WO2019109927A1 - 可金属化的防爆涂料及制备与应用、具有天线的防爆层及制备、以及3d玻璃或陶瓷机盖 - Google Patents

可金属化的防爆涂料及制备与应用、具有天线的防爆层及制备、以及3d玻璃或陶瓷机盖 Download PDF

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Publication number
WO2019109927A1
WO2019109927A1 PCT/CN2018/119281 CN2018119281W WO2019109927A1 WO 2019109927 A1 WO2019109927 A1 WO 2019109927A1 CN 2018119281 W CN2018119281 W CN 2018119281W WO 2019109927 A1 WO2019109927 A1 WO 2019109927A1
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WIPO (PCT)
Prior art keywords
explosion
weight
proof
dispersion
proof coating
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PCT/CN2018/119281
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English (en)
French (fr)
Inventor
冷世伟
刘伟
刘萌
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比亚迪股份有限公司
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Publication of WO2019109927A1 publication Critical patent/WO2019109927A1/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/12—Supports; Mounting means
    • H01Q1/22—Supports; Mounting means by structural association with other equipment or articles

Definitions

  • the present disclosure relates to the field of explosion protection of 3D glass or ceramic substrates, and in particular to metallizable explosion-proof coatings and their preparation and applications, explosion-proof layers and preparations with antennas, and 3D glass or ceramic covers.
  • the existing explosion-proof scheme for glass screens is mainly to affix explosion-proof membranes, but it is only suitable for flat surfaces, and it is not possible to provide protection for surfaces such as 3D glass or ceramics.
  • the existing antenna function realizes the technical solution with the FPC antenna, but the disadvantage is that it is suitable for the plane, relatively thick, and occupying a large space, which is in conflict with the ultra-thin design concept of the current mobile phone.
  • LDS technology but currently the technology is mainly applied to the plastic back cover with active ingredients, for glass, ceramics and other materials are still under development, no mass production technology.
  • CN103773143A discloses a white coating composition
  • a white coating composition comprising an electroless plating catalyst precursor, a binder, a solvent, with or without an auxiliary agent, and the electroless plating catalyst precursor is at least one selected from the group consisting of SnO 2 , ZnSnO 3 and ZnTiO 3 . .
  • the electroless plating catalyst precursor is contained in an amount of 100 to 300 parts by weight, the binder content is 5 to 15 parts by weight, and the auxiliary content is 0.1 to 15 parts by weight based on 100 parts by weight of the solvent;
  • the agent is selected from the group consisting of air-cured acrylic resin, UV-curable acrylic resin, heat-curable polyurethane and water-curable polyurethane, and the solvent is selected from the group consisting of water, benzene solvent, trichloroethylene, alcohol, ketone, diketone or cyclic ketone.
  • the auxiliary agent is at least one selected from the group consisting of a dispersing agent, an antifoaming agent, a leveling agent, and a viscosity modifier.
  • the composition can be bonded to the surface of the insulating substrate by curing, and then a metal layer is formed on selected areas of the surface of the insulating substrate by laser irradiation and surface electroless plating.
  • a metal layer is formed on selected areas of the surface of the insulating substrate by laser irradiation and surface electroless plating.
  • it cannot solve the explosion-proof problem of brittle materials such as 3D glass and ceramics.
  • CN201872389U discloses an explosion-proof glass comprising a glass substrate and an explosion-proof film layer adhered to the surface of the glass substrate through an adhesive layer, the explosion-proof film layer being composed of an upper explosion-proof film base layer and a metal layer adsorbed under the explosion-proof film base layer.
  • the utility model provides an explosion-proof glass by attaching an explosion-proof membrane layer to the adhesive layer, and a metal layer is added between the explosion-proof film base layer of the high polymer and the adhesive layer, and the impact and the toughness of the metal layer are used to effectively offset and decompose the impact.
  • the filming method is not suitable for a brittle material such as a curved 3D glass or ceramic, and does not provide a mobile phone antenna function.
  • the purpose of the present disclosure is to solve the problem of explosion-proof and antenna function of 3D glass, ceramic and other brittle materials, providing metallizable explosion-proof coatings and preparation and application, explosion-proof layer with antenna and preparation, and 3D glass or ceramic machine cover.
  • the explosion-proof coating can be applied to a curved glass or ceramic to form an explosion-proof coating by means of a coating material to provide an explosion-proof function for a brittle material such as 3D glass or ceramics, and an antenna structure can be simultaneously formed on the explosion-proof coating.
  • a metallizable explosion-proof paint based on the total amount of the explosion-proof paint comprising:
  • aqueous polyurethane dispersion 30-70% by weight of aqueous polyurethane dispersion, 2-20% by weight of active powder slurry, 0.1-10% by weight of adhesion promoter, 0.1-10% by weight of water-resistant auxiliaries, 0.1-5% by weight thickening , 0.1 to 5% by weight of a pH adjuster -I, 0 to 20% by weight of a coalescent and 5 to 40% by weight of water;
  • the active powder slurry comprises 30-60% by weight of an aqueous resin, 20-50% by weight of active powder, 5-20% by weight of an aqueous dispersing agent, 5-based on the total amount of the active powder slurry. 30% by weight of water and 0.1-5% by weight of pH adjuster-II;
  • the active powder comprises an oxide selected from the group consisting of metal elements of columns 9-11 of the periodic table other than copper, silicates, borates and oxalates of the metal elements of columns 9-11 of the periodic table, a hydrogenation catalyst containing a metal element of columns 9-11 of the periodic table, at least one of an ABO 2 type composite oxide having a cuprasite structure, and doped tin oxide;
  • the hydrogenation catalyst is a catalyst for hydrogenating a carbonyl-containing aldehyde, a ketone, a fatty acid or a fatty acid ester to an alcohol;
  • A is one selected from the group consisting of metal elements of columns 9, 10 and 11 of the periodic table, B is Ni, Mn, Cr, Al or Fe, and A is different from B; in the doped tin oxide, the doping element is at least one of vanadium, niobium, indium and molybdenum.
  • the aqueous resin is a water-soluble polyester resin or a water-soluble acrylic resin.
  • the water soluble polyester resin is New Jersey's SETAL 6306ss-60 resin.
  • the aqueous resin is contained in an amount of from 40 to 60% by weight.
  • the active powder has an average particle diameter of from 1 nm to 10 ⁇ m, preferably from 1 nm to 1 ⁇ m.
  • the active powder is ZnSnO 3 and/or ZnTiO 3 .
  • the active powder is present in an amount of from 20 to 45% by weight, preferably from 20 to 30% by weight or from 25 to 45% by weight, more preferably from 25 to 30% by weight.
  • the aqueous dispersant is a high molecular polymer containing a pigment affinity group.
  • the aqueous dispersant is at least one of Lubrizol 27000 and BYK 190, 191, 192, 194, preferably at least one of Lubrizol's 27000 and BYK's 191.
  • the aqueous dispersant is contained in an amount of 5 to 15% by weight, preferably 8 to 15% by weight.
  • the pH adjuster-II is an organic amine reagent, preferably ethanolamine, N,N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, aqueous ammonia and Dow Chemical AMP- At least one of 95.
  • the active slip slurry has a pH of from 7.5 to 8.5.
  • the pH adjuster-II is contained in the active slip slurry in an amount of from 0.1 to 3% by weight, preferably from 1 to 2% by weight.
  • the water is added in an amount of 5 to 25% by weight, preferably 8 to 18.5% by weight.
  • the aqueous polyurethane dispersion is a mixture of a plurality of aqueous polyurethanes, including Dispersion A, Dispersion B, and Dispersion C, wherein Dispersion A has an elongation at break of 1000-1500% and a Shore hardness of 40-50 degrees; the elongation at break of dispersion B is 100-500%, the Shore hardness is 30-60 degrees; the elongation at break of dispersion C is 100-300%, and the Shore hardness is 70-90 degrees. .
  • the dispersion A is Acure 218 resin.
  • the dispersion B is Acure 502 resin.
  • the dispersion C is Acure 806 resin.
  • the dispersion A is used in an amount of 10 to 70% by weight, preferably 15 to 65% by weight, more preferably 40 to 65% by weight, based on the total amount of the aqueous polyurethane dispersion: the amount of the dispersion B It is 10 to 50% by weight, preferably 20 to 45% by weight, more preferably 25 to 43% by weight; and the dispersion C is used in an amount of 5 to 40% by weight, preferably 5 to 20% by weight, more preferably 10 to 20% by weight. weight%.
  • the adhesion promoter is a polymer compound containing a siloxy group and a phosphoric acid group, and the polymer compound is obtained by synthesizing a silane coupling agent and a phosphate.
  • the adhesion promoter is EDL6038 and/or EDL-YH645B of Guangzhou Zhijing Co., Ltd.
  • the adhesion promoter is present in an amount of from 0.5 to 4% by weight, preferably from 2 to 3.4% by weight.
  • the water resistant adjuvant is an aqueous blocked isocyanate compound.
  • the water resistant adjuvant is Bayer's BL2706.
  • the water-resistant auxiliary is present in an amount of from 1 to 5% by weight, preferably from 1.1 to 4.8% by weight.
  • the thickener is at least one of a polyacrylate, an associative polyurethane, and a cellulose compound.
  • the thickener is X-71 from Guangzhou Co., Ltd. and Rheovis 132 from Ciba.
  • the thickener is present in an amount of from 0.2 to 3% by weight, preferably from 0.9 to 2.1% by weight.
  • the pH adjuster-I is an overbased organic amine compound.
  • the pH adjuster-I is Dow Chemical's AMP-95.
  • the pH adjuster-I content is from 0.1 to 3% by weight, preferably from 1.2 to 2.8% by weight.
  • the coalescent is an alcohol ether solvent.
  • the film forming aid is Dow Chemical's AMP-95.
  • the film-forming aid is present in an amount of from 5 to 15% by weight, preferably from 3.8 to 4.8% by weight.
  • the water is present in an amount of from 9 to 35% by weight, preferably from 9 to 20% by weight, based on the total of the explosion-proof coating.
  • a second aspect of the present disclosure provides a method of preparing the metallizable explosion-proof coating of the above-described disclosure of the present disclosure, comprising:
  • the active powder comprises an oxide selected from the group consisting of metal elements of columns 9-11 of the periodic table other than copper, silicates, borates and oxalates of the metal elements of columns 9-11 of the periodic table, a hydrogenation catalyst containing a metal element of columns 9-11 of the periodic table, at least one of an ABO 2 type composite oxide having a cuprasite structure, and doped tin oxide;
  • the hydrogenation catalyst is a catalyst for hydrogenating a carbonyl-containing aldehyde, a ketone, a fatty acid or a fatty acid ester to an alcohol;
  • A is one selected from the group consisting of metal elements of columns 9, 10 and 11 of the periodic table, B is Cu, Sn, Zn, Ti, Ni, Mn, Cr, Al or Fe, and A is different from B; in the doped tin oxide, the doping element is at least one of vanadium, niobium, indium and molybdenum;
  • step (3) sequentially adding a thickener, an adhesion promoter, a water-resistant auxiliary agent and water to the mixture obtained in the step (2), stirring uniformly and filtering to obtain a metallizable explosion-proof paint;
  • the aqueous polyurethane dispersion, the active powder slurry, the film forming aid, the thickener, the adhesion promoter, the water resistance aid and the water are added in an amount to satisfy the metallizable explosion-proof paint, and the explosion-proof Based on the total amount of the coating, 30-70% by weight of the aqueous polyurethane dispersion, 2-20% by weight of the active powder slurry, 0.1-10% by weight of the adhesion promoter, 0.1-10% by weight of the water-resistant auxiliary agent, 0.1-5 wt% thickener, 0.1-5 wt% pH adjuster-I, 0-20 wt% film former and 5-40 wt% water.
