UV)固化，然后将其表面采用同种方式涂布第二层负离子硬化涂料，烘干后UV固化，从而制得带有负离子硬化涂层的基膜；
    在基膜的另一面涂布安装胶，并与离型膜进行复合，从而制得负离子防爆膜。
  12. 一种负离子防爆膜的制备方法，其特征在于，所述方法包括如下步骤：
    将水性聚氨酯丙烯酸酯低聚物、光引发剂、负离子剂和水混合、搅拌，得到第一负离子硬化涂层混合料和第二负离子硬化涂层混合料；
    所述第一负离子硬化涂层混合料的水性负离子的含量小于所述第二负离子硬化涂层混合料中的水性负离子的含量；
    所述第一负离子硬化涂层混合料的水性负离子的粒径小于所述第二负离子硬化涂层混合料中的水性负离子的粒径；
    将所述第一负离子硬化涂层混合料涂布于基膜的一面，经烘干、固化，得到第一负离子硬化涂层；
    将所述第二负离子硬化涂层混合料涂布于所述第一负离子硬化涂层上，经烘干、固化，得到第二负离子硬化涂层；
    在所述基膜的另一面涂布安装胶，并与离型膜进行复合，从而制得负离子防爆膜。
  13. 根据权利要求12所述的制备方法，其特征在于，所述第一负离子硬化涂层的层厚度为1μm～5μm；在所述第一负离子硬化涂层中所述负离子剂的粒径为20nm～60nm，优选粒径为20nm～40nm；所述负离子剂在第一负离子硬化涂层中的质量百分含量为0.01％～0.1wt％。
  14. 根据权利要求12所述的制备方法，其特征在于，所述第二负离子硬化涂层的厚度为 1μm～5μm；在第二负离子硬化涂层中所述负离子剂的粒径为70nm～120nm，优选粒径为80nm～100nm；所述负离子剂在所述第二负离子硬化涂层中的质量百分含量为0.2％～0.5wt％。
PCT/CN2022/110016 2021-12-06 2022-08-03 一种负离子防爆膜及其制备方法 WO2023103424A1 (zh)

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