  • a third aspect of the present disclosure provides an explosion-proof layer having an antenna, comprising an explosion-proof coating formed from the metallizable explosion-proof paint described above of the present disclosure or a metallizable explosion-proof paint obtained by the above method of the present disclosure, and the explosion-proof coating An antenna formed on the layer.
  • the explosion-proof layer has a thickness of 10 to 50 ⁇ m, preferably 20 to 40 ⁇ m.
  • a fourth aspect of the present disclosure provides a method of preparing the above-described explosion-proof layer having an antenna of the present disclosure, comprising:
  • the laser irradiation conditions include: a laser wavelength of 157 nm to 10.6 ⁇ m, a laser frequency of 30-40 kHz, a laser power of 3-80 W, and a laser scanning speed of 500-8000 mm/s.
  • the method of forming the copper layer in step (c) is electroless plating or electroplating.
  • the copper layer has a thickness of 2-15 ⁇ m.
  • the method further comprises: (d) further forming a nickel layer on the copper layer.
  • the nickel layer has a thickness of from 1 to 5 ⁇ m.
  • a fifth aspect of the present disclosure provides a 3D glass or ceramic canopy, wherein the canopy comprises a 3D glass or ceramic substrate, and the above-described explosion-proof layer having an antenna of the present disclosure or an antenna having the above-described method of the present disclosure Explosion-proof layer.
  • the explosion-proof coating has a thickness of 10 to 50 ⁇ m.
  • a sixth aspect of the present disclosure provides an application of the metallizable explosion-proof coating of the present disclosure in providing curved glass or ceramic with explosion-proof and antenna functions.
  • the present disclosure provides a metallizable explosion-proof coating, which can realize an explosion-proof coating by coating the coating, and is suitable for implementing a 3D curved surface, such as 3D glass, ceramics and the like, to achieve an explosion-proof function.
  • a metallizable explosion-proof coating which can realize an explosion-proof coating by coating the coating, and is suitable for implementing a 3D curved surface, such as 3D glass, ceramics and the like, to achieve an explosion-proof function.
  • it is also possible to form an antenna on the coating providing 3D glass or ceramic and also having an antenna function.
  • a first aspect of the present disclosure provides a metallizable explosion-proof coating based on the total amount of the explosion-proof coating, comprising:
  • aqueous polyurethane dispersion 30-70% by weight of aqueous polyurethane dispersion, 2-20% by weight of active powder slurry, 0.1-10% by weight of adhesion promoter, 0.1-10% by weight of water-resistant auxiliaries, 0.1-5% by weight thickening , 0.1 to 5% by weight of a pH adjuster -I, 0 to 20% by weight of a coalescent and 5 to 40% by weight of water;
  • the active powder slurry comprises 30-60% by weight of an aqueous resin, 20-50% by weight of active powder, 5-20% by weight of an aqueous dispersing agent, 5-based on the total amount of the active powder slurry. 30% by weight of water and 0.1-5% by weight of pH adjuster-II;
  • the active powder comprises an oxide selected from the group consisting of metal elements of columns 9-11 of the periodic table other than copper, silicates, borates and oxalates of the metal elements of columns 9-11 of the periodic table, a hydrogenation catalyst containing a metal element of columns 9-11 of the periodic table, at least one of an ABO 2 type composite oxide having a cuprasite structure, and doped tin oxide;
  • the hydrogenation catalyst is a catalyst for hydrogenating a carbonyl-containing aldehyde, a ketone, a fatty acid or a fatty acid ester to an alcohol;
  • A is one selected from the group consisting of metal elements of columns 9, 10 and 11 of the periodic table, B is Cu, Sn, Zn, Ti, Ni, Mn, Cr, Al or Fe, and A is different from B; in the doped tin oxide, the doping element is at least one of vanadium, niobium, indium and molybdenum.
  • the present disclosure provides an explosion-proof protection for a brittle material such as glass or ceramic having a 3D curved surface, and adopts a measure of coating a 3D curved surface to form an explosion-proof coating, and the metallized explosion-proof coating is provided for this purpose.
  • the explosion-proof coating uses a variety of water-based polyurethane dispersions as the main resin. It can be used with a variety of related reagents to provide an explosion-proof coating with an explosion-proof function and excellent chemical resistance and adhesion on a 3D curved surface.
  • the metallizable explosion-proof coating can be applied not only to provide an explosion-proof coating for a 3D curved surface, but also to obtain an antenna by further adding a component such as the active powder slurry.
  • the active slip slurry also contains a plurality of components.
  • the aqueous resin is a water-soluble polyester resin or a water-soluble acrylic resin.
  • the aqueous resin can provide good powder dispersibility for the active powder.
  • the aqueous resin is a known material and is commercially available.
  • the preferred water-soluble polyester resin may be New Jersey's SETAL 6306ss-60 resin.
  • the content of the aqueous resin in the active slip slurry is 40 to 60% by weight.
  • the active powder in the active powder slurry, has an average particle diameter of from 1 nm to 10 ⁇ m, preferably from 1 nm to 1 ⁇ m.
  • the active powder is a known material and is commercially available.
  • the average particle diameter can be measured by a crystal laser tester, and ethanol can be used as a dispersion medium.
  • the reactive powder may be ZnSnO 3 and/or ZnTiO 3 .
  • the active powder is contained in the active powder slurry in an amount of 20 to 45% by weight, preferably 20 to 30% by weight or 25 to 45% by weight, more preferably 25 to 30% by weight.
  • the aqueous dispersant may be a high molecular polymer containing a pigment affinity group, which contributes to the dispersion of the active powder slurry, and is commercially available, such as Lubrizol's 27000, BYK's 190, 191, 192. And 194 and so on. Lubrizol's 27000 and BYK's 191 are preferred.
  • the aqueous dispersant is present in an amount of from 5 to 15% by weight, preferably from 8 to 15% by weight.
  • the pH adjuster-II may be an organic amine reagent for adjusting the pH of the active slip slurry, such as ethanolamine, N,N-dimethylethanolamine, 2-amino-2-methyl- 1-propanol, ammonia. Commercially available, for example, Dow Chemical's AMP-95 (2-amino-2-methyl-1-propanol).
  • the pH adjuster-II is used in an amount sufficient to provide the pH required for the active slip slurry, such as the pH of the active slip slurry may be 7.5-8.5.
  • the pH adjuster-II is present in an amount of from 0.1 to 3% by weight, preferably from 1 to 2% by weight.
  • the water may be deionized water in an amount of 5 to 25% by weight, preferably 8 to 18.5% by weight.
  • the total amount of each component added to the active slip slurry satisfies 100% by weight.
  • the metallizable explosion-proof coating provided by the present disclosure contains, in addition to the above-mentioned active powder slurry, other components forming an explosion-proof coating.
  • the aqueous polyurethane dispersion can serve as a host component capable of ultimately forming a coating.
  • the aqueous polyurethane dispersion is a mixture of a plurality of aqueous polyurethanes, including Dispersion A, Dispersion B, and Dispersion C, wherein Dispersion A has an elongation at break of 1000-1500% and a Shore hardness of 40-50 degrees; the elongation at break of dispersion B is 100-500%, the Shore hardness is 30-60 degrees; the elongation at break of dispersion C is 100-300%, and the Shore hardness is 70-90 degrees.
  • the dispersion A, the dispersion B and the dispersion C are all aqueous polyurethanes and are known materials, which are commercially available.
  • Acure 218 resin can be used for the dispersion A (the elongation at break is 1000-1500%, Shore The hardness is 40-50 degrees), the dispersion B is Acure 502 resin (breaking elongation is 100-500%, the Shore hardness is 30-60 degrees), and the dispersion C is Acure 806 resin (the elongation at break is 100). -300%, Shore hardness is 70-90 degrees).
  • the respective amounts of the dispersion A, the dispersion B, and the dispersion C may be based on the total amount of the dispersion A, the dispersion B, and the dispersion C based on the aqueous polyurethane dispersion.
  • the dispersion A is used in an amount of 10 to 70% by weight, preferably 15 to 65% by weight, more preferably 40 to 65% by weight; and the dispersion B is used in an amount of 10 to 50% by weight, preferably 20 to 45% by weight, more It is preferably 25 to 43% by weight; the dispersion C is used in an amount of 5 to 40% by weight, preferably 5 to 20% by weight, more preferably 10 to 20% by weight.
  • the sum of the dispersion A, the dispersion B and the dispersion C was 100% by weight.
  • the aqueous polyurethane dispersion prepared by combining the above various aqueous polyurethanes (dispersion A, dispersion B and dispersion C) having different elongation at break and Shore hardness can provide better explosion-proof effect. Explosion-proof coating.
  • the explosion-proof coating further contains other components to provide a good adhesion, weather resistance, chemical resistance, and the like of the obtained explosion-proof coating.
  • the adhesion promoter is a polymer compound containing a siloxy group and a phosphoric acid group, and is obtained by synthesizing a silane coupling agent and a phosphate. It is commercially available, for example, EDL6038 and EDL-YH645B from Guangzhou Zhijing Chemical Co., Ltd. It may be preferred that in the explosion-proof coating, the adhesion promoter is contained in an amount of from 0.5 to 4% by weight, preferably from 2 to 3.4% by weight.
  • the water-resistant auxiliary agent is an aqueous blocked isocyanate compound.
  • Known substances are commercially available, for example from Bayer's BL 2706, preferably in the explosion-proof coating, which is present in an amount of from 1 to 5% by weight, preferably from 1.1 to 4.8% by weight.
  • the thickener is at least one of a polyacrylate, an associative polyurethane, and a cellulose compound.
  • a polyacrylate for example, X-71 from Guangzhou Lianqing and Rheovis 132 from Ciba.
  • the thickener is contained in an amount of from 0.2 to 3% by weight, preferably from 0.9 to 2.1% by weight.
  • the pH adjuster-I is an overbased organic amine compound. It may also have wetting, dispersing, and is a known material, which is commercially available, for example, Dow Chemical's AMP-95.
  • the pH adjuster-I is contained in an amount of 0.1 to 3% by weight, preferably 1.2 to 2.8% by weight, to ensure that the pH of the explosion-proof coating is between 8 and 9.
  • the film-forming aid may also be contained in the explosion-proof coating of the present disclosure, preferably an alcohol ether solvent.
  • Known materials are commercially available, for example Dowol PnB (propylene glycol butyl ether) from Dow Chemical, preferably in the explosion-proof coating, the film-forming aid is present in an amount of from 5 to 15% by weight, preferably from 3.8 to 4.8. weight%.
  • the total amount of each component constituting the explosion-proof paint is 100% by weight.
  • the water is deionized water in an amount of from 9 to 35% by weight, preferably from 9 to 20% by weight.
  • a second aspect of the present disclosure provides a method of preparing a metallizable explosion-proof coating of the present disclosure, comprising:
  • the active powder comprises an oxide selected from the group consisting of metal elements of columns 9-11 of the periodic table other than copper, silicates, borates and oxalates of the metal elements of columns 9-11 of the periodic table, a hydrogenation catalyst containing a metal element of columns 9-11 of the periodic table, at least one of an ABO 2 type composite oxide having a cuprasite structure, and doped tin oxide;
  • the hydrogenation catalyst is a catalyst for hydrogenating a carbonyl-containing aldehyde, a ketone, a fatty acid or a fatty acid ester to an alcohol;
  • A is one selected from the group consisting of metal elements of columns 9, 10 and 11 of the periodic table, B is Ni, Mn, Cr, Al or Fe, and A is different from B; in the doped tin oxide, the doping element is at least one of vanadium, niobium, indium and molybdenum;
  • step (3) sequentially adding a thickener, an adhesion promoter, a water-resistant auxiliary agent and water to the mixture obtained in the step (2), stirring uniformly and filtering to obtain a metallizable explosion-proof paint;
  • the aqueous polyurethane dispersion, the active powder slurry, the film forming aid, the thickener, the adhesion promoter, the water resistance aid and the water are added in an amount to satisfy the metallizable explosion-proof paint, and the explosion-proof Based on the total amount of the coating, 30-70% by weight of the aqueous polyurethane dispersion, 2-20% by weight of the active powder slurry, 0.1-10% by weight of the adhesion promoter, 0.1-10% by weight of the water-resistant auxiliary agent, 0.1-5 wt% thickener, 0.1-5 wt% pH adjuster-I, 0-20 wt% film former and 5-40 wt% water.
  • the step (1) is for preparing the active powder slurry.
  • the specific process may include: the aqueous resin, the active powder, the aqueous dispersant, the pH adjuster-II and the water satisfying the above content, and the active powder mixture is stirred by a high-speed disperser at a rotation speed of 800 rpm for 5-20 minutes; The mixture was ground until the fineness of the active powder in the ground product was less than 20 ⁇ m, and the grinding was stopped by using a 300-mesh filter cloth to obtain the active powder slurry.
  • steps (2) and (3) are used to prepare an explosion-proof coating, and the specific process may include: an aqueous polyurethane dispersion (dispersion A, dispersion B, and dispersion C) that satisfies the above-mentioned content, and a reactive powder.
  • the slurry, the optional coalescent and water are stirred by a high speed disperser at a speed of 500-1000 rpm for 5-20 min, preferably at a speed of 700-900 rpm for 5-15 min; then at a speed of 300-700 rpm, preferably
  • the pH adjuster-I is added at 400-600 rpm to obtain the product of the step (2) having a pH of 8 to 9; the thickener and the adhesion promoter are sequentially successively rotated at a rotational speed of 300-700 rpm, preferably 400-600 rpm.
  • the water-resistant auxiliary and water are added to the product of the step (2), and then stirred by a high-speed disperser at a rotation speed of 500-1500 rpm, preferably 800-1200 rpm for 5-30 min, preferably 10-25 min; finally, a 300-mesh filter cloth is used for stirring.
  • the product is filtered to give the metallizable explosion-proof coating.
  • steps (2) and (3) The moisture in steps (2) and (3) is used twice, and the total amount satisfies the compositional definition of the metallizable explosion-proof coating.
  • a third aspect of the present disclosure provides an explosion-proof layer having an antenna comprising an explosion-proof coating formed from the metallizable explosion-proof coating of the present disclosure and an antenna formed on the explosion-proof coating.
  • the coating can be formed on a 3D curved surface and then an antenna is formed over at least a portion of the explosion-proof coating.
  • the explosion-proof layer may have a thickness of 10 to 50 ⁇ m, preferably 20 to 40 ⁇ m.
  • a fourth aspect of the present disclosure provides a method for fabricating an explosion-proof layer having an antenna according to the present disclosure, including:
  • step (a) is used to form an explosion-proof coating, which may be on a glass or ceramic body having a 3D curved surface.
  • the glass may preferably be a variety of glass materials suitable for use as a back cover for mobile phones, such as quartz glass, high silica glass, soda lime glass, lead silicate glass, aluminosilicate glass or borosilicate glass.
  • Ceramics can be selected from ceramic materials suitable for use as a back cover for mobile phones, such as alumina ceramics, silicon nitride ceramics, boron nitride ceramics, yttria ceramics or aluminum nitride ceramics.
  • the conditions of the spraying of the step (a) may include: a spray gun diameter of 1-2.5 mm; a spray gun pressure of 2-5 kg/cm 2 ; and a distance between the spray gun and the object to be coated: 10-30 cm.
  • Spraying can be accomplished by applying the metallizable explosion-proof coating to various surfaces, such as 3D curved surfaces, and then forming an explosion-proof coating that protects the 3D curved surface by baking.
  • the baking process may include a multi-stage temperature process: baking at a temperature of 60-80 ° C for 2-10 min, rising to a temperature of 100-120 ° C for 2-10 min, rising to a temperature of 150-170 ° C for 2-10 min.
  • it is baked at a temperature of 70-80 ° C for 5-10 min, raised to a temperature of 100-110 ° C for 5-10 min, and raised to a temperature of 160-170 ° C for 5-10 min.
  • the explosion-proof coating layer preferably formed may have a thickness of 10 to 50 ⁇ m.
  • the laser irradiation conditions include: a laser wavelength of 157 nm to 10.6 ⁇ m, a laser frequency of 30-40 kHz, a laser power of 3-80 W, and a laser scanning speed of 500-8000 mm. /s.
  • the method of forming the copper layer in the step (3) is electroless plating or electroplating.
  • a nickel layer is further formed on the copper layer. Electroless plating or electroplating can be used.
  • the electroless plating or electroplating method may be carried out by a conventional method, and it is preferred that the copper layer is formed to have a thickness of 2 to 15 ⁇ m and the nickel layer has a thickness of 1 to 5 ⁇ m.
  • a fifth aspect of the present disclosure provides a 3D glass or ceramic canopy, wherein the canopy comprises a 3D glass or ceramic substrate, and an explosion-proof layer of the present disclosure having an antenna.
  • the explosion-proof coating layer has a thickness of 10 to 50 ⁇ m, preferably 20 to 40 ⁇ m.
  • the explosion-proof layer having an antenna can be formed by the above-described method for preparing an explosion-proof layer having an antenna according to the present disclosure.
  • a portion of the explosion-proof coating has a metal layer forming an antenna, the metal layer having a thickness of 5 to 20 ⁇ m, and the metal layer being a copper layer or a copper-nickel layer.
  • a sixth aspect of the present disclosure provides an application of the metallizable explosion-proof coating of the present disclosure in providing curved glass or ceramic with explosion-proof and antenna functions.
  • Curved glass or ceramics such as 3D glass or ceramics, must be explosion-proof and cannot be flat.
  • the present disclosure provides a metallizable explosion-proof coating that provides an explosion-proof function to the curved surface by applying a coating on the curved surface to form a coating.
  • the antenna can be further formed on the explosion-proof coating formed by the metallizable explosion-proof coating provided by the present disclosure, thereby providing an explosion-proof and antenna function for the curved glass or ceramic, and providing a solution for the curved glass or ceramic with explosion-proof and antenna Functional method.
  • it may include:
  • the present disclosure prepares an active powder slurry.
  • composition is as follows: New Zealand's SETAL6306ss-60 resin 600g; active powder (ZnSnO 3 , average particle size 1 ⁇ m) 200g; aqueous dispersant (Lu Borun 27000) 80g, deionized water 100g; pH adjuster-II (AMP-95) : 20g.
  • the present disclosure prepares an active powder slurry.
  • composition is as follows: New Zealand's SETAL6306ss-60 resin 500g; active powder (ZnTiO 3 , average particle size 1 ⁇ m) 260g; aqueous dispersant (BYK191) 150g, deionized water 80g; pH adjuster-II (AMP-95): 10g.
  • the present disclosure prepares an active powder slurry.
  • composition is as follows: New Zealand's SETAL6306ss-60 resin 400g; active powder (ZnTiO 3 , average particle size 1 ⁇ m) 300g; aqueous dispersant (BYK191) 100g, deionized water 185g; pH adjuster-II (AMP-95): 15g.
  • Aqueous dispersion A (Acure 218 resin) 650 g; aqueous dispersion B (Acure 502 resin resin) 250 g; aqueous dispersion C (Acure 806 resin) 100 g;
  • Active powder slurry A2 160g
  • Thickener X-710, 10g; Rheovis 132 (Ciba), 5g;
  • Adhesion promoter EDL6038, 20g; EDL-YH645B, 30g;
  • Water resistant additive BL2706 (Bayer), 40g;
  • pH adjuster-I AMP-95, 20g
  • aqueous dispersion A (Acure 218 resin) 400 g
  • aqueous dispersion B (Acure 502 resin resin) 400 g
  • aqueous dispersion C (Acure 806 resin) 200 g
  • Thickener X-710, 4g; Rheovis 132 (Ciba), 20g;
  • Adhesion promoter EDL6038, 10g; EDL-YH645B, 40g;
  • Water resistant additive BL2706 (Bayer), 100g;
  • pH adjuster-I AMP-95, 30g
  • aqueous dispersion A (Acure 218 resin) 450 g
  • aqueous dispersion B (Acure 502 resin resin) 430 g
  • aqueous dispersion C (Acure 806 resin) 120 g
  • Reactive pink pulp A3 200g
  • Thickener X-710, 20g; Rheovis 132 (Ciba), 10g;
  • Adhesion promoter EDL6038, 30g; EDL-YH645B, 20g;
  • Water resistant additive BL2706 (Bayer), 20g;
  • pH adjuster-I AMP-95, 40g
  • aqueous dispersion A (Acure 218 resin) 450 g
  • aqueous dispersion B (Acure 502 resin resin) 430 g
  • aqueous dispersion C (Acure 806 resin) 120 g
  • Reactive pink pulp A3 200g
  • Thickener X-710, 20g; Rheovis 132 (Ciba), 10g;
  • Adhesion promoter EDL6038, 30g; EDL-YH645B, 20g;
  • Water resistant additive BL2706 (Bayer), 20g;
  • pH adjuster-I AMP-95, 40g
  • Spray metallized explosion-proof paint B1 on 3D glass substrate spray condition: spray gun diameter: 2 mm; spray gun pressure: 3 kg/cm 2 ; spray gun and coated object distance: 15 cm.
  • Baking baking at 80 ° C for 10 min, rising to 100 ° C for 10 min, rising to 160 ° C for 10 min, to obtain an explosion-proof coating C1.
  • Laser irradiation of the selected area of the coating C1 is as follows: the laser wavelength is 10.6 ⁇ m, the laser frequency is 30 kHz, the power is 40 W, and the scanning speed is 1500 mm/s.
  • Electroless copper plating is performed on the laser activated region to form a metallic copper layer in the selected region. Continue electroless nickel plating.
  • An explosion-proof layer having an antenna and a 3D glass having the explosion-proof layer were obtained, and the 3D glass was designated as C1-1.
  • Baking baking at 80 ° C for 5 min, rising to 110 ° C for 5 min, rising to 170 ° C for 5 min, to obtain an explosion-proof coating C2.
  • Laser irradiation of the selected area of the coating C2 is as follows: the laser wavelength is 2000 nm, the laser frequency is 40 kHz, the power is 50 W, and the scanning speed is 500 mm/s.
  • Electroless copper plating is performed on the laser activated region to form a metallic copper layer in the selected region. Continue electroless nickel plating.
  • An explosion-proof layer having an antenna and a 3D glass having the explosion-proof layer were obtained, and the 3D glass was designated as C2-1.
  • the metallized explosion-proof paint B3 is sprayed on the 3D ceramic substrate: spray conditions: spray gun diameter: 1.5 mm; spray gun pressure: 2 kg/cm 2 ; spray gun and coated object distance: 10 cm.
  • Baking baking at 80 ° C for 10 min, rising to 100 ° C for 5 min, rising to 170 ° C for 5 min, to obtain an explosion-proof coating C3.
  • Laser irradiation is performed on the selected area of the coating C3.
  • the laser irradiation conditions are: the laser wavelength is 157 nm, the laser frequency is 35 kHz, the power is 80 W, and the scanning speed is 8000 mm/s.
  • Electroless copper plating is performed on the laser activated region to form a metallic copper layer in the selected region. Continue electroless nickel plating.
  • An explosion-proof layer having an antenna and a 3D ceramic having the explosion-proof layer were obtained, and the 3D ceramic was designated as C3-1.
  • the metallized explosion-proof paint B4 is sprayed on the 3D ceramic substrate: spray condition: spray gun diameter: 2.5 mm; spray gun pressure: 4 kg/cm 2 ; spray gun and coated object distance: 25 cm.
  • Baking baking at 80 ° C for 5 min, rising to 110 ° C for 5 min, rising to 160 ° C for 10 min, to obtain an explosion-proof coating C4.
  • Laser irradiation of the selected area of the coating C4 is as follows: the laser wavelength is 5000 nm, the laser frequency is 38 kHz, the power is 3 W, and the scanning speed is 6000 mm/s.
  • Electroless copper plating is performed on the laser activated region to form a metallic copper layer in the selected region. Continue electroless nickel plating.
  • An explosion-proof layer having an antenna and a 3D ceramic having the explosion-proof layer were obtained, and the 3D ceramic was designated as C4-1.
  • the flat glass surface is affixed with a commercially available explosion-proof film and cannot form an antenna.
  • the sample is recorded as D1.
  • the specific content is: draw 5 ⁇ 5 2mm ⁇ 2mm grid on the surface of the sample, cover the grid with 3M600 tape, wipe the tape and make good contact with the grid; quickly pull up the tape from the single side of the tape in the direction of 60°, and repeat the adhesive 3 times.
  • the judgment level is 0-4, the 0 is the adhesion, and the 4 is the adhesion.
  • the adhesion of the coating is the adhesion between the coating and the glass or ceramic, and the adhesion of the coating is the adhesion between the coating forming the antenna and the coating.
  • the explosion-proof performance test was carried out using a high-altitude drop test.
  • the explosion-proof layer of the embodiment 8-11 having the antenna can be obtained and having the explosion-proof Layer of 3D glass or ceramic.
  • the explosion-proof layer has both good coating adhesion and explosion-proof performance, and can provide antenna function.
  • Comparative Example 1 A conventional explosion-proof film was attached to a conventional flat glass, an antenna could not be formed, and the adhesion level was poor.
  • Commercially available conventional explosion-proof membranes cannot be adhered to a glass or ceramic substrate on the surface of a 3D glass or ceramic, and 3D glass or ceramic cannot be used to provide an explosion-proof function.
  • Comparative Example 2 can only form an antenna on a plastic substrate, cannot form an explosion-proof film, and cannot be used to form an explosion-proof film having an antenna on 3D glass or ceramic.

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Abstract

公开了可金属化的防爆涂料及制备与应用、具有天线的防爆层及制备、以及3D玻璃或陶瓷机盖。其中，可金属化的防爆涂料包括：以所述防爆涂料的总量为基准，30-70重量％的水性聚氨酯分散体、2-20重量％的活性粉浆液、0.1-10重量％的附着力促进剂、0.1-10重量％的耐水助剂、0.1-5重量％的增稠剂、0.1-5重量％的pH调节剂-I、0-20重量％的成膜助剂和5-40重量％的水。

Description

可金属化的防爆涂料及制备与应用、具有天线的防爆层及制备、以及3D玻璃或陶瓷机盖 技术领域
本公开涉及3D玻璃或陶瓷基体的防爆领域，具体涉及可金属化的防爆涂料及制备与应用、具有天线的防爆层及制备、以及3D玻璃或陶瓷机盖。
背景技术
随着通讯技术的迅猛发展，5G通讯系统已经开始在研究中。相应的硬件也是各大手机企业研究的重要项目。其中3D玻璃、陶瓷等材料因屏蔽信号较小，外表美观等优点，成为手机屏幕、手机后盖材料的首选。
但是3D玻璃、陶瓷等材料的脆性特点导致产品易破碎，有碎片伤人等风险，因此需要防爆防护。现有的玻璃屏幕的防爆方案主要是贴防爆膜，但仅适用于平面，对于3D玻璃或陶瓷等曲面无法粘贴提供防护。
另外，现有天线功能实现的技术方案有贴FPC天线，但缺点是适用于平面，相对较厚，占有空间大，与现在手机的超薄尺寸设计理念相抵触。另外是LDS技术，但目前该技术主要应用在具有活性成分的塑胶后盖，对于玻璃、陶瓷等材料仍在开发中，无量产技术。
CN103773143A公开了一种白色涂料组合物，含有化学镀催化剂前驱体、粘结剂、溶剂，含或不含助剂，化学镀催化剂前驱体选自SnO 2、ZnSnO 3、ZnTiO 3中的至少一种。进一步地，以100重量份的溶剂为基准，化学镀催化剂前驱体的含量为100-300重量份，粘结剂的含量为5-15重量份，助剂含量为0.1-15重量份；粘结剂选自空气固化的丙烯酸树脂，UV固化的丙烯酸树脂、热固化聚氨酯和水固化聚氨酯中的任意一种，溶剂选自水、苯类溶剂、三氯乙烯、醇、酮、二酮或环酮；助剂选自分散剂、消泡剂、流平剂、粘性调节剂中的至少一种。该组合物可以通过固化粘接在绝缘基材表面，然后经激光照射和表面化学镀的方法在绝缘基材表面的选定区域形成金属层。但是不能解决3D玻璃、陶瓷等脆性材料的防爆问题。
CN201872389U公开了一种防爆玻璃，包括玻璃基板以及通过胶粘剂层粘牢在玻璃基板表面的防爆膜层，该防爆膜层由上层的防爆膜基层和吸附在防爆膜基层下方的金属层组成。该实用新型通过胶粘剂层粘贴防爆膜层的方式提供防爆玻璃，且在高聚物的防爆膜基层与胶粘剂层之间加入金属层，利用金属层的延展性和强韧度有效抵消和分解冲击。但是贴膜方式不适合具有曲面的3D玻璃、陶瓷等脆性材料，且不能提供手机天线功能。
可以看出，对于如何解决3D玻璃、陶瓷等脆性材料的防爆，以及满足该材料的天线 功能，需要提供新的技术方案。
公开内容
本公开的目的是为了解决3D玻璃、陶瓷等脆性材料的防爆和具有天线功能的问题，提供了可金属化的防爆涂料及制备与应用、具有天线的防爆层及制备、以及3D玻璃或陶瓷机盖。该防爆涂料可以应用在曲面玻璃或陶瓷上通过涂料形式形成防爆涂层实现为3D玻璃、陶瓷等脆性材料提供防爆功能且可以同时在该防爆涂层上形成天线结构。
为了实现上述目的，本公开第一方面提供一种可金属化的防爆涂料，以所述防爆涂料的总量为基准，包括：
30-70重量％的水性聚氨酯分散体、2-20重量％的活性粉浆液、0.1-10重量％的附着力促进剂、0.1-10重量％的耐水助剂、0.1-5重量％的增稠剂、0.1-5重量％的pH调节剂-I、0-20重量％的成膜助剂和5-40重量％的水；
其中，以所述活性粉浆液的总量为基准，所述活性粉浆液包含30-60重量％的水性树脂、20-50重量％的活性粉、5-20重量％的水性分散剂、5-30重量％的水和0.1-5重量％的pH调节剂-II；
其中，所述活性粉包括选自除铜以外的元素周期表第9-11列金属元素的氧化物，元素周期表第9-11列金属元素的硅酸盐、硼酸盐和草酸盐，含有元素周期表第9-11列金属元素的加氢催化剂，具有铜铁矿结构的ABO 2型复合氧化物中的至少一种，以及掺杂的氧化锡；
其中，所述加氢催化剂为使含羰基的醛、酮、脂肪酸或脂肪酸酯加氢成为醇的催化剂；A为选自元素周期表第9、10和11列金属元素中一种，B为Ni、Mn、Cr、Al或Fe，且A与B不同；所述掺杂的氧化锡中，掺杂元素为钒、锑、铟和钼中的至少一种。
优选地，所述活性粉浆液中，所述水性树脂为水溶性的聚酯树脂或水溶性的丙烯酸树脂。
优选地，所述水溶性的聚酯树脂为纽佩斯的SETAL6306ss-60树脂。
优选地，所述水性树脂的含量为40-60重量％。
优选地，所述活性粉浆液中，所述活性粉的平均粒径为1nm-10μm，优选为1nm-1μm。
优选地，所述活性粉为ZnSnO 3和/或ZnTiO 3。
优选地，所述活性粉的含量为20-45重量％，优选为20-30重量％或25～45重量％，更优选为25～30重量％。
优选地，所述活性粉浆液中，所述水性分散剂为含有颜料亲和基团的高分子聚合物。
优选地，所述活性粉浆液中，所述水性分散剂为陆博润的27000以及BYK的190、191、192、194中的至少之一，优选为陆博润的27000和BYK的191中的至少之一。
优选地，所述活性粉浆液中，所述水性分散剂的含量为5-15重量％，优选为8-15重量％。
优选地，所述pH调节剂-II为有机胺试剂，优选为乙醇胺、N,N-二甲基乙醇胺、2-氨基-2-甲基-1-丙醇、氨水和陶氏化学的AMP-95中的至少之一。
优选地，所述活性粉浆液的pH值为7.5-8.5。
优选地，所述活性粉浆液中，所述pH调节剂-II的含量为0.1-3重量％，优选为1-2重量％。
优选地，所述活性粉浆液中，所述水加入量为5-25重量％，优选为8-18.5重量％。
优选地，所述水性聚氨酯分散体为多种水性聚氨酯的混合物，包括分散体A、分散体B和分散体C，其中，分散体A的断裂伸长率为1000-1500％，肖氏硬度为40-50度；分散体B的断裂伸长率为100-500％，肖氏硬度为30-60度；分散体C的断裂伸长率为100-300％，肖氏硬度为70-90度。
优选地，所述分散体A为Acure 218树脂。
优选地，所述分散体B为Acure 502树脂。
优选地，所述分散体C为Acure 806树脂。
优选地，以所述水性聚氨酯分散体的总量为基准，分散体A的用量为10-70重量％，优选为15-65重量％，更优选为40-65重量％：分散体B的用量为10-50重量％，优选为20-45重量％，更优选为25-43重量％；分散体C的用量为5-40重量％，优选为5-20重量％，更优选为10-20重量％。
优选地，所述附着力促进剂为含有硅氧基团和磷酸基团的高分子化合物，所述高分子化合物由硅烷偶联剂与磷酸酯合成得到。
优选地，所述附着力促进剂为广州致精化股份有限公司的EDL6038和/或EDL-YH645B。
优选地，所述附着力促进剂的含量为0.5-4重量％，优选为2-3.4重量％。
优选地，所述耐水助剂为水性封闭型异氰酸酯化合物。
优选地，所述耐水助剂为拜耳的BL2706。
优选地，所述耐水助剂的含量为1-5重量％，优选为1.1-4.8重量％。
优选地，所述增稠剂为聚丙烯酸酯、缔合型聚氨酯和纤维素化合物中的至少一种。
优选地，所述增稠剂为广州联固化学的X-71和/或汽巴公司的Rheovis132。
优选地，所述增稠剂的含量为0.2-3重量％，优选为0.9-2.1重量％。
优选地，所述pH调节剂-I为高碱性有机胺化合物。
优选地，所述pH调节剂-I为陶氏化学的AMP-95。
优选地，所述pH调节剂-I含量为0.1-3重量％，优选为1.2-2.8重量％。
优选地，所述成膜助剂为醇醚溶剂。
优选地，所述成膜助剂为陶氏化学的AMP-95。
优选地，所述成膜助剂的含量为5-15重量％，优选为3.8-4.8重量％。
优选地，以所述防爆涂料的总量为基准，所述水的含量为9-35重量％，优选为9-20重量％。
本公开第二方面提供一种制备本公开上述的可金属化的防爆涂料的方法，包括：
(1)将水性树脂、活性粉、水性分散剂、pH调节剂-II和水进行混合、研磨和过滤，得到活性粉浆液；其中，水性树脂、活性粉、水性分散剂、pH调节剂-II和水的投料量满足所述活性粉浆液包含30-60重量％的水性树脂、20-50重量％的活性粉、5-20重量％的水性分散剂、5-30重量％的水和0.1-5重量％的pH调节剂-II；
其中，所述活性粉包括选自除铜以外的元素周期表第9-11列金属元素的氧化物，元素周期表第9-11列金属元素的硅酸盐、硼酸盐和草酸盐，含有元素周期表第9-11列金属元素的加氢催化剂，具有铜铁矿结构的ABO 2型复合氧化物中的至少一种，以及掺杂的氧化锡；
其中，所述加氢催化剂为使含羰基的醛、酮、脂肪酸或脂肪酸酯加氢成为醇的催化剂；A为选自元素周期表第9、10和11列金属元素中一种，B为Cu、Sn、Zn、Ti、Ni、Mn、Cr、Al或Fe，且A与B不同；所述掺杂的氧化锡中，掺杂元素为钒、锑、铟和钼中的至少一种；
(2)将水性聚氨酯分散体、所述活性粉浆液、成膜助剂和水进行混合并加入pH调节剂-I调节pH值为8-9；
(3)顺次将增稠剂、附着力促进剂、耐水助剂和水加入步骤(2)得到的混合物中搅拌均匀并过滤，得到可金属化的防爆涂料；
其中，水性聚氨酯分散体、所述活性粉浆液、成膜助剂、增稠剂、附着力促进剂、耐水助剂和水的加入量满足所述可金属化的防爆涂料中，以所述防爆涂料的总量为基准，含有30-70重量％的水性聚氨酯分散体、2-20重量％的活性粉浆液、0.1-10重量％的附着力促进剂、0.1-10重量％的耐水助剂、0.1-5重量％的增稠剂、0.1-5重量％的pH调节剂-I、0-20重量％的成膜助剂和5-40重量％的水。
本公开第三方面提供一种具有天线的防爆层，包括由本公开上述的可金属化的防爆涂料或采用本公开上述方法得到的可金属化的防爆涂料形成的防爆涂层和在所述防爆涂层上形成的天线。
优选地，所述防爆层的厚度为10-50μm，优选为20-40μm。
本公开第四方面提供一种制备本公开的上述具有天线的防爆层的方法，包括：
(a)将本公开上述的可金属化的防爆涂料或本公开上述的方法得到的可金属化的防爆涂料喷涂在玻璃或陶瓷体上，并烘烤形成防爆涂层；
(b)在所述防爆涂层的选定区域上进行激光照射，得到激光活化区；
(c)在所述激光活化区形成铜层。
优选地，步骤(b)中，所述激光照射的条件包括：激光波长为157nm-10.6μm，激光频率为30-40kHz，激光功率为3-80W，激光扫描速度为500-8000mm/s。
优选地，步骤(c)中形成铜层的方法为化学镀或电镀。
优选地，在步骤(c)中，所述铜层的厚度为2-15μm。
优选地，所述方法还包括：(d)在所述铜层上再形成镍层。
优选地，所述镍层的厚度为1-5μm。
本公开第五方面提供一种3D玻璃或陶瓷机盖，其中，该机盖包括3D玻璃或陶瓷的基体，和本公开的上述具有天线的防爆层或采用本公开上述的方法得到的具有天线的防爆层。
优选地，所述防爆涂层的厚度为10-50μm。
本公开第六方面提供一种本公开的可金属化的防爆涂料在提供曲面玻璃或陶瓷具有防爆和天线功能中的应用。
通过上述技术方案，本公开提供可金属化的防爆涂料，可以实现通过涂覆该涂料形成防爆涂层，适合实施于3D曲面，如3D玻璃、陶瓷等脆性材料实现具有防爆功能。同时，该还可以在该涂层上形成天线，提供3D玻璃或陶瓷还具有天线功能。
本公开的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本公开的实践了解到。
公开详细描述
下面描述的实施例是示例性的，旨在用于解释本公开，而不能理解为对本公开的限制。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本公开第一方面提供一种可金属化的防爆涂料，以所述防爆涂料的总量为基准，包括：
30-70重量％的水性聚氨酯分散体、2-20重量％的活性粉浆液、0.1-10重量％的附着力促进剂、0.1-10重量％的耐水助剂、0.1-5重量％的增稠剂、0.1-5重量％的pH调节剂-I、0-20重量％的成膜助剂和5-40重量％的水；
其中，以所述活性粉浆液的总量为基准，所述活性粉浆液包含30-60重量％的水性树脂、20-50重量％的活性粉、5-20重量％的水性分散剂、5-30重量％的水和0.1-5重量％的pH调节剂-II；
其中，所述活性粉包括选自除铜以外的元素周期表第9-11列金属元素的氧化物，元素周期表第9-11列金属元素的硅酸盐、硼酸盐和草酸盐，含有元素周期表第9-11列金属元素的加氢催化剂，具有铜铁矿结构的ABO 2型复合氧化物中的至少一种，以及掺杂的氧化锡；
其中，所述加氢催化剂为使含羰基的醛、酮、脂肪酸或脂肪酸酯加氢成为醇的催化剂；A为选自元素周期表第9、10和11列金属元素中一种，B为Cu、Sn、Zn、Ti、Ni、Mn、Cr、Al或Fe，且A与B不同；所述掺杂的氧化锡中，掺杂元素为钒、锑、铟和钼中的至少一种。
本公开为解决具有3D曲面的玻璃、陶瓷等脆性材料得到防爆防护，采取在3D曲面上涂覆涂料形成防爆涂层的措施，为此提供所述可金属化的防爆涂料。该防爆涂料选用多种水性聚氨酯分散体作为主体树脂，与多种相关试剂相搭配，可以应用提供在3D曲面上形成具有防爆功能且耐化学药水、附着力优异的防爆涂层。
本公开中，所述可金属化的防爆涂料不仅可以适用于为3D曲面提供防爆涂层，而且可以通过添加组分如所述活性粉浆液，使获得的涂层可以进一步形成天线。所述活性粉浆液也包含多种组分。优选地，所述活性粉浆液中，所述水性树脂为水溶性的聚酯树脂或水溶性的丙烯酸树脂。所述水性树脂可以为所述活性粉提供良好的粉料分散性。所述水性树脂为已知物质，可以商购获得，例如优选的水溶性的聚酯树脂可以是纽佩斯的SETAL6306ss-60树脂。
本公开中，优选地，所述活性粉浆液中，所述水性树脂的含量为40-60重量％。
本公开中，优选地，所述活性粉浆液中，所述活性粉的平均粒径为1nm-10μm，优选为1nm-1μm。所述活性粉是已知物质，可以商购获得。平均粒径可以采用晶态激光测试仪测定，可以以乙醇为分散介质。例如所述活性粉可以是ZnSnO 3和/或ZnTiO 3。
本公开中，优选地，所述活性粉浆液中，所述活性粉的含量为20-45重量％，优选为20-30重量％或25～45重量％，更优选25～30重量％。
本公开中，所述水性分散剂可以是含有颜料亲和基团的高分子聚合物，有助于所述活性粉浆液分散，可以商购获得，如陆博润的27000，BYK的190、191、192和194等。优选陆博润的27000和BYK的191。优选地，所述水性分散剂的含量为5-15重量％，优选为8-15重量％。
本公开中，所述pH调节剂-II可以是用于调节所述活性粉浆液的pH值的有机胺试剂，如乙醇胺、N,N-二甲基乙醇胺、2-氨基-2-甲基-1-丙醇、氨水。可以商购获得，例如陶氏化学的AMP-95(2-氨基-2-甲基-1-丙醇)。所述pH调节剂-II的用量满足提供所述活性粉浆液需要的pH值即可，如所述活性粉浆液pH值可以为7.5-8.5。优选地，所述pH调节剂-II的含量为0.1-3重量％，优选为1-2重量％。
本公开中，优选地，水可以是去离子水，加入量为5-25重量％，优选为8-18.5重量％。
本公开中，加入所述活性粉浆液的各组分的总量满足100重量％。
本公开提供的可金属化的防爆涂料中，除上述活性粉浆液外，还包含形成防爆涂层的其他组分。所述水性聚氨酯分散体可以作为能够最终形成涂层的主体组分。优选地，所述水性聚氨酯分散体为多种水性聚氨酯的混合物，包括分散体A、分散体B和分散体C，其中，分散体A的断裂伸长率为1000-1500％，肖氏硬度为40-50度；分散体B的断裂伸长率为100-500％，肖氏硬度为30-60度；分散体C的断裂伸长率为100-300％，肖氏硬度为70-90度。所述分散体A、分散体B和分散体C都是水性聚氨酯，是已知物质，可以商购获得，例如可以分散体A选用Acure 218树脂(断裂伸长率为1000-1500％，肖氏硬度为40-50度)，分散体B选用Acure 502树脂(断裂伸长率为100-500％，肖氏硬度为30-60度)，分散体C选用Acure 806树脂(断裂伸长率为100-300％，肖氏硬度为70-90度)。
本公开中，所述分散体A、分散体B和分散体C各自用量可以以所述水性聚氨酯分散体为基准，即所述分散体A、分散体B和分散体C的总量为基准，分散体A的用量为10-70重量％，优选为15-65重量％，更优选为40-65重量％；分散体B的用量为10-50重量％，优选为20-45重量％，更优选为25-43重量％；分散体C的用量为5-40重量％，优选为5-20重量％，更优选为10-20重量％。所述分散体A、分散体B和分散体C的总和为100重量％。选择上述多种具有不同断裂伸长率和肖氏硬度的水性聚氨酯(分散体A、分散体B和分散体C)组配而成的所述水性聚氨酯分散体，可以提供形成具有更好防爆效果的防爆涂层。
本公开中，所述防爆涂料还包含其他组分以提供可以获得的防爆涂层具有好的附着力、耐候性、耐化学药水性等。
本公开中，优选地，所述附着力促进剂为含有硅氧基团和磷酸基团的高分子化合物，由硅烷偶联剂与磷酸酯合成得到。可以商购获得，例如广州致精化股份有限公司的EDL6038和EDL-YH645B。可以优选所述防爆涂料中，所述附着力促进剂的含量为0.5-4重量％，优选为2-3.4重量％。
本公开的所述防爆涂料中优选地，所述耐水助剂为水性封闭型异氰酸酯化合物。为已知物质，可以商购获得，例如拜耳的BL2706，优选所述防爆涂料中，所述耐水助剂的含量为1-5重量％，优选为1.1-4.8重量％。
本公开的所述防爆涂料中优选地，所述增稠剂为聚丙烯酸酯、缔合型聚氨酯和纤维素化合物中的至少一种。为已知物质，可以商购获得，例如广州联固化学的X-71和汽巴公司的Rheovis132。优选所述防爆涂料中，所述增稠剂的含量为0.2-3重量％，优选为0.9-2.1重量％。
本公开的所述防爆涂料中优选地，所述pH调节剂-I为高碱性有机胺化合物。可以还 同时具有润湿、分散作用，为已知物质，可以商购获得，例如陶氏化学的AMP-95。优选所述防爆涂料中，所述pH调节剂-I的含量为0.1-3重量％，优选为1.2-2.8重量％，保证所述防爆涂料的pH在8-9之间即可。
本公开的所述防爆涂料中还可以含有所述成膜助剂，优选为醇醚溶剂。为已知物质，可以商购获得，例如陶氏化学的Dowanol PnB(丙二醇丁醚)，优选所述防爆涂料中，所述成膜助剂的含量为5-15重量％，优选为3.8-4.8重量％。
本公开中，组成所述防爆涂料的各组分的总量为100重量％。优选地，水为去离子水，含量为9-35重量％，优选为9-20重量％。
本公开第二方面提供一种本公开的可金属化的防爆涂料的制备方法，包括：
(1)将水性树脂、活性粉、水性分散剂、pH调节剂-II和水进行混合、研磨和过滤，得到活性粉浆液；其中，水性树脂、活性粉、水性分散剂、pH调节剂-II和水的投料量满足所述活性粉浆液包含30-60重量％的水性树脂、20-50重量％的活性粉、5-20重量％的水性分散剂、5-30重量％的水和0.1-5重量％的pH调节剂-II；
其中，所述活性粉包括选自除铜以外的元素周期表第9-11列金属元素的氧化物，元素周期表第9-11列金属元素的硅酸盐、硼酸盐和草酸盐，含有元素周期表第9-11列金属元素的加氢催化剂，具有铜铁矿结构的ABO 2型复合氧化物中的至少一种，以及掺杂的氧化锡；
其中，所述加氢催化剂为使含羰基的醛、酮、脂肪酸或脂肪酸酯加氢成为醇的催化剂；A为选自元素周期表第9、10和11列金属元素中一种，B为Ni、Mn、Cr、Al或Fe，且A与B不同；所述掺杂的氧化锡中，掺杂元素为钒、锑、铟和钼中的至少一种；
(2)将水性聚氨酯分散体、所述活性粉浆液、可选的成膜助剂和水进行混合并加入pH调节剂-I调节pH值为8-9；
(3)顺次将增稠剂、附着力促进剂、耐水助剂和水加入步骤(2)得到的混合物中搅拌均匀并过滤，得到可金属化的防爆涂料；
其中，水性聚氨酯分散体、所述活性粉浆液、成膜助剂、增稠剂、附着力促进剂、耐水助剂和水的加入量满足所述可金属化的防爆涂料中，以所述防爆涂料的总量为基准，含有30-70重量％的水性聚氨酯分散体、2-20重量％的活性粉浆液、0.1-10重量％的附着力促进剂、0.1-10重量％的耐水助剂、0.1-5重量％的增稠剂、0.1-5重量％的pH调节剂-I、0-20重量％的成膜助剂和5-40重量％的水。
本公开提供的上述方法中，步骤(1)用于制备所述活性粉浆液。具体过程可以包括：将满足上述含量的水性树脂、活性粉、水性分散剂、pH调节剂-II和水，采用高速分散机在转速为800rpm下搅拌5-20min得活性粉混合物；采用篮式研磨机将该混合物进行研磨，直至研磨产物中活性粉的细度低于20μm时停止研磨；采用300目滤布将研磨产物进行过滤， 得到所述活性粉浆液。
本公开中，步骤(2)和(3)用于制得防爆涂料，具体过程可以包括：将满足上述含量限定的水性聚氨酯分散体(分散体A、分散体B和分散体C)、活性粉浆液、可选的成膜助剂和水，采用高速分散机在转速为500-1000rpm下搅拌5-20min，优选转速为700-900rpm下搅拌5-15min；然后在转速为300-700rpm，优选为400-600rpm下加入pH调节剂-I，得到pH值为8～9的步骤(2)产物；继续在转速为300-700rpm，优选为400-600rpm下顺次将增稠剂、附着力促进剂、耐水助剂和水加入步骤(2)的产物中，然后采用高速分散机在转速为500-1500rpm，优选800-1200rpm下搅拌5-30min，优选10-25min；最后采用300目滤布将搅拌产物进行过滤，得到所述可金属化的防爆涂料。
步骤(2)和(3)中水分两次使用，总量满足所述可金属化的防爆涂料的组成限定。
本公开第三方面提供一种具有天线的防爆层，包括由本公开的可金属化的防爆涂料形成的防爆涂层和在所述防爆涂层上形成的天线。该涂层可以形成在3D曲面上，然后在该防爆涂层的至少部分区域上形成天线。所述防爆层的厚度可以为10-50μm，优选为20-40μm。
本公开第四方面提供一种本公开的具有天线的防爆层的制备方法，包括：
(a)将本公开的可金属化的防爆涂料喷涂在玻璃或陶瓷体上，并烘烤形成防爆涂层；
(b)在所述防爆涂层的选定区域上进行激光照射，得到激光活化区；
(c)在所述激光活化区形成铜层。
本公开中，步骤(a)用于形成防爆涂层，可以在具有3D曲面的玻璃或陶瓷体上。玻璃可以优选为各种适用于做手机后盖的玻璃材料，例如石英玻璃、高硅氧玻璃、钠钙玻璃、铅硅酸盐玻璃、铝硅酸盐玻璃或硼硅酸盐玻璃。陶瓷可以选用适用于做手机后盖的陶瓷材料，例如氧化铝陶瓷、氮化硅陶瓷、氮化硼陶瓷、氧化铍陶瓷或氮化铝陶瓷。
本公开中，步骤(a)的喷涂的条件可以包括：喷枪直径1-2.5mm；喷枪压力：2-5kg/cm 2；喷枪与被涂物距离：10-30cm。喷涂可以实现将所述可金属化的防爆涂料涂覆在各种表面，如3D曲面上，然后通过烘烤形成可以防护3D曲面的防爆涂层。所述烘烤的过程可以包括多段温度过程：在温度60-80℃下烘烤2-10min、升至温度100-120℃烘烤2-10min，升至温度150-170℃烘烤2-10min；优选地，在温度70-80℃下烘烤5-10min、升至温度100-110℃烘烤5-10min，升至温度160-170℃烘烤5-10min。
本公开中，优选形成的所述防爆涂层的厚度可以为10-50μm。
本公开中，优选地，步骤(b)中，所述激光照射的条件包括：激光波长为157nm-10.6μm，激光频率为30-40kHz，激光功率为3-80W，激光扫描速度为500-8000mm/s。
本公开中，优选地，步骤(3)中形成铜层的方法为化学镀或电镀。
本公开中，优选地，在所述铜层上再形成镍层。可以采用化学镀或电镀。
本公开中，所述化学镀或电镀的方法采用常规的方法即可，优选形成的铜层的厚度为2-15μm，镍层的厚度为1-5μm。
本公开第五方面提供一种3D玻璃或陶瓷机盖，其中，该机盖包括3D玻璃或陶瓷的基体，和本公开的具有天线的防爆层。
本公开中，优选地，所述防爆涂层的厚度为10-50μm，优选为20-40μm。
本公开中，所述具有天线的防爆层可以通过本公开上述的具有天线的防爆层的制备方法形成。
本公开中，在所述防爆涂层的局部有形成天线的金属层，金属层的厚度为5～20μm，金属层为铜层或铜-镍层。
本公开第六方面提供一种本公开的可金属化的防爆涂料在提供曲面玻璃或陶瓷具有防爆和天线功能中的应用。
曲面玻璃或陶瓷，例如3D玻璃或陶瓷要具备防爆功能，不能采取平面的贴膜方式。本公开提供了可金属化的防爆涂料，可以通过在曲面上实施涂料形成涂层的方式为曲面提供防爆功能。并且在本公开提供的可金属化的防爆涂料形成的防爆涂层上还可以进一步形成天线，从而实现为曲面玻璃或陶瓷提供防爆和天线功能，提供了一种解决曲面玻璃或陶瓷具有防爆和天线功能的方法。具体地，可以包括：
(i)将本公开的可金属化的防爆涂料喷涂在曲面玻璃或陶瓷体上，并烘烤形成防爆涂层；
(ii)在所述防爆涂层的选定区域上进行激光照射，得到激光活化区；
(iii)在所述激光活化区形成铜层。
具体的条件如上所述，不在赘述。
以下将通过实施例对本公开进行详细描述。
以下实施例和对比例中，原料为市售品。
实施例1
说明本公开制备活性粉浆料。
组分如下：纽佩斯的SETAL6306ss-60树脂600g；活性粉(ZnSnO 3，平均粒径1μm)200g；水性分散剂(陆博润27000)80g，去离子水100g；pH调节剂-II(AMP-95)：20g。
制备：将上述组分混合并采用高速分散机以转速800rpm搅拌10min得活性粉混合物，pH＝8.5；再采用篮式研磨机将该混合物进行研磨，直至研磨产物中活性粉的细度低于20μm时停止研磨，采用300目滤布过滤，得到活性粉浆液A1。
实施例2
说明本公开制备活性粉浆料。
组分如下：纽佩斯的SETAL6306ss-60树脂500g；活性粉(ZnTiO 3，平均粒径1μm)260g；水性分散剂(BYK191)150g，去离子水80g；pH调节剂-II(AMP-95)：10g。
制备：将上述组分混合并采用高速分散机以转速800rpm搅拌20min得活性粉混合物，pH＝7.5；再采用篮式研磨机将该混合物进行研磨，直至研磨产物中活性粉的细度低于20μm时停止研磨，采用300目滤布过滤，得到活性粉浆液A2。
实施例3
说明本公开制备活性粉浆料。
组分如下：纽佩斯的SETAL6306ss-60树脂400g；活性粉(ZnTiO 3，平均粒径1μm)300g；水性分散剂(BYK191)100g，去离子水185g；pH调节剂-II(AMP-95)：15g。
制备：将上述组分混合并采用高速分散机以转速800rpm搅拌20min得活性粉混合物，pH＝8.1；再采用篮式研磨机将该混合物进行研磨，直至研磨产物中活性粉的细度低于20μm时停止研磨，采用300目滤布过滤，得到活性粉浆液A3。
实施例4
说明本公开制备可金属化的防爆涂料。
组分如下：
水性分散体A(Acure 218树脂)650g；水性分散体B(Acure502树脂树脂)250g；水性分散体C(Acure 806树脂)100g；
活性粉浆液A2：160g；
增稠剂：X-710，10g；Rheovis132(汽巴公司)，5g；
附着力促进剂：EDL6038，20g；EDL-YH645B，30g；
耐水助剂：BL2706(拜耳)，40g；
pH调节剂-I：AMP-95，20g；
成膜助剂：Dowanol PnB，60g；
去离子水：200g。
制备：
(1)将上述的组分水性分散体(A、B和C)、活性粉浆液A2、成膜助剂和部分水，采用高速分散机在800rpm下搅拌10min；
(2)转速为500rpm下，加入pH调节剂，pH值为8.6；
(3)转速为500rpm下，依顺序加入增稠剂、附着力促进剂、耐水助剂和剩余水；再采用高速分散机900rpm下搅拌30min；
(4)采用300目滤布过滤，得到可金属化的防爆涂料B1。
实施例5
说明本公开制备可金属化的防爆涂料。
组分如下：水性分散体A(Acure 218树脂)400g；水性分散体B(Acure502树脂树脂)400g；水性分散体C(Acure 806树脂)200g；
活性粉色浆A1：400g；
增稠剂：X-710，4g；Rheovis132(汽巴公司)，20g；
附着力促进剂：EDL6038，10g；EDL-YH645B，40g；
耐水助剂：BL2706(拜耳)，100g；
pH调节剂-I：AMP-95，30g；
成膜助剂：Dowanol PnB，100g；
去离子水：400g。
制备：
(1)将上述的组分水性分散体(A、B和C)、活性粉浆液A1、成膜助剂和部分水，采用高速分散机在700rpm下搅拌20min；
(2)转速为400rpm下，加入pH调节剂，pH值为8.1；
(3)转速为400rpm下，依顺序加入增稠剂、附着力促进剂、耐水助剂和剩余水；再采用高速分散机1100rpm下搅拌20min；
(4)采用300目滤布过滤，得到可金属化的防爆涂料B2。
实施例6
说明本公开制备可金属化的防爆涂料。
组分如下：水性分散体A(Acure 218树脂)450g；水性分散体B(Acure502树脂树脂)430g；水性分散体C(Acure 806树脂)120g；
活性粉色浆A3：200g；
增稠剂：X-710，20g；Rheovis132(汽巴公司)，10g；
附着力促进剂：EDL6038，30g；EDL-YH645B，20g；
耐水助剂：BL2706(拜耳)，20g；
pH调节剂-I：AMP-95，40g；
成膜助剂：Dowanol PnB，80g；
去离子水：135g。
制备：
(1)将上述的组分水性分散体(A、B和C)、活性粉浆液A3、成膜助剂和部分水，采用高速分散机在700rpm下搅拌20min；
(2)转速为400rpm下，加入pH调节剂，pH值为9.0；
(3)转速为400rpm下，依顺序加入增稠剂、附着力促进剂、耐水助剂和剩余水；再采用高速分散机1100rpm下搅拌20min；
(4)采用300目滤布过滤，得到可金属化的防爆涂料B3。
实施例7
说明本公开制备可金属化的防爆涂料。
组分如下：水性分散体A(Acure 218树脂)450g；水性分散体B(Acure502树脂树脂)430g；水性分散体C(Acure 806树脂)120g；
活性粉色浆A3：200g；
增稠剂：X-710，20g；Rheovis132(汽巴公司)，10g；
附着力促进剂：EDL6038，30g；EDL-YH645B，20g；
耐水助剂：BL2706(拜耳)，20g；
pH调节剂-I：AMP-95，40g；
去离子水：135g。
制备：
(1)将上述的组分水性分散体(A、B和C)、活性粉浆液A3和部分水，采用高速分散机在700rpm下搅拌20min；
(2)转速为400rpm下，加入pH调节剂，pH值为8.7；
(3)转速为400rpm下，依顺序加入增稠剂、附着力促进剂、耐水助剂和剩余水；再采用高速分散机1100rpm下搅拌20min；
(4)采用300目滤布过滤，得到可金属化的防爆涂料B4。
实施例8
用于说明制备具有天线的防爆层和带有该防爆层的3D玻璃。
1)将可金属化的防爆涂料B1采用喷涂方式，喷涂于3D玻璃基材：喷涂条件为：喷枪直径：2mm；喷枪压力：3kg/cm 2；喷枪与被涂物距离：15cm。
烘烤：80℃烘烤10min、升至100℃烘烤10min，升至160℃烘烤10min，得到防爆涂层C1。
2)将涂层C1选定区域激光照射，激光照射条件为：激光波长为10.6μm，激光频率30kHz，功率为40W，扫描速度为1500mm/s。
3)对激光活化的区域进行化学镀铜，在选定区域形成金属铜层。继续进行化学镀镍。
得到具有天线的防爆层和具有该防爆层的3D玻璃，3D玻璃记为C1-1。
实施例9
用于说明制备具有天线的防爆层和带有该防爆层的3D玻璃。
1)将可金属化的防爆涂料B2采用喷涂方式，喷涂于3D玻璃基材：喷涂条件为：喷枪直径：2mm；喷枪压力：4kg/cm 2；喷枪与被涂物距离：20cm。；
烘烤：80℃烘烤5min、升至110℃烘烤5min，升至170℃烘烤5min，得到防爆涂层C2。
2)将涂层C2选定区域激光照射，激光照射条件为：激光波长为2000nm，激光频率40kHz，功率为50W，扫描速度为500mm/s。
3)对激光活化的区域进行化学镀铜，在选定区域形成金属铜层。继续进行化学镀镍。
得到具有天线的防爆层和具有该防爆层的3D玻璃，3D玻璃记为C2-1。
实施例10
用于说明制备具有天线的防爆层和带有该防爆层的3D陶瓷。
1)将可金属化的防爆涂料B3采用喷涂方式，喷涂于3D陶瓷基材：喷涂条件为：喷枪直径：1.5mm；喷枪压力：2kg/cm 2；喷枪与被涂物距离：10cm。
烘烤：80℃烘烤10min、升至100℃烘烤5min，升至170℃烘烤5min，得到防爆涂层C3。
2)将涂层C3选定区域激光照射，激光照射条件为：激光波长为157nm，激光频率35kHz，功率为80W，扫描速度为8000mm/s。
3)对激光活化的区域进行化学镀铜，在选定区域形成金属铜层。继续进行化学镀镍。
得到具有天线的防爆层和具有该防爆层的3D陶瓷，3D陶瓷记为C3-1。
实施例11
用于说明制备具有天线的防爆层和带有该防爆层的3D陶瓷。
1)将可金属化的防爆涂料B4采用喷涂方式，喷涂于3D陶瓷基材：喷涂条件为：喷 枪直径：2.5mm；喷枪压力：4kg/cm 2；喷枪与被涂物距离：25cm。
烘烤：80℃烘烤5min、升至110℃烘烤5min，升至160℃烘烤10min，得到防爆涂层C4。
2)将涂层C4选定区域激光照射，激光照射条件为：激光波长为5000nm，激光频率38kHz，功率为3W，扫描速度为6000mm/s。
3)对激光活化的区域进行化学镀铜，在选定区域形成金属铜层。继续进行化学镀镍。
得到具有天线的防爆层和具有该防爆层的3D陶瓷，3D陶瓷记为C4-1。
对比例1
平面玻璃表面贴市售常用的防爆膜，不能形成天线。样品记为D1。
对比例2
采用LDS技术，在塑胶基材上进行金属化，化学镀铜后化学镀镍，样品记为D2。
实施例12
涂层及镀层外观测试
通过目测方式，观察得到的涂层及镀层外观，是否有鼓泡、变色等异常，记入表1。
表1
Figure PCTCN2018119281-appb-000001
涂层及镀层附着力测试
采用GB/T 9286-1998附着力测试标准测试涂层和镀层的附着力。
具体内容为：在样品表面划5×5个2mm×2mm的网格，用3M600胶带覆盖格子，擦拭胶带与格子完全良好接触；从胶带单边以60°方向迅速拉起胶带，并重复粘揭3次。判断等级为0-4级，0级为附着力强，4级为附着力弱。结果见表2、3。
涂层附着力为涂层与玻璃或陶瓷之间的附着力，镀层附着力为形成天线的镀层与涂层之间的附着力。
表2涂层附着力测试
Figure PCTCN2018119281-appb-000002
表3镀层附着力测试
Figure PCTCN2018119281-appb-000003
防爆性能测试
采用高空跌落试验进行防爆性能测试。
具体参数为：高度120cm，负载1000g重量的样品跌落试验，观察样品破碎后状态。仍是整体，无碎片分离，记为OK，否则记为NG。结果见表4。
表4防爆性能测试
Figure PCTCN2018119281-appb-000004
通过实施例、对比例和表1-4的结果可以看出，采用本公开实施例4-7提供的可金属化的防爆涂料，可以得到实施例8-11具有天线的防爆层和具有该防爆层的3D玻璃或陶瓷。防爆层能够同时具有好的涂层附着力和防爆性能，且能够提供天线功能。
对比例1在常规的平面玻璃上粘贴常规的防爆膜，不能形成天线，且附着力等级差。市售常规的防爆膜不能在3D玻璃或陶瓷的表面上实施与玻璃或陶瓷基体紧密贴合，不能应用3D玻璃或陶瓷提供防爆功能。
对比例2只能在塑胶基材上形成天线，不能形成防爆膜，且不能用于在3D玻璃或陶瓷上形成具有天线的防爆膜。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本公开的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本公开的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本公开的限制，本领域的普通技术人员在本公开的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (67)

  1. 一种可金属化的防爆涂料，其中，以所述防爆涂料的总量为基准，所述防爆涂料包括：
    30-70重量％的水性聚氨酯分散体、2-20重量％的活性粉浆液、0.1-10重量％的附着力促进剂、0.1-10重量％的耐水助剂、0.1-5重量％的增稠剂、0.1-5重量％的pH调节剂-I、0-20重量％的成膜助剂和5-40重量％的水；
    其中，以所述活性粉浆液的总量为基准，所述活性粉浆液包含30-60重量％的水性树脂、20-50重量％的活性粉、5-20重量％的水性分散剂、5-30重量％的水和0.1-5重量％的pH调节剂-II；
    其中，所述活性粉包括选自除铜以外的元素周期表第9-11列金属元素的氧化物，元素周期表第9-11列金属元素的硅酸盐、硼酸盐和草酸盐，含有元素周期表第9-11列金属元素的加氢催化剂，具有铜铁矿结构的ABO 2型复合氧化物中的至少一种，以及掺杂的氧化锡；
    其中，所述加氢催化剂为使含羰基的醛、酮、脂肪酸或脂肪酸酯加氢成为醇的催化剂；A为选自元素周期表第9、10和11列金属元素中一种，B为Ni、Mn、Cr、Al或Fe，且A与B不同；所述掺杂的氧化锡中，掺杂元素为钒、锑、铟和钼中的至少一种。
  2. 根据权利要求1所述的防爆涂料，其中，所述活性粉浆液中，所述水性树脂为水溶性的聚酯树脂或水溶性的丙烯酸树脂。
  3. 根据权利要求1或2所述的防爆涂料，其中，所述水溶性的聚酯树脂为纽佩斯的SETAL6306ss-60树脂。
  4. 根据权利要求1-3中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述水性树脂的含量为40-60重量％。
  5. 根据权利要求1-4中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述活性粉的平均粒径为1nm-10μm。
  6. 根据权利要求1-5中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述活性粉的平均粒径为1nm-1μm。
  7. 根据权利要求1-6中任一项所述的防爆涂料，其中，所述活性粉为ZnSnO 3和/或ZnTiO 3。
  8. 根据权利要求1-7中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述活性粉的含量为20-45重量％。
  9. 根据权利要求1-8中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述活性粉的含量为20-30重量％。
  10. 根据权利要求1-9中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述活性粉的含量为25-30重量％。
  11. 根据权利要求1-10中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述水性分散剂为含有颜料亲和基团的高分子聚合物。
  12. 根据权利要求1-11中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述水性分散剂为陆博润的27000以及BYK的190、191、192、194中的至少之一。
  13. 根据权利要求1-12中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述水性分散剂为陆博润的27000和BYK的191中的至少之一。
  14. 根据权利要求1-13中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述水性分散剂的含量为5-15重量％。
  15. 根据权利要求1-14中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述水性分散剂的含量为8-15重量％。
  16. 根据权利要求1-15中任一项所述的防爆涂料，其中，所述pH调节剂-II为有机胺试剂。
  17. 根据权利要求1-16中任一项所述的防爆涂料，其中，所述pH调节剂-II为乙醇胺、N,N-二甲基乙醇胺、2-氨基-2-甲基-1-丙醇、氨水和陶氏化学的AMP-95中的至少之一。
  18. 根据权利要求1-17中任一项所述的防爆涂料，其中，所述活性粉浆液的pH值为7.5-8.5。
  19. 根据权利要求1-18中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述pH调节剂-II的含量为0.1-3重量％。
  20. 根据权利要求1-19中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述pH调节剂-II的含量为1-2重量％。
  21. 根据权利要求1-20中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述水加入量为5-25重量％。
  22. 根据权利要求1-21中任一项所述的防爆涂料，其中，所述活性粉浆液中，所述水加入量为8-18.5重量％。
  23. 根据权利要求1-22中任一项所述的防爆涂料，其中，所述水性聚氨酯分散体包括分散体A、分散体B和分散体C，其中，所述分散体A的断裂伸长率为1000-1500％，肖氏硬度为40-50度；所述分散体B的断裂伸长率为100-500％，肖氏硬度为30-60度；所述分散体C的断裂伸长率为100-300％，肖氏硬度为70-90度。
  24. 根据权利要求1-23中任一项所述的防爆涂料，其中，所述分散体A为Acure 218树脂。
  25. 根据权利要求1-24中任一项所述的防爆涂料，其中，所述分散体B为Acure 502树脂。
  26. 根据权利要求1-25中任一项所述的防爆涂料，其中，所述分散体C为Acure 806树脂。
  27. 根据权利要求1-26中任一项所述的防爆涂料，其中，以所述水性聚氨酯分散体的总量为基准，所述分散体A的用量为10-70重量％。
  28. 根据权利要求1-27中任一项所述的防爆涂料，其中，以所述水性聚氨酯分散体的总量为基准，所述分散体A的用量为15-65重量％。
  29. 根据权利要求1-28中任一项所述的防爆涂料，其中，以所述水性聚氨酯分散体的总量为基准，所述分散体A的用量为40-65重量％。
  30. 根据权利要求1-29中任一项所述的防爆涂料，其中，以所述水性聚氨酯分散体的总量为基准，所述分散体B的用量为10-50重量％。
  31. 根据权利要求1-30中任一项所述的防爆涂料，其中，以所述水性聚氨酯分散体的总量为基准，所述分散体B的用量为20-45重量％。
  32. 根据权利要求1-31中任一项所述的防爆涂料，其中，以所述水性聚氨酯分散体的总量为基准，所述分散体B的用量为25-43重量％。
  33. 根据权利要求1-32中任一项所述的防爆涂料，其中，以所述水性聚氨酯分散体的总量为基准，所述分散体C的用量为5-40重量％。
  34. 根据权利要求1-33中任一项所述的防爆涂料，其中，以所述水性聚氨酯分散体的总量为基准，所述分散体C的用量为5-20重量％。
  35. 根据权利要求1-34中任一项所述的防爆涂料，其中，以所述水性聚氨酯分散体的总量为基准，所述分散体C的用量为10-20重量％。
  36. 根据权利要求1-35中任一项所述的防爆涂料，其中，所述附着力促进剂为含有硅氧基团和磷酸基团的高分子化合物，所述高分子化合物由硅烷偶联剂与磷酸酯合成得到。
  37. 根据权利要求1-36中任一项所述的防爆涂料，其中，所述附着力促进剂为广州致精化股份有限公司的EDL6038和/或EDL-YH645B。
  38. 根据权利要求1-37中任一项所述的防爆涂料，其中，所述附着力促进剂的含量为0.5-4重量％。
  39. 根据权利要求1-38中任一项所述的防爆涂料，其中，所述附着力促进剂的含量为2-3.4重量％。
  40. 根据权利要求1-39中任一项所述的防爆涂料，其中，所述耐水助剂为水性封闭型异氰酸酯化合物。
  41. 根据权利要求1-40中任一项所述的防爆涂料，其中，所述耐水助剂为拜耳的BL2706。
  42. 根据权利要求1-41中任一项所述的防爆涂料，其中，所述耐水助剂的含量为1-5重量％。
  43. 根据权利要求1-42中任一项所述的防爆涂料，其中，所述耐水助剂的含量为1.1-4.8重量％。
  44. 根据权利要求1-43中任一项所述的防爆涂料，其中，所述增稠剂为聚丙烯酸酯、缔合型聚氨酯和纤维素化合物中的至少一种。
  45. 根据权利要求1-44中任一项所述的防爆涂料，其中，所述增稠剂为广州联固化学的X-71和/或汽巴公司的Rheovis132。
  46. 根据权利要求1-45中任一项所述的防爆涂料，其中，所述增稠剂的含量为0.2-3重量％。
  47. 根据权利要求1-46中任一项所述的防爆涂料，其中，所述增稠剂的含量为0.9-2.1重量％。
  48. 根据权利要求1-47中任一项所述的防爆涂料，其中，所述pH调节剂-I为高碱性有机胺化合物。
  49. 根据权利要求1-48中任一项所述的防爆涂料，其中，所述pH调节剂-I为陶氏化学的AMP-95。
  50. 根据权利要求1-49中任一项所述的防爆涂料，其中，所述pH调节剂-I含量为0.1-3重量％。
  51. 根据权利要求1-50中任一项所述的防爆涂料，其中，所述pH调节剂-I含量为1.2-2.8重量％。
  52. 根据权利要求1-51中任一项所述的防爆涂料，其中，所述成膜助剂为醇醚溶剂。
  53. 根据权利要求1-52中任一项所述的防爆涂料，其中，所述成膜助剂为陶氏化学的AMP-95。
  54. 根据权利要求1-53中任一项所述的防爆涂料，其中，所述成膜助剂的含量为5-15重量％。
  55. 根据权利要求1-54中任一项所述的防爆涂料，其中，所述成膜助剂的含量为3.8-4.8重量％。
  56. 根据权利要求1-55中任一项所述的防爆涂料，其中，以所述防爆涂料的总量为基准，所述水的含量为9-35重量％。
  57. 根据权利要求1-56中任一项所述的防爆涂料，其中，以所述防爆涂料的总量为基准，所述水的含量为9-20重量％。
  58. 一种制备权利要求1-57中任一项所述的可金属化的防爆涂料的方法，其中，包括：
    (1)将水性树脂、活性粉、水性分散剂、pH调节剂-II和水进行混合、研磨和过滤，得到活性粉浆液；其中，所述水性树脂、所述活性粉、所述水性分散剂、所述pH调节剂-II和所述水的投料量满足所述活性粉浆液包含30-60重量％的所述水性树脂、20-50重量％的所述活性粉、5-20重量％的所述水性分散剂、5-30重量％的所述水和0.1-5重量％的所述pH调节剂-II；
    其中，所述活性粉包括选自除铜以外的元素周期表第9-11列金属元素的氧化物，元素周期表第9-11列金属元素的硅酸盐、硼酸盐和草酸盐，含有元素周期表第9-11列金属元素的加氢催化剂，具有铜铁矿结构的ABO 2型复合氧化物中的至少一种，以及掺杂的氧化锡；
    其中，所述加氢催化剂为使含羰基的醛、酮、脂肪酸或脂肪酸酯加氢成为醇的催化剂；A为选自元素周期表第9、10和11列金属元素中一种，B为Cu、Sn、Zn、Ti、Ni、Mn、Cr、Al或Fe，且A与B不同；所述掺杂的氧化锡中，掺杂元素为钒、锑、铟和钼中的至少一种；
    (2)将水性聚氨酯分散体、所述活性粉浆液、成膜助剂和水进行混合并加入pH调节剂-I调节pH值为8-9；
    (3)顺次将增稠剂、附着力促进剂、耐水助剂和水加入步骤(2)得到的混合物中搅拌均匀并过滤，得到可金属化的防爆涂料；
    其中，所述水性聚氨酯分散体、所述活性粉浆液、所述成膜助剂、所述增稠剂、所述附着力促进剂、所述耐水助剂和所述水的加入量满足所述可金属化的防爆涂料中，以所述防爆涂料的总量为基准，含有30-70重量％的所述水性聚氨酯分散体、2-20重量％的所述活性粉浆液、0.1-10重量％的所述附着力促进剂、0.1-10重量％的所述耐水助剂、0.1-5重量％的所述增稠剂、0.1-5重量％的所述pH调节剂-I、0-20重量％的所述成膜助剂和5-40重量％的所述水。
  59. 一种具有天线的防爆层，其中，包括由权利要求1-57中任一项所述的可金属化的防爆涂料或采用权利要求58所述的方法得到的可金属化的防爆涂料形成的防爆涂层和在所述防爆涂层上形成的天线。
  60. 根据权利要求59所述的具有天线的防爆层，其中，所述防爆层的厚度为10-50μm。
  61. 根据权利要求59或60所述的具有天线的防爆层，其中，所述防爆层的厚度为20-40μm。
  62. 一种制备权利要求59-61中任一项所述的具有天线的防爆层的方法，其中，包括：
    (a)将权利要求1-57中任一项所述的可金属化的防爆涂料或采用权利要求58所述的方法得到的可金属化的防爆涂料喷涂在玻璃或陶瓷体上，并烘烤形成防爆涂层；
    (b)在所述防爆涂层的选定区域上进行激光照射，得到激光活化区；
    (c)在所述激光活化区形成铜层。
  63. 根据权利要求62所述的方法，其中，在步骤(c)中，所述铜层的厚度为2-15μm。
  64. 根据权利要求62或63所述的方法，其中，还包括：
    (d)在所述铜层上再形成镍层。
  65. 根据权利要求62-64中任一项所述的方法，其中，所述镍层的厚度为1-5μm。
  66. 一种3D玻璃或陶瓷机盖，其中，所述机盖包括3D玻璃或陶瓷的基体和权利要求59-61中任一项所述的具有天线的防爆层或采用权利要求62-65中任一项所述的方法得到的具有天线的防爆层。
  67. 一种权利要求1-57中任一项所述的可金属化的防爆涂料在提供曲面玻璃或陶瓷具有防爆和天线功能中的应用。
PCT/CN2018/119281 2017-12-06 2018-12-05 可金属化的防爆涂料及制备与应用、具有天线的防爆层及制备、以及3d玻璃或陶瓷机盖 WO2019109927A1 (zh)

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